Analysis of ZDDP Content and Thermal Decomposition in Motor Oils Using NAA and NMR

NASA Astrophysics Data System (ADS)

Ferguson, S.; Johnson, J.; Gonzales, D.; Hobbs, C.; Allen, C.; Williams, S.

Zinc dialkyldithiophosphates (ZDDPs) are one of the most common anti-wear additives present in commercially-available motor oils. The ZDDP concentrations of motor oils are most commonly determined using inductively coupled plasma atomic emission spectroscopy (ICP-AES). As part of an undergraduate research project, we have determined the Zn concentrations of eight commercially-available motor oils and one oil additive using neutron activation analysis (NAA), which has potential for greater accuracy and less sensitivity to matrix effects as compared to ICP-AES. The 31P nuclear magnetic resonance (31P-NMR) spectra were also obtained for several oil additive samples which have been heated to various temperatures in order to study the thermal decomposition of ZDDPs.

[Photometric determination of butyl "aeroflot" flotation agent (sodium dibutyl dithiophosphate) in the air of work zone and skin washings].

PubMed

Dorogova, V B; Kucheriavykh, E I; Sokolova, T V

1989-01-01

Photometric procedure of butyl "aeroflot" identification in the work zone air and in wash-out from workers' integument was developed, The procedure was based on the formation of yellow- and orange-dyed copper dibutyl dithiophosphate under butyl "aeroflot" interaction with copper sulphate with the subsequent photometry of dyed solutions for the wavelength of 420 nm in the 10-mm cell. Buffer solution with pH-9.2 was used as an absorbing solution for the workplace air sampling and integument wash-out.

Effect of three typical sulfide mineral flotation collectors on soil microbial activity.

PubMed

Guo, Zunwei; Yao, Jun; Wang, Fei; Yuan, Zhimin; Bararunyeretse, P; Zhao, Yue

2016-04-01

The sulfide mineral flotation collectors are wildly used in China, whereas their toxic effect on soil microbial activity remains largely unexplored. In this study, isothermal microcalorimetric technique and soil enzyme assay techniques were employed to investigate the toxic effect of typical sulfide mineral flotation collectors on soil microbial activity. Soil samples were treated with different concentrations (0-100 μg•g - 1 soil) of butyl xanthate, butyl dithiophosphate, and sodium diethyldithiocarbamate. Results showed a significant adverse effect of butyl xanthate (p < 0.05), butyl dithiophosphate, and sodium diethyldithiocarbamate (p < 0.01) on soil microbial activity. The growth rate constants k decreased along with the increase of flotation collectors concentration from 20.0 to 100.0 μg•g(-1). However, the adverse effects of these three floatation collectors showed significant difference. The IC 20 of the investigated flotation reagents followed such an order: IC 20 (butyl xanthate) > IC 20 (sodium diethyldithiocarbamate) > IC 20 (butyl dithiophosphate) with their respective inhibitory concentration as 47.03, 38.36, and 33.34 μg•g(-1). Besides, soil enzyme activities revealed that these three flotation collectors had an obvious effect on fluorescein diacetate hydrolysis (FDA) enzyme and catalase (CAT) enzyme. The proposed methods can provide meaningful toxicological information of flotation reagents to soil microbes in the view of metabolism and biochemistry, which are consistent and correlated to each other.

Non-chromatographic speciation analysis of mercury by flow injection on-line preconcentration in combination with chemical vapor generation atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Wu, Hong; Jin, Yan; Han, Weiying; Miao, Qiang; Bi, Shuping

2006-07-01

A novel non-chromatographic approach for direct speciation of mercury, based on the selective retention inorganic mercury and methylmercury on the inner wall of a knotted reactor by using ammonium diethyl dithiophosphate and dithizone as complexing agents respectively, was developed for flow injection on-line sorption preconcentration coupled with chemical vapor generation non-dispersive atomic fluorescence spectrometry. With the sample pH kept at 2.0, the preconcentration of inorganic mercury on the inner walls of the knotted reactor was carried out based on the exclusive retention of Hg-DDP complex in the presence of methylmercury via on-line merging the sample solution with ammonium diethyl dithiophosphate solution, and selective preconcentration methylmercury was achieved with dithizone instead of ammonium diethyl dithiophosphate. A 15% (v/v) HCl was introduced to elute the retained mercury species and merge with KBH 4 solution for atomic fluorescence spectrometry detection. Under the optimal experimental conditions, the sample throughputs of inorganic mercury and methylmercury were 30 and 20 h - 1 with the enhancement factors of 13 and 24. The detection limits were found to be 3.6 ng l - 1 for Hg 2+ and 2.0 ng l - 1 for CH 3Hg +. The precisions (RSD) for the 11 replicate measurements of each 0.2 μg l - 1 of Hg 2+ and CH 3Hg + were 2.2% and 2.8%, respectively. The developed method was validated by the analysis of certified reference materials (simulated natural water, rice flour and pork) and by recovery measurements on spiked samples, and was applied to the determination of inorganic mercury and methylmercury in biological and environmental water samples.

40 CFR 721.10125 - Alkenedioic acid, dialkyl ester, reaction products with polyaminocarbomonocycle and alkenoic acid...

Code of Federal Regulations, 2010 CFR

2010-07-01

..., reaction products with polyaminocarbomonocycle and alkenoic acid alkyl ester (generic). 721.10125 Section... Substances § 721.10125 Alkenedioic acid, dialkyl ester, reaction products with polyaminocarbomonocycle and.... (1) The chemical substances identified generically as alkenedioic acid, dialkyl ester, reaction...

40 CFR 721.10125 - Alkenedioic acid, dialkyl ester, reaction products with polyaminocarbomonocycle and alkenoic acid...

Code of Federal Regulations, 2011 CFR

2011-07-01

..., reaction products with polyaminocarbomonocycle and alkenoic acid alkyl ester (generic). 721.10125 Section... Substances § 721.10125 Alkenedioic acid, dialkyl ester, reaction products with polyaminocarbomonocycle and.... (1) The chemical substances identified generically as alkenedioic acid, dialkyl ester, reaction...

Large-scale Manufacturing of Nanoparticulate-based Lubrication Additives for Improved Energy Efficiency and Reduced Emissions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erdemir, Ali

This project was funded under the Department of Energy (DOE) Lab Call on Nanomanufacturing for Energy Efficiency and was directed toward the development of novel boron-based nanocolloidal lubrication additives for improving the friction and wear performance of machine components in a wide range of industrial and transportation applications. Argonne's research team concentrated on the scientific and technical aspects of the project, using a range of state-of-the art analytical and tribological test facilities. Argonne has extensive past experience and expertise in working with boron-based solid and liquid lubrication additives, and has intellectual property ownership of several. There were two industrial collaboratorsmore » in this project: Ashland Oil (represented by its Valvoline subsidiary) and Primet Precision Materials, Inc. (a leading nanomaterials company). There was also a sub-contract with the University of Arkansas. The major objectives of the project were to develop novel boron-based nanocolloidal lubrication additives and to optimize and verify their performance under boundary-lubricated sliding conditions. The project also tackled problems related to colloidal dispersion, larger-scale manufacturing and blending of nano-additives with base carrier oils. Other important issues dealt with in the project were determination of the optimum size and concentration of the particles and compatibility with various base fluids and/or additives. Boron-based particulate additives considered in this project included boric acid (H{sub 3}BO{sub 3}), hexagonal boron nitride (h-BN), boron oxide, and borax. As part of this project, we also explored a hybrid MoS{sub 2} + boric acid formulation approach for more effective lubrication and reported the results. The major motivation behind this work was to reduce energy losses related to friction and wear in a wide spectrum of mechanical systems and thereby reduce our dependence on imported oil. Growing concern over greenhouse gas emissions was also a major reason. The transportation sector alone consumes about 13 million barrels of crude oil per day (nearly 60% of which is imported) and is responsible for about 30% of the CO{sub 2} emission. When we consider manufacturing and other energy-intensive industrial processes, the amount of petroleum being consumed due to friction and wear reaches more than 20 million barrels per day (from official energy statistics, U.S. Energy Information Administration). Frequent remanufacturing and/or replacement of worn parts due to friction-, wear-, and scuffing-related degradations also consume significant amounts of energy and give rise to additional CO{sub 2} emission. Overall, the total annual cost of friction- and wear-related energy and material losses is estimated to be rather significant (i.e., as much as 5% of the gross national products of highly industrialized nations). It is projected that more than half of the total friction- and wear-related energy losses can be recovered by developing and implementing advanced friction and wear control technologies. In transportation vehicles alone, 10% to 15% of the fuel energy is spent to overcome friction. If we can cut down the friction- and wear-related energy losses by half, then we can potentially save up to 1.5 million barrels of petroleum per day. Also, less friction and wear would mean less energy consumption as well as less carbon emissions and hazardous byproducts being generated and released to the environment. New and more robust anti-friction and -wear control technologies may thus have a significant positive impact on improving the efficiency and environmental cleanliness of the current legacy fleet and future transportation systems. Effective control of friction in other industrial sectors such as manufacturing, power generation, mining and oil exploration, and agricultural and earthmoving machinery may bring more energy savings. Therefore, this project was timely and responsive to the energy and environmental objectives of DOE and our nation. In this project, most of the boron-based materials with known and potential anti-friction and -wear properties have been manufactured as colloidal additives and tested for their effectiveness in controlling friction and wear. Unlike other anti-friction and -wear additives, which consist of zinc, molybdenum, sulfur, phosphorus, and even chlorine, lubricious boron compounds considered in this project are made of boron, oxygen, nitrogen, and hydrogen, which are more environmentally benign. Among others, boric acid is a natural mineral (known in mineralogy as "sassolite"). Based on our earlier exploratory research, it was found to offer the best overall prospect in terms of performance improvements, environmental friendliness, and ease of manufacturing and, hence, cost effectiveness. Hexagonal boron nitride and borax also offered good prospects for improving the tribological properties of lubricated sliding surfaces. Boron oxide particles were found to be rather hard and somewhat abrasive and, hence, were not considered beyond the initial screening studies. In our bench-top tribological evaluation, we also demonstrated that those additives which worked well with engine oils could work equally well with very common gear oils. When added at appropriate concentrations, such gear oils were found to provide significant resistance to micropitting and scuffing failures in bench-top tribological test systems. Their traction coefficients were also reduced substantially and their scuffing limits were improved considerably. Such impressive tribological behavior of boron-based additives may have been due to their high chemical affinities to interact with sliding contact surfaces and to form slick and protective boundary films. Indeed, our surface studies have confirmed that most of the boron-based nanoparticulate additives prepared in our project possess a strong tendency to form a boron-rich boundary film on sliding contact surfaces. It is believed that the formation of such slick and highly durable boundary films is perhaps one of the fundamental reasons for their superior anti-friction, -wear, and -scuffing performance. Boron-based additives developed under this project have shown potential to reduce or replace the uses of environmentally unsafe sulfur- and phosphorus-bearing anti-wear and friction additives, such as zinc dialkyl dithiophosphate (ZDDP) and molybdenum dialkyl dithiocarbamate (MoDTC), in current lubricating oils. Because ZDDP and MoDTC were suspected of adversely impacting the performance of after-treatment catalysts in current engines, the Environmental Protection Agency (EPA) and other regulatory agencies are demanding that the concentrations of these catalysts in current oils be curtailed drastically. The boron-based nano-additives developed in this project may help reduce the use of ZDDP and MoDTC additives and, hence, help ease the poisoning effects on after-treatment catalysts. When used as lubricity additives, these boron additives can chemically interact with sliding or contacting surfaces and form a protective and slick boundary film, which can, in turn, help reduce friction and wear and increase resistance to scuffing. In the cases of traditional anti-friction and -wear additives mentioned, such protective boundary films result from phosphorus, sulfur, and other elements in the additive package, and again they have been under increased scrutiny in recent years, mainly because of their adverse effects on after-treatment devices. Overall, the boron-based nano-additive technology of this project was shown to hold promise for a broad range of industrial and transportation applications where lower friction and higher resistance to wear and scuffing are needed. Due to more stringent operating conditions of modern machinery, rolling, rotating, and sliding components have been failing to meet the projected lifetimes, mainly because of failures related to mechanical wear, corrosion, and scuffing. The novel boron-based additive technology developed under this project may help such machine components to function reliably by cutting down the friction and wear losses and by increasing resistance to scuffing.« less

40 CFR 721.10413 - Fluorinated dialkyl ketone (generic) (P-10-135).

Code of Federal Regulations, 2014 CFR

2014-07-01

...) (P-10-135). 721.10413 Section 721.10413 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10413 Fluorinated dialkyl ketone (generic) (P-10-135). (a) Chemical... as fluorinated dialkyl ketone (PMN P-10-135) is subject to reporting under this section for the...

40 CFR 721.10072 - Benzene, 1,1′-methylenebis[4-isocyanato-, polymer with benzenedicarboxylic acid, butyl dialkyl...

Code of Federal Regulations, 2010 CFR

2010-07-01

...-isocyanato-, polymer with benzenedicarboxylic acid, butyl dialkyl ester, poly[oxy(methyl-1,2-ethanediyl)], .alpha.-hydro-.omega.-hydroxy-, oxirane, alkyl-, polymer with oxirane, ether with propanepolyol and...-isocyanato-, polymer with benzenedicarboxylic acid, butyl dialkyl ester, poly[oxy(methyl-1,2-ethanediyl...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Landauer, Alexander K.; Barnhill, William C.; Qu, Jun

Here we examine the elasticity, hardness, and resistance-to-plastic-deformation (P/S 2) measured via nanoindentation of several tribofilms and correlates these properties to friction and wear behavior. The tribofilms were generated by ball-on-plate reciprocating sliding lubricated by a base oil containing an ionic liquid, phosphonium-organophosphate or ammonium-organophosphate, zinc dialkyldithiophosphate (ZDDP), or combination of IL and ZDDP. Nanoindentation was conducted at room and elevated temperatures. While there seems little correlation between the tribofilm hardness and tribological behavior, a higher modulus generally leads to better friction and wear performance. Interestingly, a lower P/S 2 ratio tends to reduce friction and improve wear protection, whichmore » is in an opposite trend as reported for bulk materials. Ultimately, this is likely attributable to the dynamic, self-healing characteristics of tribofilms.« less

40 CFR 721.10413 - Fluorinated dialkyl ketone (generic) (P-10-135).

Code of Federal Regulations, 2013 CFR

2013-07-01

...) (P-10-135). 721.10413 Section 721.10413 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10413 Fluorinated dialkyl ketone (generic) (P-10-135). (a) Chemical... as fluorinated dialkyl ketone (PMN P-10-135) is subject to reporting under this section for the...

40 CFR 721.10413 - Fluorinated dialkyl ketone (generic) (P-10-135).

Code of Federal Regulations, 2012 CFR

2012-07-01

...) (P-10-135). 721.10413 Section 721.10413 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10413 Fluorinated dialkyl ketone (generic) (P-10-135). (a) Chemical... as fluorinated dialkyl ketone (PMN P-10-135) is subject to reporting under this section for the...

Dialkyl dicyanofumarates and dicyanomaleates as versatile building blocks for synthetic organic chemistry and mechanistic studies

PubMed Central

Heimgartner, Heinz

2017-01-01

The scope of applications of dialkyl dicyanofumarates and maleates as highly functionalized electron-deficient dipolarophiles, dienophiles and Michael acceptors is summarized. The importance for the studies on reaction mechanisms of cycloadditions is demonstrated. Multistep reactions with 1,2-diamines and β-aminoalcohols leading to diverse five- and six-membered heterocycles are discussed. Applications of dialkyl dicyanofumarates as oxidizing agents in the syntheses of disulfides and diselenides are described. The reactions with metallocenes leading to charge-transfer complexes with magnetic properties are also presented. PMID:29114328

Flame-retardant copolymers of dialkyl (meth)acryloyloxyalkyl phosphate or dialkyl (meth)acryloyloxyalkyl phosphonate monomers and polymer foams based made therefrom

DOEpatents

Qi, Yudong; Li, Yan; Bunker, Shana P.; Costeux, Stephane; Morgan, Ted A.

2017-12-12

Polymer foam bodies are made from phosphorus-containing thermoplastic random copolymers of a dialkyl (meth)acryloyloxyalkyl phosph(on)ate. Foam bodies made from these copolymers exhibit increased limiting oxygen indices and surprisingly have good properties. In certain embodiments, the phosphorus-containing thermoplastic copolymer is blended with one or more other polymers and formed into nanofoams.

The neurotoxin diethyl dithiophosphate impairs glutamate transport in cultured Bergmann glia cells.

PubMed

Olivares-Bañuelos, Tatiana N; Martínez-Hernández, Isabel; Hernández-Kelly, Luisa C; Chi-Castañeda, Donají; Vega, Libia; Ortega, Arturo

2018-06-13

Glutamate, the main excitatory neurotransmitter in the vertebrate Central Nervous System, is involved in almost every aspect of brain physiology, and its signaling properties are severely affected in most neurodegenerative diseases. This neurotransmitter has to be efficiently removed from the synaptic cleft in order to prevent an over-stimulation of glutamate receptors that leads to neuronal death. Specific sodium-dependent membrane transporters, highly enriched in glial cells, elicit the clearance of glutamate. Once internalized, it is metabolized to glutamine by the glia-enriched enzyme Glutamine synthetase. Accumulated glutamine is released into the extracellular space for its uptake into pre-synaptic neurons and its conversion to glutamate that is packed into synaptic vesicles completing the glutamate/glutamine cycle. Diverse chemical compounds, like organophosphates, directly affect brain chemistry by altering levels of neurotransmitters in the synaptic cleft. Organophosphate compounds are widely used as pesticides, and all living organisms are continuously exposed to these substances, either in a direct or indirect manner. Its metabolites, like the diethyl dithiophosphate, are capable of causing brain damage through diverse mechanisms including perturbation of neuronal-glial cell interactions and have been associated with attention-deficit disorders and other mental illness. In order to characterize the neurotoxic mechanisms of diethyl dithiophosphate, we took advantage of the well characterized model of chick cerebellar Bergmann glia cultures. A significant impairment of [ 3 H] d-Aspartate transport was found upon exposure to the metabolite. These results indicate that glia cells are targets of neurotoxic substances such as pesticides and that these cells might be critically involved in the associated neuronal death. Copyright © 2018 Elsevier Ltd. All rights reserved.

Continuous removal of ore floatation reagents by an anaerobic-aerobic biological filter.

PubMed

Cheng, Huang; Lin, Hai; Huo, Hanxin; Dong, Yingbo; Xue, Qiuyu; Cao, Lixia

2012-06-01

A laboratory scale up-flow anaerobic-aerobic biological filter was constructed to treat synthetic ore floatation wastewater. Volcanic stone was applied as packing media for aerobic section. Biodegradation of some common ore floatation reagents as potassium ethyl xanthate dithiophosphate and turpentine were evaluated. An average COD reduction rate of 88.7% for potassium ethyl xanthate by the biofilter was obtained at HRT of 6h, air water flow ratio of 10:1 and pH of 7. Its effluent COD concentration varied between 17 and 43 mg/L. Xanthates and dithiophosphate were found to be easily biodegradable, whereas turpentine was not favorable for microorganism to digest. The performance of the reactor fluctuated slightly within the temperature range of 10-35 °C. Operation of the biofilter was sensitive to influent pH values. A neutral to weak basic influent was preferred for biofilter to maintain an efficient operation. Anaerobic treatment was able to enhance the biodegradability of influents significantly. Copyright © 2012 Elsevier Ltd. All rights reserved.

Methods of producing sulfate salts of cations from heteroatomic compounds and dialkyl sulfates and uses thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2015-09-29

Methods of preparing sulfate salts of heteroatomic compounds using dialkyl sulfates as a primary reactant are disclosed. Also disclosed are methods of making ionic liquids from the sulfate salts of the heteroatomic compound, and electrochemical cells comprising the ionic liquids.

Formation of carbonaceous nano-layers under high interfacial pressures during lubrication with mineral and bio-based oils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baltrus, John P.

In order to better protect steel surfaces against wear under high loads, understanding of chemical reactions between lubricants and metal at high interfacial pressures and elevated temperatures needs to be improved. Solutions at 5 to 20 wt. % of zinc di-2-ethylhexyl dithio phosphate (ZDDP) and chlorinated paraffins (CP) in inhibited paraffinic mineral oil (IPMO) and inhibited soy bean oil (ISBO) were compared on a Twist Compression Tribotester (TCT) at 200 MPa. Microscopy of wear tracks after 10 seconds tribotesting showed much smoother surface profiles than those of unworn areas. X-ray photoelectron spectroscopy (XPS) coupled with Ar-ion sputtering demonstrated that additivemore » solutions in ISBO formed 2–3 times thicker carbon-containing nano-layers compared to IPMO. The amounts of Cl, S or P were unexpectedly low and detectable only on the top surface with less than 5 nm penetration. CP blends in IPMO formed more inorganic chlorides than those in ISBO. It can be concluded that base oils are primarily responsible for the thickness of carbonaceous nano-layers during early stages of severe boundary lubrication, while CP or ZDDP additive contributions are important, but less significant.« less

Determination of cadmium in seawater by chelate vapor generation atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Sun, Rui; Ma, Guopeng; Duan, Xuchuan; Sun, Jinsheng

2018-03-01

A method for the determination of cadmium in seawater by chelate vapor generation (Che-VG) atomic fluorescence spectrometry is described. Several commercially available chelating agents, including ammonium pyrrolidine dithiocarbamate (APDC), sodium dimethyl dithiocarbamate (DMDTC), ammonium dibutyl dithiophosphate (DBDTP) and sodium O,O-diethyl dithiophosphate (DEDTP), are compared with sodium diethyldithiocarbamate (DDTC) for the Che-VG of cadmium, and results showed that DDTC and DEDTP had very good cadmium signal intensity. The effect of the conditions of Che-VG with DDTC on the intensity of cadmium signal was investigated. Under the optimal conditions, 85 ± 3% Che-VG efficiency is obtained for cadmium. The detection limit (3σ) obtained in the optimal conditions was 0.19 ng ml- 1. The relative standard deviation (RSD, %) for ten replicate determinations at 2 ng ml- 1 Cd was 3.42%. The proposed method was successfully applied to the ultratrace determination of cadmium in seawater samples by the standard addition method.

Method of synthesizing pyrite nanocrystals

DOEpatents

Wadia, Cyrus; Wu, Yue

2013-04-23

A method of synthesizing pyrite nanocrystals is disclosed which in one embodiment includes forming a solution of iron (III) diethyl dithiophosphate and tetra-alkyl-ammonium halide in water. The solution is heated under pressure. Pyrite nanocrystal particles are then recovered from the solution.

Synthesis of 3-iodoindoles by the Pd/Cu-catalyzed coupling of N,N-dialkyl-2-iodoanilines and terminal acetylenes, followed by electrophilic cyclization.

PubMed

Yue, Dawei; Yao, Tuanli; Larock, Richard C

2006-01-06

[reaction: see text] 3-Iodoindoles have been prepared in excellent yields by coupling terminal acetylenes with N,N-dialkyl-o-iodoanilines in the presence of a Pd/Cu catalyst, followed by an electrophilic cyclization of the resulting N,N-dialkyl-o-(1-alkynyl)anilines using I2 in CH2Cl2. Aryl-, vinylic-, alkyl-, and silyl-substituted terminal acetylenes undergo this process to produce excellent yields of 3-iodoindoles. The reactivity of the carbon-nitrogen bond cleavage during cyclization follows the following order: Me > n-Bu, Me > Ph, and cyclohexyl > Me. Subsequent palladium-catalyzed Sonogashira, Suzuki, and Heck reactions of the resulting 3-iodoindoles proceed smoothly in good yields.

Three-component synthesis of dialkyl 2-(alkylimino-methylene)3- (2,2,5-trimethyl-4,6-dioxo-1,3-dioxan-5-yl)-succinates.

PubMed

Yavari, Issa; Zare, Hasan; Mohtat, Bita

2006-05-01

The adduct produced in the reaction between alkyl isocyanides and dialkyl acetylenedicarboxylates was trapped by 2,2,5-trimethyl-1,3-dioxane-4,6-dione (methyl Meldrum's acid), to afford highly functionalized ketenimines in good yields.

Compatibility of Anti-Wear Additives with Non-Ferrous Engine Bearing Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, Jun; Zhou, Yan

Investigate the compatibility of engine lubricant antiwear (AW) additives, specifically conventional zinc dialkyldithiophosphate (ZDDP) and newly developed ionic liquids (ILs), with selected non-ferrous engine bearing alloys, specifically aluminum and bronze alloys that are commonly used in connecting rod end journal bearings and bushings, to gain fundamental understanding to guide future development of engine lubricants

Improving Tribological Properties of Multialkylated Cyclopentanes under Simulated Space Environment: Two Feasible Approaches.

PubMed

Fan, Xiaoqiang; Wang, Liping; Li, Wen; Wan, Shanhong

2015-07-08

Space mechanisms require multialkylated cyclopentanes (MACs) more lubricious, more reliable, more durable, and better adaptive to harsh space environments. In this study, two kinds of additives were added into MACs for improving the tribological properties under simulated space environments: (a) solid nanoparticles (tungsten disulfide (WS2), tungsten trioxide (WO3), lanthanum oxide (La2O3), and lanthanum trifluoride (LaF3)) for steel/steel contacts; (b) liquid additives like zinc dialkyldithiophosphate (ZDDP) and molybdenum dialkyldithiocarbamate (MoDTC) for steel/steel and steel/diamond-like carbon (DLC) contacts. The results show that, under harsh simulated space environments, addition of the solid nanoparticles into MACs allows the wear to be reduced by up to one order magnitude, while liquid additives simultaneously reduce friction and wear by 80% and 93%, respectively. Friction mechanisms were proposed according to surface/interface analysis techniques, such as X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS). The role of solid nanoparticles in reducing friction and wear mainly depends on their surface enhancement effect, and the liquid additives are attributed to the formation of tribochemical reaction film derived from ZDDP and MoDTC on the sliding surfaces.

Safety Assessment of Dialkyl Sulfosuccinate Salts as Used in Cosmetics.

PubMed

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

2016-11-01

The Cosmetic Ingredient Review (CIR) Expert Panel (Panel) assessed the safety of 8 dialkyl sulfosuccinate salts for use in cosmetics, finding that these ingredients are safe in cosmetics in the present practices of use and concentration when formulated to be nonirritating. The dialkyl sulfosuccinate salts primarily function as surfactants in cosmetics. The Panel reviewed the new and existing available animal and clinical data in making its determination of safety. The Panel found it appropriate to extrapolate the data on diethylhexyl sodium sulfosuccinate to assess the safety of the entire group because all of the diesters are of a similar alkyl chain length, all are symmetrically substituted, and all have similar functions in cosmetic formulations. © The Author(s) 2016.

Base-catalyzed bicyclization of dialkyl glutaconates with cinnamoylacetamides: a synthetic strategy for isoquinolinedione derivatives.

PubMed

Li, Lei; Zhao, Yu-Long; Wang, He; Li, Yi-Jin; Xu, Xianxiu; Liu, Qun

2014-06-21

We report here that polysubstituted dihydroisoquinolones and isoquinolones can be constructed by the one-pot reaction of the readily available acyclic α,β-unsaturated carbonyl precursors and dialkyl glutaconates under mild basic conditions (1-45 min for the former vs. 1-6 h for the latter) via the domino process involving [3+3] annulation/intramolecular aza-cyclization.

Inverse-Micelle-Encapsulated Water-Enabled Bond Breaking of Dialkyl Diselenide/Disulfide: A Critical Step for Synthesizing High- Quality Gold Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zaluzhna, Oksana; Li, Ying; Allison, Thomas C.

2012-10-09

Inverse-micelle-encapsulated water formed in the two-phase Brust-Schiffrin method (BSM) synthesis of Au nanoparticles (NPs) is identified as essential for dialkyl diselenide/disulfide to react with the Au(III) complex in which the Se-Se/S-S bond is broken, leading to formation of higher-quality Au NPs.

Final safety assessment of thiodipropionic acid and its dialkyl esters as used in cosmetics.

PubMed

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

2010-07-01

Dilauryl thiodipropionate (DLTDP), dicetyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and ditridecyl thiodipropionate are dialkyl esters of their respective alcohols and thiodipropionic acid (TDPA) used in cosmetics. Ingested DLTDP was excreted in the urine as TDPA. Single-dose acute oral and parenteral studies and subchronic and chronic repeated dose oral studies did not suggest significant toxicity. Neither DLTDP nor TDPA was irritating to animal skin or eyes and they were not sensitizers. TDPA was neither a teratogen nor a reproductive toxicant. Genotoxicity studies were negative for TDPA and DLTDP. Clinical testing demonstrated some evidence of irritation but no sensitization or photosensitization. The Cosmetic Ingredient Review Expert Panel considered that the data from DLTDP reasonably may be extrapolated to the other dialkyl esters and concluded that these ingredients were safe for use in cosmetic products that are formulated to be nonirritating.

Water Soluble Phosphane-Gold(I) Complexes. Applications as Recyclable Catalysts in a Three-component Coupling Reaction and as Antimicrobial and Anticancer Agents

PubMed Central

Elie, Benelita T.; Levine, Chaya; Ubarretxena-Belandia, Iban; Varela-Ramírez, Armando; Aguilera, Renato J.; Ovalle, Rafael; Contel, María

2013-01-01

Water-soluble compounds of the type [AuCl(PR3)] with alkyl-bis-(m-sulfonated-phenyl)-(mC6H4SO3Na)2 and dialkyl-(m-sulfonated-phenyl)-(mC6H4SO3Na) (R = nBu, Cp) phosphanes have been prepared. Dialkyl-phosphane compounds generate water-soluble nanoparticles of 10-15 nm radius when dissolved in water. These air-stable complexes have been evaluated as catalysts in the synthesis of propargylamines via a three-component coupling reaction of aldehydes, amines and alkynes in water. The antimicrobial activity of the new complexes against Gram-positive and Gram-negative bacteria and yeast has been evaluated. The new compounds display moderate to high antibacterial activity. The more lipophilic compounds are also potent against fungi. Their cytotoxic properties have been analyzed in vitro utilizing human Jurkat T-cell acute lymphoblastic leukemia cells. Compounds with dialkyl-(m-sulfonated-phenyl)-(mC6H4SO3Na) phosphanes displayed moderate to high cytotoxicity on this cell line. Death cell mechanism occurs mainly by early apoptosis. The catalytic/biological activity of the previously described compound with commercial m-trisulfonated-triphenylphosphine [AuCl(TPPTS)] (6) has been also evaluated to compare the effects of the higher basicity and lipophilicity of the alkyl- and di-alkyl-(m-sulfonated-phenyl) phosphanes on these new compounds. PMID:23524957

Poly(silylene)vinylenes from ethynylhydridosilanes

DOEpatents

Barton, Thomas J.; Ijadi-Maghsoodi, Sina

1992-11-10

Catalytic polymerization of dialkyl-, alkylaryl- or diaryldiethynylhydridosilanes cleanly affords soluble poly(silylene)vinylenes which can be shaped as fibers, films and bulk objects and thermally converted to silicon carbide.

Analysis of nucleotides and oligonucleotides immobilized as self-assembled monolayers by static secondary ion mass spectrometry.

PubMed

Patrick, J S; Cooks, R G; Pachuta, S J

1994-11-01

Nucleic acid constituents can be bound to a metal surface in the form of self-assembled monolayers. Binding is achieved either through ionic interactions with a self-assembled 2-aminoethanethiol monolayer or by direct covalent binding of a dithiophosphate oligonucleotide to a metal surface through a sulfur-metal bond. Nucleotides, polynucleotides (both normal and a dithiophosphate analog) and double-stranded DNA have all been bound to surfaces. When the surfaces are interrogated using static secondary ion mass spectrometry (SIMS), the surface-bound nucleic acid constituents are observed in the form of the characteristic protonated nucleic acid base ions (BH2+). While a silver foil substrate was found to provide the highest absolute signal, vapor-deposited gold yields the best signal-to-noise ratio for ionically bound deoxyguanosine monophosphate. Under comparable conditions, a Cs+ projectile produces a 10-fold increase in the secondary ion signal relative to a Ga+ projectile. The experiment has been extended to a triple-quadrupole instrument where tandem mass spectrometric experiments on ionically immobilized dGMP showed the characteristic loss of ammonia from the released BH2+ ion. When a 'biomimetic' surface formed by ionically immobilizing double-stranded DNA is exposed to a solution containing ethidium bromide, ions corresponding to the non-covalent adduct are readily detectable using SIMS. This adduct and the nucleic acid constituents can be monitored at levels below 10 fmol.

Closer insight into the reactivity of TMP-dialkyl zincates in directed ortho-zincation of anisole: experimental evidence of amido basicity and structural elucidation of key reaction intermediates.

PubMed

Clegg, William; Conway, Ben; Hevia, Eva; McCall, Matthew D; Russo, Luca; Mulvey, Robert E

2009-02-18

The new dialkyl(aryl) lithium zincates [(THF)(2)Li(C(6)H(4)-OMe)MeZnMe] (4), [(TMEDA)Li(C(6)H(4)-OMe)MeZnMe] (6), [(THF)(3)Li(C(6)H(4)-OMe)(t)BuZn(t)Bu] (7), and [(PMDETA)Li(C(6)H(4)-OMe)(t)BuZn(t)Bu] (8) have been prepared by co-complexation reactions of lithiated anisole with the relevant dialkylzinc compound and the relevant Lewis base. These new heterobimetallic compounds have been characterized in solution using (1)H, (13)C{H}, and (7)Li NMR spectroscopy, and the molecular structures of 6 and 8 have been elucidated by X-ray crystallography. In 6 the distinct metals are connected through the anisole ligand which binds in an ambidentate fashion (through carbon-zinc and oxygen-lithium contacts) and also through one of the methyl groups, to close a [LiOCCZnC] six-membered ring; whereas 8 displays an open structure where anisole connects the two metals (in the same mode as in 6) but with the tert-butyl groups exclusively bonded terminally to zinc. Reactivity studies of zincates 4 and 7 with the amine TMP(H) supply experimental evidence that these heterobimetallic compounds are intermediates in the two-step deprotonation reaction of anisole by TMP-dialkyl zincates and show the relevance of the alkyl groups in the efficiency of TMP-dialkyl zincate bases. In addition, important solvent effects have also been evaluated. When hexane is added to THF solutions of compounds 4 or 7, the homoleptic tetraorganozincate [(THF)(2)Li(2)Zn(C(6)H(4)-OMe)(4)] (5) is obtained as the result of a disproportionation process. This lithium-rich zincate has also been spectroscopically and crystallographically characterized.

Thin-film transistors based on poly(3,3‴-dialkyl-quarterthiophene) and zinc oxide nanowires with improved ambient stability

NASA Astrophysics Data System (ADS)

Vieira, Sara M. C.; Hsieh, Gen-Wen; Unalan, Husnu E.; Dag, Sefa; Amaratunga, Gehan A. J.; Milne, William I.

2011-03-01

The ambient stability of thin-film transistors (TFTs) based on zinc oxide (ZnO) nanowires embedded in poly(3,3‴-dialkyl-quarterthiophene) was monitored through time dependence of electrical characteristics over a period of 16 months. The hybrid-based TFT showed an initial hole mobility in the linear regime of 4.2×10-4 cm2/V s. After 16 months storage in ambient conditions (exposed to air, moisture, and light) the mobility decreased to 2.3×10-5 cm2/V s. Comparatively the organic-based TFT lost total carrier mobility after one month storage making the hybrid-based TFTs more suitable for transistor applications when improved stability combined with structural flexibility are required.

Regio- and Stereochemical Control in Ocimene Polymerization by Half-Sandwich Rare-Earth Metal Dialkyl Complexes.

PubMed

Peng, Deqian; Du, Gaixia; Zhang, Pengfei; Yao, Bo; Li, Xiaofang; Zhang, Shaowen

2016-06-01

The polymerization of ocimene has been first achieved by half-sandwich rare-earth metal dialkyl complexes in combination with activator and Al(i) Bu3 . The regio- and stereoselectivity in the ocimene polymerization can be controlled by tuning the cyclopentadienyl ligand and the central metal of the complex. The chiral cyclopentadienyl-ligated Sc complex 1 prepares syndiotactic cis-1,4-polyocimene (cis-1,4-selectivity up to 100%, rrrr = 100%), while the corresponding Lu, Y, and Dy complexes 2-4 and the achiral pentamethylcyclopentadienyl Sc, Lu, and Y complexes 5-7 afford isotactic trans-1,2-polyocimenes (trans-1,2-selectivity up to 100%, mm = 100%). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhayal, Rajendra S.; Liao, Jian-Hong; Kahlal, Samia

An air- and moisture-stable nanoscale polyhydrido copper cluster [Cu 32(H) 20{S 2P(O i Pr) 2 } 12 ] (1 H) was synthesized and structurally characterized. The molecular structure of 1 H exhibits a hexacapped pseudo-rhombohedral core of 14 Cu atoms sandwiched between two nestlike triangular cupola fragments of (2x9) Cu atoms in an elongated triangular gyrobicupola polyhedron. The discrete Cu 32 cluster is stabilized by 12 dithiophosphate ligands and a record number of 20 hydride ligands, which were found by high-resolution neutron diffraction to exhibit tri-, tetra-, and pentacoordinated hydrides in capping and interstitial modes. We conclude that this resultmore » was further supported by a density functional theory investigation on the simplified model [Cu 32(H) 20(S 2PH 2) 12].« less

Synthesis of 3,5-Isoxazolidinediones and 1H-2,3-Benzoxazine-1,4(3H)-diones from Aliphatic Oximes and Dicarboxylic Acid Chlorides

PubMed Central

2015-01-01

The synthesis of the title compounds was carried out by reacting dicarboxylic acid chlorides with oximes in the presence of excess triethylamine. Disubstituted malonyl chlorides gave 2-alkenyl-4,4-dialkyl-3,5-isoxazolidinediones (8a–f) and 2,2′-ethylidene-bis[4,4-dialkyl-3,5-isoxazolidinedione]s (9a–f). Compounds 9 were formed from 8 and its N-unsubstituted 3,5-isoxazolidinedione decomposition product. Phthaloyl chlorides reacted with acetone oxime to yield 3-(1-methylethenyl)-1H-2,3-benzoxazine-1,4(3H)-diones (16a–e). Products 16 spontaneously decomposed to give N-unsubstituted 1H-2,3-benzoxazine-1,4(3H)-diones (17a–e) at rates that were dependent on temperature and solvent. Kinetic studies showed that two of the compounds decomposed by zero-order kinetics under neutral conditions. Butanedioyl chloride did not produce a cyclic product. PMID:24620711

Synthesis and dynamic NMR study of ketenimines derived from tert-butyl isocyanide, alkyl 2-arylamino-2-oxo-acetates, and dialkyl acetylenedicarboxylates.

PubMed

Yavari, Issa; Nasiri, Farough; Djahaniani, Horieh

2004-01-01

The adduct produced in the reaction between tert-butyl isocyanide and dialkyl acetylenedicarboxylates was trapped by alkyl 2-arylamino-2-oxo-acetates. When the aryl group is 2-methyl-6-nitrophenyl or 2,6-di-isopropylphenyl, the product exists as two stable rotamers at room temperature as a result of restricted rotation around the Ar-N single bond. When the aryl group is 1-naphthyl or 8-quinolinyl, dynamic NMR effects are observed in the 1H NMR spectra. The calculated free-energy of activation for interconversion of the rotational isomers in 1-naphthyl and 8-quinolinyl derivatives amounts to about 99+/-2 and 68.5+/-2 kJ mol(-1), respectively.

From ether to acid: A plausible degradation pathway of glycerol dialkyl glycerol tetraethers

NASA Astrophysics Data System (ADS)

Liu, Xiao-Lei; Birgel, Daniel; Elling, Felix J.; Sutton, Paul A.; Lipp, Julius S.; Zhu, Rong; Zhang, Chuanlun; Könneke, Martin; Peckmann, Jörn; Rowland, Steven J.; Summons, Roger E.; Hinrichs, Kai-Uwe

2016-06-01

Glycerol dialkyl glycerol tetraethers (GDGTs) are ubiquitous microbial lipids with extensive demonstrated and potential roles as paleoenvironmental proxies. Despite the great attention they receive, comparatively little is known regarding their diagenetic fate. Putative degradation products of GDGTs, identified as hydroxyl and carboxyl derivatives, were detected in lipid extracts of marine sediment, seep carbonate, hot spring sediment and cells of the marine thaumarchaeon Nitrosopumilus maritimus. The distribution of GDGT degradation products in environmental samples suggests that both biotic and abiotic processes act as sinks for GDGTs. More than a hundred newly recognized degradation products afford a view of the stepwise degradation of GDGT via (1) ether bond hydrolysis yielding hydroxyl isoprenoids, namely, GDGTol (glycerol dialkyl glycerol triether alcohol), GMGD (glycerol monobiphytanyl glycerol diether), GDD (glycerol dibiphytanol diether), GMM (glycerol monobiphytanol monoether) and bpdiol (biphytanic diol); (2) oxidation of isoprenoidal alcohols into corresponding carboxyl derivatives and (3) chain shortening to yield C39 and smaller isoprenoids. This plausible GDGT degradation pathway from glycerol ethers to isoprenoidal fatty acids provides the link to commonly detected head-to-head linked long chain isoprenoidal hydrocarbons in petroleum and sediment samples. The problematic C80 to C82 tetraacids that cause naphthenate deposits in some oil production facilities can be generated from H-shaped glycerol monoalkyl glycerol tetraethers (GMGTs) following the same process, as indicated by the distribution of related derivatives in hydrothermally influenced sediments.

TSCA Section 21 Petition to Promulgate Regulations Governing PVCs

EPA Pesticide Factsheets

This petition requests EPA to promulgate regulations governing the safe treatment, storage and disposal of polyvinyl chloride (PVC), vinyl chloride and associated dialkyl- and alkylarylesters of 1,2-benzenedicarboxylic acid.

40 CFR 721.5980 - Dialkyl phosphorodithioate phosphate compounds.

Code of Federal Regulations, 2010 CFR

2010-07-01

... any information on methods for protecting against such risk, into an MSDS as described at § 721.72(c... compounds. 721.5980 Section 721.5980 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... manner or method of manufacture, import, or processing associated with any use of these substances...

URINARY BIOMARKERS OF DI-ISONONYL PHTHALATE IN RATS

EPA Science Inventory

Commercial di-isononyl phthalate (DiNP) is a mixture of various branched-chain dialkyl phthalates mainly containing ninecarbon alkyl isomers. At high doses in rodents, DiNP is a carcinogen, and a developmental toxicant. After exposure, the diester isomers are de-esterified to for...

Synthesis of 3,5-isoxazolidinediones and 1H-2,3-benzoxazine-1,4(3H)-diones from aliphatic oximes and dicarboxylic acid chlorides.

PubMed

Izydore, Robert A; Jones, Joseph T; Mogesa, Benjamin; Swain, Ira N; Davis-Ward, Ronda G; Daniels, Dwayne L; Kpakima, Felicia Frazier; Spaulding-Phifer, Sharnelle T

2014-04-04

The synthesis of the title compounds was carried out by reacting dicarboxylic acid chlorides with oximes in the presence of excess triethylamine. Disubstituted malonyl chlorides gave 2-alkenyl-4,4-dialkyl-3,5-isoxazolidinediones (8a-f) and 2,2'-ethylidene-bis[4,4-dialkyl-3,5-isoxazolidinedione]s (9a-f). Compounds 9 were formed from 8 and its N-unsubstituted 3,5-isoxazolidinedione decomposition product. Phthaloyl chlorides reacted with acetone oxime to yield 3-(1-methylethenyl)-1H-2,3-benzoxazine-1,4(3H)-diones (16a-e). Products 16 spontaneously decomposed to give N-unsubstituted 1H-2,3-benzoxazine-1,4(3H)-diones (17a-e) at rates that were dependent on temperature and solvent. Kinetic studies showed that two of the compounds decomposed by zero-order kinetics under neutral conditions. Butanedioyl chloride did not produce a cyclic product.

Direct catalytic asymmetric alpha-amination of aldehydes.

PubMed

List, Benjamin

2002-05-22

The first direct catalytic asymmetric alpha-amination of aldehydes is described herein. alpha-Unbranched aldehydes react in this novel proline-catalyzed reaction with dialkyl azodicarboxylates to give alpha-amino aldehydes in excellent yields and enantioselectivities.

A Phosphine-mediated Synthesis of 2,3,4,5-tetra-substituted N-hydroxypyrroles from α-oximino Ketones and Dialkyl Acetylenedicarboxylates Under Ionic Liquid Green-media.

PubMed

Shahvelayati, Ashraf S; Ghazvini, Maryam; Yadollahzadeh, Khadijeh; Delbari, Akram S

2018-01-01

The development of multicomponent reactions (MCRs) in the presence of task-specific ionic liquids (ILs), used not only as environmentally benign reaction media, but also as catalysts, is a new approach that meet with the requirements of sustainable chemistry. In recent years, the use of ionic liquids as a green media for organic synthesis has become a chief study area. This is due to their unique properties such as non-volatility, non-flammability, chemical and thermal stability, immiscibility with both organic compounds and water and recyclability. Ionic liquids are used as environmentally friendly solvents instead of hazardous organic solvents. We report the condensation reaction between α-oximinoketone and dialkyl acetylene dicarboxylate in the presence of triphenylphosphine to afford substituted pyrroles under ionic liquid conditions in good yields. Densely functionalized pyrroles was easily prepared from reaction of α-oximinoketones, dialkyl acetylene dicarboxylate in the presence of triphenylphosphine in a quantitative yield under ionic liquid conditions at room temperature. In conclusion, ionic liquids are indicated as a useful and novel reaction medium for the selective synthesis of functionalized pyrroles. This reaction medium can replace the use of hazardous organic solvents. Easy work-up, synthesis of polyfunctional compounds, decreased reaction time, having easily available-recyclable ionic liquids, and good to high yields are advantages of present method. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer

NASA Astrophysics Data System (ADS)

Wolf, Jan-Christoph; Etter, Raphael; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

2016-07-01

An active capillary plasma ionization (ACI) source was coupled to a handheld mass spectrometer (Mini 10.5; Aston Labs, West Lafayette, IN, USA) and applied to the direct gas-phase detection and quantification of chemical warfare agent (CWA) related chemicals. Complementing the discontinuous atmospheric pressure interface (DAPI) of the Mini 10.5 mass spectrometer with an additional membrane pump, a quasi-continuous sample introduction through the ACI source was achieved. Nerve agent simulants (three dialkyl alkylphosphonates, a dialkyl phosporamidate, and the pesticide dichlorvos) were detected at low gas-phase concentrations with limits of detection ranging from 1.0 μg/m3 to 6.3 μg/m3. Our results demonstrate a sensitivity enhancement for portable MS-instrumentation by using an ACI source, enabling direct, quantitative measurements of volatile organic compounds. Due to its high sensitivity, selectivity, low power consumption (<80 W) and weight (<13 kg), this instrumentation has the potential for direct on-site CWA detection as required by military or civil protection.

Palladium(II) complexes with R(2)edda derived ligands. Part IV. O,O'-dialkyl esters of (S,S)-ethylenediamine-N,N'-di-2-(4-methyl)-pentanoic acid dihydrochloride and their palladium(II) complexes: synthesis, characterization and in vitro antitumoral activity against chronic lymphocytic leukemia (CLL) cells.

PubMed

Vujić, Jelena M; Cvijović, Milica; Kaluderović, Goran N; Milovanović, Marija; Zmejkovski, Bojana B; Volarević, Vladislav; Arsenijević, Nebojsa; Sabo, Tibor J; Trifunović, Srećko R

2010-09-01

Four novel bidentate N,N'-ligand precursors, including O,O'-dialkyl esters (alkyl = ethyl, n-propyl, n-butyl and n-pentyl), L1 x 2 HCl-L4 x 2 HCl, of (S,S)-ethylenediamine-N,N'-di-2-(4-methyl)-pentanoic acid dihydrochloride [(S,S)-H(4)eddl]Cl(2) and the corresponding palladium(II) complexes 1-4, were prepared and characterized by IR, (1)H NMR and (13)C NMR spectroscopy and elemental analysis. In vitro cytotoxicity of all compounds was determined against chronic lymphocytic leukemia cells (CLL). The compounds were found to exhibit higher antitumoral activity than cisplatin. The most active compound 2, [PdCl(2){(S,S)-nPr(2)eddl}], was found to be 13.6 times more active than cisplatin on CLL cells. 2010 Elsevier Masson SAS. All rights reserved.

IMPROVED CLEANUP AND DETERMINATION METHOD OF DIALKYL PHOSPHATES IN THE URINE OF CHILDREN EXPOSED TO ORGANOPHOSPHORUS INSECTICIDES. (R825171)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

40 CFR 721.10072 - Benzene, 1,1′-methylenebis[4-isocyanato-, polymer with benzenedicarboxylic acid, butyl dialkyl...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzene, 1,1â²-methylenebis[4... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10072 Benzene, 1,1′-methylenebis[4... to reporting. (1) The chemical substance identified generically as benzene, 1,1′-methylenebis[4...

40 CFR 721.10072 - Benzene, 1,1′-methylenebis[4-isocyanato-, polymer with benzenedicarboxylic acid, butyl dialkyl...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Benzene, 1,1â²-methylenebis[4... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10072 Benzene, 1,1′-methylenebis[4... to reporting. (1) The chemical substance identified generically as benzene, 1,1′-methylenebis[4...

Design, microwave-mediated synthesis and biological evaluation of novel 4-aryl(alkyl)amino-3-nitroquinoline and 2,4-diaryl(dialkyl)amino-3-nitroquinolines as anticancer agents.

PubMed

Chauhan, Monika; Rana, Anil; Alex, Jimi Marin; Negi, Arvind; Singh, Sandeep; Kumar, Raj

2015-02-01

Design, microwave-assisted synthesis of novel 4-aryl (alkyl)amino-3-nitroquinoline (1a-1l) and 2,4-diaryl (dialkyl)amino-3-nitroquinolines (2a-2k and 3a) via regioselective and complete nucleophilic substitution of 2,4-dichloro-3-nitroquinoline, respectively in water are presented. The newly synthesized compounds were evaluated for the first time for antiproliferative activity against EGFR overexpressing human lung (A-549 and H-460) and colon (HCT-116-wild type and HCT-116-p53 null) cancer cell lines. Some notions about structure-activity relationships (SAR) are presented. Compounds 2e, 2f, 2j and 3a overall exhibited excellent anticancer activity comparable to erlotinib which was used as a positive control. Molecular modeling studies disclosed the recognition pattern of the compounds and also supported the observed SAR. Copyright © 2014 Elsevier Inc. All rights reserved.

Widespread occurrence of structurally diverse tetraether membrane lipids: Evidence for the ubiquitous presence of low-temperature relatives of hyperthermophiles

PubMed Central

Schouten, Stefan; Hopmans, Ellen C.; Pancost, Richard D.; Damsté, Jaap S. Sinninghe

2000-01-01

Isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs) and branched glycerol dialkyl diethers are main membrane constituents of cultured hyperthermophilic archaea and eubacteria, respectively, and are found in environments with temperatures >60°C. Recently, we developed a new technique for the analysis of intact core tetraether lipids in cell material and sediments. The application of this technique to recent sediments shows that known and newly identified isoprenoid and branched GDGTs are widespread in low-temperature environments (<20°C) and are structurally far more diverse than previously thought. Their distribution indicates the ubiquitous environmental presence of as yet uncultivated, nonthermophilic organisms that may have independently evolved from hyperthermophilic archaea and eubacteria. The structures of some of the new GDGTs point to the hybridization of both typical archaeal and eubacterial biosynthetic pathways in single organisms. PMID:11121044

Tribological properties of limonene bisphosphonates

USDA-ARS?s Scientific Manuscript database

Limonene was chemically modified by reacting it with dialkyl phosphites of varying alkyl structures under inert atmosphere in the presence of free radical initiators. The reaction gave a mixture of mono- and di-adduct products, and was optimized to produce only the diadduct product limonene bisphosp...

Continuous formation of N-chloro-N,N-dialkylamine solutions in well-mixed meso-scale flow reactors

PubMed Central

Jolley, Katherine E

2015-01-01

Summary The continuous flow synthesis of a range of organic solutions of N,N-dialkyl-N-chloramines is described using either a bespoke meso-scale tubular reactor with static mixers or a continuous stirred tank reactor. Both reactors promote the efficient mixing of a biphasic solution of N,N-dialkylamine in organic solvent, and aqueous sodium hypochlorite to achieve near quantitative conversions, in 72–100% in situ yields, and useful productivities of around 0.05 mol/h with residence times from 3 to 20 minutes. Initial calorimetric studies have been carried out to inform on reaction exotherms, rates and safe operation. Amines which partition mainly in the organic phase require longer reaction times, provided by the CSTR, to compensate for low mass transfer rates in the biphasic system. The green metrics of the reaction have been assessed and compared to existing procedures and have shown the continuous process is improved over previous procedures. The organic solutions of N,N-dialkyl-N-chloramines produced continuously will enable their use in tandem flow reactions with a range of nucleophilic substrates. PMID:26734089

New bis(alkythio) fatty acid methyl esters

USDA-ARS?s Scientific Manuscript database

The addition reaction of dimethyl disulfide (DMDS) to mono-unsaturated fatty acid methyl esters is well-known for analytical purposes to determine the position of double bonds by mass spectrometry. In this work, the classical iodine-catalyzed reaction is expanded to other dialkyl disulfides (RSSR), ...

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2012 CFR

2012-10-01

... Amyl methyl ketone, see Methyl amyl ketone D Animal and Fish oils, n.o.s. D (see also Oil, edible, or...-Butyl formate D n-Butyl formate @D Butyl heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone... Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate, see Dialkyl(C7-C13) phthalates Diisononyl...

The Holocene Records of Glycerol Dialkyl Glycerol Tetraethers From the Northern Chukchi Sea

NASA Astrophysics Data System (ADS)

Park, Y.; Yamamoto, M.; Nam, S.; Polyak, L. V.

2013-12-01

We analyzed glycerol dialkyl glycerol tetraethers (GDGTs) in Cores HOTRAX 05-01 JPC5 and JPC 8, and ARA02B 01-GC in the northern Chukchi Sea. All of the three cores showed a similar changing pattern in GDGT composition during the Holocene. In the beginning of early Holocene, both isoprenoid and branched GDGT concentrations were low, and BIT and CBT were relatively high. The similar composition is found in modern sediments from the western Arctic Ocean north of 75°N, suggesting that the northern Chukchi Sea was covered by perennial sea ice. GDGT concentration increased, and BIT and CBT decreased during the early Holocene and reached the same level as those in modern sediments at 8 ka. TEX86 and CBT/MBT indices showed millennial-scale variation. We interpret that these proxies did not simply indicate temperatures but were affected by the relative contribution of different sediment sources. Millennial-scale variability likely reflected changes in sediment transport in the northern Chukchi Sea.

Design, synthesis and evaluation of dialkyl 4-(benzo[d][1,3]dioxol-6-yl)-1,4-dihydro-2,6-dimethyl-1-substituted pyridine-3,5-dicarboxylates as potential anticonvulsants and their molecular properties prediction.

PubMed

Prasanthi, G; Prasad, K V S R G; Bharathi, K

2013-08-01

The present study is on the development of dialkyl 4-(benzo[d][1,3]dioxol-6-yl)-1,4-dihydro-2,6-dimethyl-1-substituted pyridine-3,5-dicarboxylate derivatives as isosteric analogues of isradipine and nifedipine, by the replacement of benzofurazanyl and 2-nitrophenyl groups respectively with benzo[d][1,3]dioxo-6-yl group, as potential anticonvulsants. Fivfteen new derivatives (8a-8o) were synthesized and tested for anticonvulsant activity using maximal electroshock and subcutaneous pentylenetetrazole induced seizure methods. Compound 8f possessing free NH group in 1,4-dihydropyridine ring, diethyl ester functionality at the positions 3 and 5 showed significant anticonvulsant and antioxidant activities. This was also supported by molecular properties prediction data. Selected compounds were evaluated for antinociceptive activity in capsaicin induced nociception assay at 10 mg/kg body weight, but displayed no significant activity at the tested dose. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

APOPTOSIS OF CEREBELLAR GRANULE CELLS INDUCED BY ORGANOTIN COMPOUNDS FOUND IN DRINKING WATER: INVOLVEMENT OF MAP KINASES.

EPA Science Inventory

Mono- and dialkyl organotins have been found in drinking water in homes and businesses served by PVC pipes. Because the structurally related trialkyl organotins (eg. trimethyltin, tributyltin) are well known neurotoxicants, there is concern over the potential for the mono- and di...

40 CFR 721.10072 - Benzene, 1,1′-methylenebis[4-isocyanato-, polymer with benzenedicarboxylic acid, butyl dialkyl...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Benzene, 1,1â²-methylenebis[4... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10072 Benzene, 1,1′-methylenebis[4... to reporting. (1) The chemical substance identified generically as benzene, 1,1′-methylenebis[4...

Syntheses of calix[4]pyrroles by amberlyst-15 catalyzed cyclocondensations of pyrrole with selected ketones.

PubMed

Chauhan, Shive Murat Singh; Garg, Bhaskar; Bisht, Tanuja

2007-11-09

A facile and efficient protocol is reported for the synthesis of calix[4]pyrroles and N-confused calix[4]pyrroles in moderate to excellent yields by reaction of dialkyl or cycloalkyl ketones with pyrrole catalyzed by reusable Amberlyst(TM)-15 under eco-friendly conditions.

Synthesis and characterization of phosphonates from methyl linoleate and vegetable oils

USDA-ARS?s Scientific Manuscript database

Phosphonates were synthesized on a medium scale (~200 g) from three lipids: methyl linoleate (MeLin), high-oleic sunflower oil (HOSO), and soybean oil (SBO), and three dialkyl phosphites: methyl, ethyl, and n-butyl, using radical initiator. A staged addition of the lipid and the initiator was needed...

Predicting the Migration Rate of Dialkyl Organotins from PVC Pipe into Water

EPA Science Inventory

Organotins (OTs) are additives widely used as thermal and light stabilizers in polyvinyl chloride (PVC) plastics. OTs can leach into water flowing through PVC pipes. This work examines the leaching rates of two neurotoxic OTs, dimethyl tin (DMT) and dibutyl tin (DBT), from PVC pi...

40 CFR 721.10072 - Benzene, 1,1′-methylenebis[4-isocyanato-, polymer with benzenedicarboxylic acid, butyl dialkyl...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Benzene, 1,1â²-methylenebis[4... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10072 Benzene, 1,1′-methylenebis[4... to reporting. (1) The chemical substance identified generically as benzene, 1,1′-methylenebis[4...

40 CFR 721.9795 - Benzenesulfonic acid, 2,2′-(1,2-ethenediyl)bis[(4,6-dichloro-1,3,5-triazin-2-yl) amino...

Code of Federal Regulations, 2010 CFR

2010-07-01

... benzenesulfonic acid, 2,2′-(1,2-ethenediyl)bis[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-, disodium salt... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzenesulfonic acid, 2,2â²-(1,2-ethenediyl)bis[(4,6-dichloro-1,3,5-triazin-2-yl) amino]-, disodium salt, substituted with dialkyl amines...

Synthesis and characterization of phosphonates from methyl linoleate and vegetable oils

USDA-ARS?s Scientific Manuscript database

Phosphonates were synthesized on a medium scale (~200 g) from three lipids–methyl linoleate (MeLin), high-oleic sunflower oil (HOSO) and soybean oil (SBO), and three dialkyl phosphites–methyl, ethyl and n-butyl, using a radical initiator. A staged addition of the lipid and the initiator was used to ...

40 CFR 721.9795 - Benzenesulfonic acid, 2,2′-(1,2-ethenediyl)bis[(4,6-dichloro-1,3,5-triazin-2-yl) amino...

Code of Federal Regulations, 2011 CFR

2011-07-01

... benzenesulfonic acid, 2,2′-(1,2-ethenediyl)bis[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-, disodium salt... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzenesulfonic acid, 2,2â²-(1,2-ethenediyl)bis[(4,6-dichloro-1,3,5-triazin-2-yl) amino]-, disodium salt, substituted with dialkyl amines...

Synthesis and characterization of phosphonates from methyl linoleate and vegetable oils

USDA-ARS?s Scientific Manuscript database

Phosphonates were synthesized on a medium scale (~200 g) from three lipids: methyl linoleate (MeLin), high-oleic sunflower oil (HOSO) and soybean oil (SBO), and three dialkyl phosphites: methyl, ethyl and n-butyl, using a radical initiator. A staged addition of the lipid and the initiator to the dia...

75 FR 34045 - Sodium 1,4-Dialkyl Sulfosuccinates; Exemption from the Requirement of a Tolerance

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-16

....'' This includes exposure through drinking water and in residential settings, but does not include... the inert ingredient through food, drinking water, and through other exposures that occur as a result.... Dietary exposure from food and feed uses and drinking water. Since an endpoint for risk assessment was not...

Ionic Liquids as Energetic Materials

DTIC Science & Technology

2007-03-01

triazolium halide that can be synthesized from the electrophilic fluorination and quaternization of the amino-substituted triazole. Metathesis with a...silver salt such as silver nitrate forms the nitrate salt. By electrophilic difluoroamination of 1 -alkyl-3-nitro- 1,2,4-triazole, 1,4-dialkyl-3-nitro...nonaromatic salts (1-7) described in Table 1. The presence of small amounts of fluorine in the substituent arm contributes to the thermal stability and has

Synthesis of organosilicon derivatives of [1]benzothieno[3,2-b][1]-benzothiophene for efficient monolayer Langmuir-Blodgett organic field effect transistors.

PubMed

Borshchev, O V; Sizov, A S; Agina, E V; Bessonov, A A; Ponomarenko, S A

2017-01-16

For the first time, the synthesis of organosilicon derivatives of dialkyl[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) capable of forming a semiconducting monolayer at the water-air interface is reported. Self-assembled monolayer organic field-effect transistors prepared from these materials using the Langmuir-Blodgett technique showed high hole mobilities and excellent air stability.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shao, Huifang; Lam, William; Remias, Joseph

Mobile source emissions standards are becoming more stringent and particulate emissions from gasoline direct injection (GDI) engines represent a particular challenge. Gasoline particulate filter (GPF) is deemed as one possible technical solution for particulate emissions reduction. In this work, a study was conducted on eight formulations of lubricants to determine their effect on GDI engine particulate emissions and GPF performance. Accelerated ash loading tests were conducted on a 2.4L GDI engine with engine oil injection in gasoline fuel by 2%. The matrix of eight formulations was designed with changing levels of sulfated ash (SASH) level, Zinc dialkyldithiophosphates (ZDDP) level andmore » detergent type. Comprehensive evaluations of particulates included mass, number, size distribution, composition, morphology and soot oxidation properties. GPF performance was assessed through filtration efficiency, back pressure and morphology. It was determined that oil formulation affects the particulate emission characteristics and subsequent GPF performance.« less

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Amyl methyl ketone, see Methyl amyl ketone D Animal and Fish oils, n.o.s. D (see also Oil, edible, or...-Butyl formate D n-Butyl formate @D Butyl heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone... Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate, see Dialkyl(C7-C13) phthalates Diisononyl...

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2011 CFR

2011-10-01

... Amyl methyl ketone, see Methyl amyl ketone D Animal and Fish oils, n.o.s. D (see also Oil, edible, or...-Butyl formate D n-Butyl formate @D Butyl heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone... Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate, see Dialkyl(C7-C13) phthalates Diisononyl...

PROCESS FOR UTILIZING ORGANIC ORTHOPHOSPHATE EXTRACTANTS

DOEpatents

Grinstead, R.R.

1958-11-11

A process is presented for recovering uranium from its ores, the steps comprising producing the uranium in solution in the trivalent state, extracting the uranium from solution in an lmmiscible organic solvent extract phase which lncludes mono and dialkyl orthophosphorlc acid esters having a varying number of carbon atoms on the alkyl substituent, amd recovering the uranium from tbe extract phase.

Aromatic/aliphatic diamine derivatives for advanced compositions and polymers

NASA Technical Reports Server (NTRS)

Delozier, Donovan M. (Inventor); Connell, John W. (Inventor); Smith, Jr., Joseph G. (Inventor); Watson, Kent A. (Inventor)

2010-01-01

Novel compositions of matter comprise certain derivatives of 9,9-dialkyl fluorene diamine (AFDA). The resultant compositions, whether compositions of matter or monomers that are subsequently incorporated into a polymer, are unique and useful in a variety of applications. Useful applications of AFDA-based material include heavy ion radiation shielding components and components of optical and electronic devices.

77 FR 32965 - Certain New Chemicals; Receipt and Status Information

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-04

... importer P-12-0214 03/01/2012 05/01/2012 CBI Laundry and auto Carbohydrate polymers dish wash with acrylic... salt (1:2) initiate. P12-0215 03/01/2012 05/01/2012 CBI Laundry and auto Carbohydrate, polymers dish............ 04/25/2012 04/17/2012 (G) Barium, dialkyl 2-sulfobutanedioate phosphate complexes. P-09-0384...

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2014 CFR

2014-10-01

... Amyl methyl ketone, see Methyl amyl ketone D Animal and Fish oils, n.o.s. D (see also Oil, edible, or...-Butyl formate D n-Butyl formate @D Butyl heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone... Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate, see Dialkyl(C7-C13) phthalates Diisononyl...

Determination and identification of malathion, ethion and dichlorovos using ion mobility spectrometry.

PubMed

Jafari, Mohammad T

2006-07-15

Positive ion mobility spectra of different organophosphorus pesticides such as malathion (s-(1,2-dicarb-ethoxyethyl) o,o-dimethyl dithiophosphate), ethion (o,o,o',o'-tetraethyl s,s'-methylene bis(phosphorodithioate)) and dichlorovos (2,2-dichlorovinyl dimethyl phosphate) have been studied in air at ambient pressure using ion mobility spectrometry method with (63)Ni ionization source. The limits of quantification (LOQs) were 1.0 x 10(-9), 1.0 x 10(-9) and 5.0 x 10(-9)g for malathion, ethion and dichlorovos, respectively. The working range of these compounds was about three orders of magnitude and the relative standard deviation (R.S.D.) of repeatability at the 5 microg ml(-1) level were all below 15%. Furthermore, in this study, the influences of IMS cell temperature on the ion mobility spectra of these compounds were investigated.

A practical derivatization LC/MS approach for determination of trace level alkyl sulfonates and dialkyl sulfates genotoxic impurities in drug substances.

PubMed

An, Jianguo; Sun, Mingjiang; Bai, Lin; Chen, Ted; Liu, David Q; Kord, Alireza

2008-11-04

Derivatization LC/MS methodology has been developed for the determination of a group of commonly encountered alkyl esters of sulfonates or sulfates in drug substances at low ppm levels. This general method uses trimethylamine as the derivatizing reagent for ethyl/propyl/isopropyl esters and triethylamine for methyl esters. The resulting quaternary ammonium derivatization products are highly polar (ionic) and can be retained by a hydrophilic interaction liquid chromatography (HILIC) column and readily separated from the main interfering active pharmaceutical ingredient (API) peak that is usually present at very high concentration. The method gives excellent sensitivity for all the alkyl esters at typical target analyte level of 1-2 ppm when the API samples were prepared at 5mg/mL. The recoveries at 1-2 ppm were generally above 85% for all the alkyl esters in the various APIs tested. The injection precisions of the lowest concentration standards were excellent with R.S.D.=0.4-4%. A linear range for concentrations from 0.2 to 20 ppm has been established with R(2)>or=0.99. This general method has been tested in a number of API matrices and used successfully for determination of alkyl sulfonates or dialkyl sulfates in support of API batch releases at GlaxoSmithKline.

Interface engineering in high-performance low-voltage organic thin-film transistors based on 2,7-dialkyl-[1]benzothieno[3,2-b][1]benzothiophenes.

PubMed

Amin, Atefeh Y; Reuter, Knud; Meyer-Friedrichsen, Timo; Halik, Marcus

2011-12-20

We investigated two different (2,7-dialkyl-[1]benzothieno[3,2-b][1]benzothiophenes; C(n)-BTBT-C(n), where n = 12 or 13) semiconductors in low-voltage operating thin-film transistors. By choosing functional molecules in nanoscaled hybrid dielectric layers, we were able to tune the surface energy and improve device characteristics, such as leakage current and hysteresis. The dipolar nature of the self-assembled molecules led to a shift in the threshold voltage. All devices exhibited high charge carrier mobilities of 0.6-7.0 cm(2) V(-1) s(-1). The thin-film morphology of BTBT was studied by means of atomic force microscopy (AFM), presented a dependency upon the surface energy of the self-assembled monolayer (SAM) hybrid dielectrics but not upon the device performance. The use of C(13)-BTBT-C(13) on hybrid dielectrics of AlO(x) and a F(15)C(18)-phosphonic acid monolayer led to devices with a hole mobility of 1.9 cm(2) V(-1) s(-1) at 3 V, on/off ratio of 10(5), small device-device variation of mobility, and a threshold voltage of only -0.9 V, thus providing excellent characteristics for further integration. © 2011 American Chemical Society

Synthesis of 5-acyl-6-[2-hydroxy-3-(amino)propylamino]-1,3-dialkyl-1H-pyrimidine-2,4-diones.

PubMed

Singh, Palwinder; Paul, Kamaldeep; Holzer, Wolfgang

2005-11-07

A stepwise synthetic approach involving substitution of 6-chloro-1,3-dialkyluracils (5 and 6) with 3-(tert-amino)-2-hydroxypropylamines and subsequent acylation at C5 of uracil has been used to synthesize pyrimidinediones 27-33 in 61-89% overall yield. The conformational aspects of the new molecules based upon NMR data have been discussed.

PRECIPITATION OF ZIRCONIUM, NIOBIUM, AND RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Wilson, A.S.

1958-08-12

An improvement on the"head end process" for decontaminating dissolver solutions of their Zr, Ni. and Ru values. The process consists in adding a water soluble symmetrical dialkyl ketone. e.g. acetone, before the formation of the manganese dioxide precipitate. The effect is that upon digestion, the ruthenium oxide does not volatilize, but is carried on the manganese dioxide precipitate.

System and process for production of magnesium metal and magnesium hydride from magnesium-containing salts and brines

DOEpatents

McGrail, Peter B.; Nune, Satish K.; Motkuri, Radha K.; Glezakou, Vassiliki-Alexandra; Koech, Phillip K.; Adint, Tyler T.; Fifield, Leonard S.; Fernandez, Carlos A.; Liu, Jian

2016-11-22

A system and process are disclosed for production of consolidated magnesium metal products and alloys with selected densities from magnesium-containing salts and feedstocks. The system and process employ a dialkyl magnesium compound that decomposes to produce the Mg metal product. Energy requirements and production costs are lower than for conventional processing.

Versatile organoaluminium catalysts based on heteroscorpionate ligands for the preparation of polyesters.

PubMed

Martínez, J; Martínez de Sarasa Buchaca, M; de la Cruz-Martínez, F; Alonso-Moreno, C; Sánchez-Barba, L F; Fernandez-Baeza, J; Rodríguez, A M; Rodríguez-Diéguez, A; Castro-Osma, J A; Otero, A; Lara-Sánchez, A

2018-05-22

A series of alkyl aluminium complexes based on heteroscorpionate ligands were designed as catalysts for the ring-opening polymerisation of cyclic esters and ring-opening copolymerisation of epoxides and anhydrides. Treatment of AlX3 (X = Me, Et) with ligands bpzbeH [bpzbe = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide], bpzteH [bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-para-tolylethoxide], and (R,R)-bpzmmH [(R,R)-bpzmm = (1R)-1-{(1R)-6,6-dimethyl-bicyclo[3.1.1]-2-hepten-2-yl}-2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide] for 2 hours at 0 °C afforded the mononuclear dialkyl aluminium complexes [AlMe2{κ2-bpzbe}] (1), [AlEt2{κ2-bpzbe}] (2), [AlMe2{κ2-(R,R)-bpzmm}] (3) and [AlEt2{κ2-(R,R)-bpzmm}] (4), and the dinuclear dialkyl complexes [AlMe2{κ2-bpzte}]2 (5) and [AlEt2{κ2-bpzte}]2 (6). The molecular structures of the new complexes were determined by spectroscopic methods and confirmed by X-ray crystallography. The alkyl-containing aluminium complexes can act as highly efficient single-component initiators for the ring-opening polymerisation of ε-caprolactone and l-lactide and for the ring-opening copolymerisation of cyclohexene oxide and phthalic anhydride to give a range of biodegradable polyesters.

Degradable conjugated polymers for the selective sorting of semiconducting carbon nanotubes

DOEpatents

Gopalan, Padma; Arnold, Michael Scott; Kansiusarulsamy, Catherine Kanimozhi; Brady, Gerald Joseph; Shea, Matthew John

2018-04-10

Conjugated polymers composed of bi-pyridine units linked to 9,9-dialkyl fluorenyl-2,7-diyl units via imine linkages along the polymer backbone are provided. Also provided are semiconducting single-walled carbon nanotubes coated with the conjugated polymers and methods of sorting and separating s-SWCNTs from a sample comprising a mixture of s-SWCNTs and metallic single-walled carbon nanotubes using the conjugated polymers.

Copper-Catalyzed Electrophilic Amination of Organoaluminum Nucleophiles with O-Benzoyl Hydroxylamines.

PubMed

Zhou, Shuangliu; Yang, Zhiyong; Chen, Xu; Li, Yimei; Zhang, Lijun; Fang, Hong; Wang, Wei; Zhu, Xiancui; Wang, Shaowu

2015-06-19

A copper-catalyzed electrophilic amination of aryl and heteroaryl aluminums with N,N-dialkyl-O-benzoyl hydroxylamines that affords the corresponding anilines in good yields has been developed. The catalytic reaction proceeds very smoothly under mild conditions and exhibits good substrate scope. Moreover, the developed catalytic system is also well suited for heteroaryl aluminum nucleophiles, providing facile access to heteroaryl amines.

S-alkynyl esters of phosphorus thioacids as inhibitors of cholinesterases and as promising physiologically active compounds

NASA Astrophysics Data System (ADS)

Brestkin, A. P.; Vikhreva, L. A.; Godovikov, Nikolai N.; Zhukovskii, Yu G.; Kabachnik, Martin I.; Moralev, S. N.; Rosengart, V. I.; Sherstobitov, O. E.

1991-08-01

Data are given in the review on the anticholinesterase activity of 58 specially synthesised esters of phosphorus thioacids containing an acetylenic bond in the thioester group. It was established that compounds containing an acetylenic group in the β and especially in the α position of the thioester residue display an inhibitory action many times greater than that of their saturated analogues. A phosphorylated enzyme is formed by the reaction of the acetylenic organophosphorus inhibitors (OPIs) with the enzymes as in the case of reaction with the saturated analogues. It was shown that the acetylenic organophosphorus inhibitors possess high biological activity both for mammals and for arthropods. On replacing the phosphoryl oxygen (P=O) by sulphur (P=S) the toxicity of the acetylenic organophosphorus inhibitors for mammals was sharply reduced but was little changed for arthropods. This raises the possibility of obtaining highly selective insecto-acaricides. The mechanism of the antienzymic action of the acetylenic OPIs and the mechanism of detoxication of diethyl S-hexynyl dithiophosphate are considered. The bibliography includes 44 references.

Method for the concentration and separation of actinides from biological and environmental samples

DOEpatents

Horwitz, E. Philip; Dietz, Mark L.

1989-01-01

A method and apparatus for the quantitative recover of actinide values from biological and environmental sample by passing appropriately prepared samples in a mineral acid solution through a separation column of a dialkyl(phenyl)-N,N-dialylcarbamoylmethylphosphine oxide dissolved in tri-n-butyl phosphate on an inert substrate which selectively extracts the actinide values. The actinide values can be eluted either as a group or individually and their presence quantitatively detected by alpha counting.

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.

General synthesis of 2,1-benzisoxazoles (anthranils) from nitroarenes and benzylic C-H acids in aprotic media promoted by combination of strong bases and silylating agents.

PubMed

Wiȩcław, Michał; Bobin, Mariusz; Kwast, Andrzej; Bujok, Robert; Wróbel, Zbigniew; Wojciechowski, Krzysztof

2015-11-01

Carbanions of phenylacetonitriles, benzyl sulfones, and dialkyl benzylphosphonates add nitroarenes at the ortho-position to the nitro group to form [Formula: see text]-adducts that, upon treatment with trialkylchlorosilane and additional base (t-BuOK or DBU), transform into 3-aryl-2,1-benzisoxazoles in moderate-to-good yields.

Mono-, di- and trimethylated homologues of isoprenoid tetraether lipid cores in archaea and environmental samples: mass spectrometric identification and significance.

PubMed

Knappy, Chris; Barillà, Daniela; Chong, James; Hodgson, Dominic; Morgan, Hugh; Suleman, Muhammad; Tan, Christine; Yao, Peng; Keely, Brendan

2015-12-01

Higher homologues of widely reported C(86) isoprenoid diglycerol tetraether lipid cores, containing 0-6 cyclopentyl rings, have been identified in (hyper)thermophilic archaea, representing up to 21% of total tetraether lipids in the cells. Liquid chromatography-tandem mass spectrometry confirms that the additional carbon atoms in the C(87-88) homologues are located in the etherified chains. Structures identified include dialkyl and monoalkyl ('H-shaped') tetraethers containing C(40-42) or C(81-82) hydrocarbons, respectively, many representing novel compounds. Gas chromatography-mass spectrometric analysis of hydrocarbons released from the lipid cores by ether cleavage suggests that the C(40) chains are biphytanes and the C(41) chains 13-methylbiphytanes. Multiple isomers, having different chain combinations, were recognised among the dialkyl lipids. Methylated tetraethers are produced by Methanothermobacter thermautotrophicus in varying proportions depending on growth conditions, suggesting that methylation may be an adaptive mechanism to regulate cellular function. The detection of methylated lipids in Pyrobaculum sp. AQ1.S2 and Sulfolobus acidocaldarius represents the first reported occurrences in Crenarchaeota. Soils and aquatic sediments from geographically distinct mesotemperate environments that were screened for homologues contained monomethylated tetraethers, with di- and trimethylated structures being detected occasionally. The structural diversity and range of occurrences of the C(87-89) tetraethers highlight their potential as complementary biomarkers for archaea in natural environments. Copyright © 2015 John Wiley & Sons, Ltd.

Sources and transport of microbial tetraether membrane lipids in Karst Systems

NASA Astrophysics Data System (ADS)

Jex, C.; Blyth, A. J.; McDonald, J.; Woltering, M.; Khan, S.; Baker, A.

2014-12-01

Speleothems preserve organic biomarkers, proxies for surface climate. Microbial-derived lipids, specifically glycerol dialkyl glycerol tetraetheral (GDGT) lipids have been identified in cave deposits and shown to correlate well with surface air temperature using the archaea-derived isoprenoid '(i)GDGT' index of TEX86 and the bacteria derived branched '(b)GDGT' index of MBT/CBT of modern speleothems [1]. Two competing sources for GDGTs in karst systems have been suggested: 1) A soil derived microbial signal dominated by bGDGTs; and 2) An in situ signal dominated by iGDGTs, representative of archaea existing within the cave or overlying bedrock [2]. These findings are yet to be thoroughly tested by characterising the seasonal nature of GDGTs in caves to establish the source and transport pathways within these complex fractured rock systems. Here, we address this and present the results of a yearlong monitoring campaign of GDGTs within two contrasting cave sites from the Yarrangobilly Caves in Kosciuszko national park, SE Australia. The caves are located at a high altitude, semi-arid site. Harriewood cave is dominated by discrete infiltration events throughout the year. Above the cave there are thin soils consisting of loose shallow scree, steep slopes and sparse shrub vegetation. The surface above Jillabenan is characterised by thick red clays of moderate to no slope and Eucalypt dominated forest. As such, these caves provide ideal test sites to characterise the variability in GDGT signals that may be a result of non-temperature related factors, including varying inputs (groundwater vs. in situ growth) or site-specific hydrological conditions. We present data obtained from within the cave: drip waters and in situ collection of GDGTs formed on filter papers left inside the cave throughout the year, and externally sourced signals from soils and their leachates. We also identify key differences in soil pH and cave air temperatures that are best predicted by using cave specific GDGT calibrations of [1]. [1] Blyth et al. 2013. Calibrating the glycerol dialkyl glycerol tetraether temperature signal in speleothems. Geochim Cosmochim Ac. 109, 312-328. [2] Blyth et al. 2014. Contrasting distributions of glycerol dialkyl glycerol tetraethers (GDGTs) in speleothems and associated soils, Org Geochem, 69, 1-10.

Copper-catalyzed oxidative C-O bond formation of 2-acyl phenols and 1,3-dicarbonyl compounds with ethers: direct access to phenol esters and enol esters.

PubMed

Park, Jihye; Han, Sang Hoon; Sharma, Satyasheel; Han, Sangil; Shin, Youngmi; Mishra, Neeraj Kumar; Kwak, Jong Hwan; Lee, Cheong Hoon; Lee, Jeongmi; Kim, In Su

2014-05-16

A copper-catalyzed oxidative coupling of 2-carbonyl-substituted phenols and 1,3-dicarbonyl compounds with a wide range of dibenzyl or dialkyl ethers is described. This protocol provides an efficient preparation of phenol esters and enol esters in good yields with high chemoselectivity. This method represents an alternative protocol for classical esterification reactions.

USSR and Eastern Europe Scientific Abstracts Chemistry No. 53

DTIC Science & Technology

1977-03-23

EFFECTIVENESS OF N,N-DIALKYL-N’-ARYLGUANIDINES AGAINST POWDERY MILDEW OF CUCUMBERS Moscow KHIM. SREDSTVA ZASHCHITY RAST. [CHEMICAL SUBSTANCES FOR PLANT... powdery mildew of cucumbers. A number of compounds are discovered which are similar in effectiveness to caratan (ethanol). A study is made of the...RELATIONSHIP BETWEEN THE CONTENT OF TOTAL NITROGEN, PROTEIN AND GLUTEN IN WINTER WHEAT GRAIN Moscow KHIMIYA V SEL’SKOM KHOZYAYSTVE in Russian Vol

A dehydrogenative cross-coupling reaction between aromatic aldehydes or ketones and dialkyl H-phosphonates for formyl or acylphenylphosphonates.

PubMed

Huang, Xing-Fen; Wu, Qing-Lai; He, Jian-Shi; Huang, Zhi-Zhen

2015-04-21

A novel DCC reaction between aromatic aldehydes or ketones and H-phosphonates has been developed for the synthesis of p-formyl or p-acylphenylphosphonates. The synthetic method has excellent para regioselectivities, good yields, and broad substrate scopes and is more benign to the environment. The DCC reaction also tolerates many functional groups, and results in a series of new p-formyl and p-acylphenylphosphonates, which should be important building blocks for the synthesis of versatile arylphosphonate derivatives.

Rhizospheric effects on the microbial community of e-waste-contaminated soils using phospholipid fatty acid and isoprenoid glycerol dialkyl glycerol tetraether analyses.

PubMed

Song, Mengke; Cheng, Zhineng; Luo, Chunling; Jiang, Longfei; Zhang, Dayi; Yin, Hua; Zhang, Gan

2018-04-01

We performed the study of rhizospheric effects on soil microbial community structure, including bacteria, fungi, actinomycete, and archaea, at an electronic waste (e-waste) recycling site by analyzing the phospholipid fatty acid (PLFA) and isoprenoid glycerol dialkyl glycerol tetraether (GDGT) contents. By comparing PLFA and isoprenoid GDGT profiles of rhizospheric and surrounding bulk soils of 11 crop species, we observed distinct microbial community structures. The total PLFA concentration was significantly higher in rhizospheric soils than in non-rhizospheric soils, whereas no obvious difference was found in the total isoprenoid GDGT concentrations. The microbial community structure was also different, with higher ratios of fungal-to-bacterial PLFAs (F/B) and lower relative abundance of Gram-positive bacteria in rhizospheric soils. The extent of rhizospheric effects varied among plant species, and Colocasia esculenta L. had the greatest positive effects on the total microbial biomass. Dissolved organic carbon and pH were the main environmental factors affecting the microbial community represented by PLFAs, while the archaeal community was influenced by copper and zinc in all soils. These results offer a comprehensive view of rhizospheric effects on microbes in heavy metal and persistent organic pollutant co-contaminated soil, and provide fundamental knowledge regarding microbial ecology in e-waste-contaminated soils.

The Preparation and Characterization of Tetrafluoro-lambda 6-Sulfanes

NASA Astrophysics Data System (ADS)

Zhong, Linbin

Synthetic access to systematically substituted tetrafluoro-λ6-sulfanes was challenging and the research in this area had been largely abandoned. The original reports of disubstituted-tetrafluoro-λ6-sulfanes were limited to substitution by diphenyl and dialkyl groups. The dialkyl-tetrafluoro-λ6-sulfanes were reactive while the diphenyl substituted compounds showed decreased reactivity. In this dissertation, the systematic substitution on tetrafluoro-λ6-sulfanes has enabled the studies of the substitution effects on reactivity. The synthesis of substituted-tetrafluoro-λ6-sulfanyl chlorides were facilitated by a convenient preparation of CF3SF4Cl and aryl-SF4Cl. The scope and limits of the free radical promoted reaction of these compounds were explored by addition to alkenes and alkynes. Especially interesting is that several of the resulting adducts were crystallized in non-centrosymmetric structures. Novel polymers linked by SF4 groups were also prepared. As a derivative of SF5Cl, substituted-tetrafluoro-λ6-sulfanes are expected to have similar reactivity, specifically, when the trans-(trifluoromethyl)-tetrafluoro-λ6-sulfanyl is incorporated into to molecules. The physicochemical properties of these compounds may surpass those of the SF5 analogs. Subsequent transformations of the addition products, such as the preparations of alkyl-SF4Cl substituted alkenes, alkynes, carboxylic acid, ketones, and aldehydes will be described.

XRD, TEM, and thermal analysis of Arizona Ca-montmorillonites modified with didodecyldimethylammonium bromide.

PubMed

Sun, Zhiming; Park, Yuri; Zheng, Shuilin; Ayoko, Godwin A; Frost, Ray L

2013-10-15

An Arizona SAz-2 calcium montmorillonite was modified by a typical dialkyl cationic surfactant (didodecyldimethylammonium bromide, abbreviated to DDDMA) through direct ion exchange. The obtained organoclays were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), high-resolution thermogravimetric analysis (HR-TG), and infrared emission spectroscopy (IES). The intercalation of surfactants greatly increased the basal spacing of the interlayers and the conformation arrangement of the loaded surfactant were assessed based on the XRD and TEM measurements. This work shows that the dialkyl surfactant can be directly intercalated into the montmorillonite without first undergoing Na(+) exchange. Moreover, the thermal stability of organoclays and the different arrangements of the surfactant molecules intercalated in the SAz-2 Ca-montmorillonite were determined by a combination of TG and IES techniques. The detailed conformational ordering of different intercalated surfactants under different conditions was also studied. The surfactant molecule DDDMA has proved to be thermally stable even at 400°C which indicates that the prepared organoclay is stable to significantly high temperatures. This study offers new insights into the structure and thermal stabilities of SAz-2 Ca-montmorillonite modified with DDDMA. The experimental results also confirm the potential applications of organic SAz-2 Ca-montmorillonites as adsorbents and polymer-clay nanocomposites. Copyright © 2013 Elsevier Inc. All rights reserved.

[Cu 32(H) 20{S 2P(O i Pr) 2 } 12 ]: The Largest Number of Hydrides Recorded in a Molecular Nanocluster by Neutron Diffraction

DOE PAGES

Dhayal, Rajendra S.; Liao, Jian-Hong; Kahlal, Samia; ...

2015-04-20

An air- and moisture-stable nanoscale polyhydrido copper cluster [Cu 32(H) 20{S 2P(O i Pr) 2 } 12 ] (1 H) was synthesized and structurally characterized. The molecular structure of 1 H exhibits a hexacapped pseudo-rhombohedral core of 14 Cu atoms sandwiched between two nestlike triangular cupola fragments of (2x9) Cu atoms in an elongated triangular gyrobicupola polyhedron. The discrete Cu 32 cluster is stabilized by 12 dithiophosphate ligands and a record number of 20 hydride ligands, which were found by high-resolution neutron diffraction to exhibit tri-, tetra-, and pentacoordinated hydrides in capping and interstitial modes. We conclude that this resultmore » was further supported by a density functional theory investigation on the simplified model [Cu 32(H) 20(S 2PH 2) 12].« less

Tribology. Mechanisms of antiwear tribofilm growth revealed in situ by single-asperity sliding contacts.

PubMed

Gosvami, N N; Bares, J A; Mangolini, F; Konicek, A R; Yablon, D G; Carpick, R W

2015-04-03

Zinc dialkyldithiophosphates (ZDDPs) form antiwear tribofilms at sliding interfaces and are widely used as additives in automotive lubricants. The mechanisms governing the tribofilm growth are not well understood, which limits the development of replacements that offer better performance and are less likely to degrade automobile catalytic converters over time. Using atomic force microscopy in ZDDP-containing lubricant base stock at elevated temperatures, we monitored the growth and properties of the tribofilms in situ in well-defined single-asperity sliding nanocontacts. Surface-based nucleation, growth, and thickness saturation of patchy tribofilms were observed. The growth rate increased exponentially with either applied compressive stress or temperature, consistent with a thermally activated, stress-assisted reaction rate model. Although some models rely on the presence of iron to catalyze tribofilm growth, the films grew regardless of the presence of iron on either the tip or substrate, highlighting the critical role of stress and thermal activation. Copyright © 2015, American Association for the Advancement of Science.

International Conference on Organometallic Chemistry (13th) Held in Torino, Europe on 4-9 September 1988. Abstracts

DTIC Science & Technology

1988-09-09

On Synthesis Of Dialkyl d-Trimethylsilyloxyalkylphosphonates Zhao Yong-Zhen and Li Zhong- Rua Dpartment o chemistry, Hua Zhong Normal University, Wuhan...Jose Vicente. Jose-AntelC hAd. Na-Yeij~xa Qhicote. Ju~an-Francisco Gutliez-Jugo. Carmen Ramirez do Arel lano. Departamento do Oulmica InordanIca...Peruzzini, Jos& Antonio Ramirez , Alberto Vacca, Francesco Vizza and Fabrizio Zanobini, Istituto per lo Studio della Stereochimica ed Energetica dei

Nondestructive Early Detection of Metal Corrosion in Pigmented Coatings with Fluorescent Smart Materials

DTIC Science & Technology

2012-05-01

reacted with various ketones and aldehydes to form a wide variety of hydrazone dyes (tables 1 and 2). Table 1. Rhodamine B dyes. Dyes Synthesized...reacted with various diphenyl and dialkyl ketones to determine the impact of bulky groups on dye-metal binding. Electronic effects were probed as the...hydrazide precursors were reacted with various aldehydes that contained substituted phenyl rings. Fluorescence measurements were used to determine the

Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

NASA Technical Reports Server (NTRS)

Jahnke, Linda L.; Eder, Wolfgang; Huber, Robert; Hinrichs, Kai-Uwe; Hayes, John M.; Cady, Sherry L.; DesMarais, David J.; Hope, Janet M.; Summons, Roger E.

2001-01-01

Extremely thermophilic microbial communities associated with the siliceous vent walls and outflow channel of Octopus Spring, Yellowstone National Park, have been examined for lipid biomarker and carbon isotopic signatures. These data were compared with that obtained from representatives of three Aquificales genera. Thermocrinis ruber, Thermocrinis sp. HI, Hydrogenobacter thermophilus, Aquifex pyrophilus and Aquifex aeolicus all contained phospholipids composed not only of the usual ester-linked fatty acids, but also ether-linked alkyl moieties. The fatty acids of all cultured organisms were dominated by very distinct pattern of n-C-20:1 and cy-C-21 compounds. The alkyl glycerol ethers were present primarily as C-18:0 monoethers with the exception of the Aquifex spp. in which dialkyl glycerol ethers with a boarder carbon-number distribution were also present. These Aquificales biomarker lipids were the major constituents in the lipid extracts of the Octopus Spring microbial samples. Two natural samples, a microbial biofilm growing in association with deposition of amorphous silica on the vent walls at 92 C, and the well-known "pink-streamer community" (PSC), siliceous filaments of a microbial consortia growing in the outflow channel at 87 C were analyzed. Both the biofilm and PSC samples contained mono- and dialkyl glycerol ethers with a prevalence of C-18 and C-20 alkyls. Phospholipid fatty acids were comprised of both the characteristic. Additional information is contained in the original extended abstract.

Phosphonic acid: preparation and applications.

PubMed

Sevrain, Charlotte M; Berchel, Mathieu; Couthon, Hélène; Jaffrès, Paul-Alain

2017-01-01

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H 3 PO 3 ) and that produce a phosphonic acid functional group simultaneously to the formation of the P-C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids.

An enantioselective approach to the preparation of chiral sulfones by Ir-catalyzed asymmetric hydrogenation.

PubMed

Peters, Byron K; Zhou, Taigang; Rujirawanich, Janjira; Cadu, Alban; Singh, Thishana; Rabten, Wangchuk; Kerdphon, Sutthichat; Andersson, Pher G

2014-11-26

Several chiral sulfonyl compounds were prepared using the iridium catalyzed asymmetric hydrogenation reaction. Vinylic, allylic and homoallylic sulfone substitutions were investigated, and high enantioselectivity is maintained regardless of the location of the olefin with respect to the sulfone. Impressive stereoselectivity was obtained for dialkyl substitutions, which typically are challenging substrates in the hydrogenation. As expected, the more bulky Z-substrates were hydrogenated slower than the corresponding E isomers, and in slightly lower enantioselectivity.

Nondestructive Early Detection of Metal Corrosion in Pigmented Coatings with Fluorescent Smart Materials (First-year Report)

DTIC Science & Technology

2012-05-01

reacted with various ketones and aldehydes to form a wide variety of hydrazone dyes (tables 1 and 2). Table 1. Rhodamine B dyes. Dyes Synthesized...reacted with various diphenyl and dialkyl ketones to determine the impact of bulky groups on dye-metal binding. Electronic effects were probed as the...hydrazide precursors were reacted with various aldehydes that contained substituted phenyl rings. Fluorescence measurements were used to determine the

Nickel(II) and copper(II) complexes of N,N-dialkyl-N‧-3-chlorobenzoylthiourea: Synthesis, characterization, crystal structures, Hirshfeld surfaces and antimicrobial activity

NASA Astrophysics Data System (ADS)

Binzet, Gun; Gumus, Ilkay; Dogen, Aylin; Flörke, Ulrich; Kulcu, Nevzat; Arslan, Hakan

2018-06-01

We synthesized four new N,N-dialkyl-N‧-3-chlorobenzoylthiourea ligands (Alkyl: Dimethyl, diethyl, di-n-propyl and di-n-butyl) and their metal complexes with copper and nickel atoms. The structure of all synthesized compounds was fully characterized by physicochemical, spectroscopic and single crystal X-ray diffraction analysis techniques. The physical, spectral and analytical data of the newly synthesized metal complexes have shown the formation of 1:2 (metal:ligand) ratio. The benzoylthiourea ligands coordinate with metal atoms through oxygen and sulphur atoms. The metal atoms are in slightly distorted square-planar coordination geometry in Ni(II) or Cu(II) complex. Two oxygen and two sulphur atoms are mutually cis to each other in Ni(II) or Cu(II) complex. The intermolecular contacts in the compounds, which are HL1 and HL3, were examined by Hirshfeld surfaces and fingerprint plots using the data obtained from X-ray single crystal diffraction measurement. Besides these, their antimicrobial activities against Gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus, Streptococcus pyogenes and Enterococcus faecalis) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and anti-yeast activity (Candida glabrata, Candida parapsilosis and Candida albicans) were investigated. This exhibited some promising results towards testing organism. Among all the compounds, Ni(L1)2 complex showed high activity against Bacillus subtilis with MIC values at 7.81 μg/mL.

Ubiquitous production of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in global marine environments: a new source indicator for brGDGTs

NASA Astrophysics Data System (ADS)

Xiao, Wenjie; Wang, Yinghui; Zhou, Shangzhe; Hu, Limin; Yang, Huan; Xu, Yunping

2016-10-01

Presumed source specificity of branched glycerol dialkyl glycerol tetraethers (brGDGTs) from bacteria thriving in soil/peat and isoprenoid GDGTs (iGDGTs) from aquatic organisms led to the development of several biomarker proxies for biogeochemical cycle and paleoenvironmental reconstructions. However, recent studies reveal that brGDGTs are also produced in aquatic environments besides soils and peat. Here we examined three cores from the Bohai Sea, and found distinct difference in brGDGT compositions varying with the distance from the Yellow River mouth. We thus propose an abundance ratio of hexamethylated to pentamethylated brGDGT (IIIa / IIa) to evaluate brGDGT sources. The compilation of globally distributed 1354 marine sediments and 589 soils shows that the IIIa / IIa ratio is generally < 0.59 in soils and 0.59-0.92 and > 0.92 in marine sediments with and without significant terrestrial inputs, respectively. Such disparity confirms the existence of two sources for brGDGTs, a terrestrial origin with lower IIIa / IIa and a marine origin with higher IIIa / IIa, which is likely attributed to a generally higher pH and the production of brGDGTs in cold deep water in marine waters. The application of the IIIa / IIa ratio to the East Siberian Arctic Shelf proves it to be a sensitive source indicator for brGDGTs, which is helpful for accurate estimation of organic carbon source and paleoclimates in marine settings.

Methods to Measure, Predict and Relate Friction, Wear and Fuel Economy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gravante, Steve; Fenske, George; Demas, Nicholas

High-fidelity measurements of the coefficient of friction and the parasitic friction power of the power cylinder components have been made for the Isuzu 5.2L 4H on-highway engine. In particular, measurements of the asperity friction coefficient were made with test coupons using Argonne National Lab’s (ANL) reciprocating test rig for the ring-on-liner and skirt-on-liner component pairs. These measurements correlated well with independent measurements made by Electro-Mechanical Associates (EMA). In addition, surface roughness measurements of the Isuzu components were made using white light interferometer (WLI). The asperity friction and surface characterization are key inputs to advanced CAE simulation tools such as RINGPAKmore » and PISDYN which are used to predict the friction power and wear rates of power cylinder components. Finally, motored friction tests were successfully performed to quantify the friction mean effective pressure (FMEP) of the power cylinder components for various oils (High viscosity 15W40, low viscosity 5W20 with friction modifier (FM) and specially blended oil containing consisting of PAO/ZDDP/MoDTC) at 25, 50, and 110°C.« less

Method for producing high carrier concentration p-Type transparent conducting oxides

DOEpatents

Li, Xiaonan; Yan, Yanfa; Coutts, Timothy J.; Gessert, Timothy A.; Dehart, Clay M.

2009-04-14

A method for producing transparent p-type conducting oxide films without co-doping plasma enhancement or high temperature comprising: a) introducing a dialkyl metal at ambient temperature and a saturated pressure in a carrier gas into a low pressure deposition chamber, and b) introducing NO alone or with an oxidizer into the chamber under an environment sufficient to produce a metal-rich condition to enable NO decomposition and atomic nitrogen incorporation into the formed transparent metal conducting oxide.

A nickel catalyst for the addition of organoboronate esters to ketones and aldehydes.

PubMed

Bouffard, Jean; Itami, Kenichiro

2009-10-01

A Ni(cod)(2)/IPr catalyst promotes the intermolecular 1,2-addition of arylboronate esters to unactivated aldehydes and ketones. Diaryl, alkyl aryl, and dialkyl ketones show good reactivity under mild reaction conditions (< or = 80 degrees C, nonpolar solvents, no strong base or acid additives). A dramatic ligand effect favors either carbonyl addition (IPr) or C-OR cross-coupling (PCy(3)) with aryl ether substrates. A Ni(0)/Ni(II) catalytic cycle initiated by the oxidative cyclization of the carbonyl substrate is proposed.

Drilling fluid containing a copolymer filtration control agent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lucas, J. M.

1985-10-15

The invention relates to an aqueous drilling fluid composition, a filtration control agent for utilization in said aqueous drilling fluid, and a method of forming a filter cake on the wall of a well for the reduction of filtrate from said drilling fluid, by utilization of a copolymer of: a (meth) acrylamido alkyl sulfonic acid or alkali metal salt thereof; and N, N-dialkyl (meth) acrylamide. The copolymer may be cross-linked with N,N'-methylenebisacrylamide or other appropriate cross-linking agent.

Highly soluble [1]benzothieno[3,2-b]benzothiophene (BTBT) derivatives for high-performance, solution-processed organic field-effect transistors.

PubMed

Ebata, Hideaki; Izawa, Takafumi; Miyazaki, Eigo; Takimiya, Kazuo; Ikeda, Masaaki; Kuwabara, Hirokazu; Yui, Tatsuto

2007-12-26

2,7-Dialkyl[1]benzothieno[3,2-b]benzothiophenes were tested as solution-processible molecular semiconductors. Thin films of the organic semiconductors deposited on Si/SiO2 substrates by spin coating have well-ordered structures as confirmed by XRD analysis. Evaluations of the devices under ambient conditions showed typical p-channel FET responses with the field-effect mobility higher than 1.0 cm2 V-1 s-1 and Ion/Ioff of approximately 10(7).

Method for the concentration and separation of actinides from biological and environmental samples

DOEpatents

Horwitz, E.P.; Dietz, M.L.

1989-05-30

A method and apparatus for the quantitative recover of actinide values from biological and environmental sample by passing appropriately prepared samples in a mineral acid solution through a separation column of a dialkyl(phenyl)-N,N-dialylcarbamoylmethylphosphine oxide dissolved in tri-n-butyl phosphate on an inert substrate which selectively extracts the actinide values. The actinide values can be eluted either as a group or individually and their presence quantitatively detected by alpha counting. 3 figs.

Distribution of branched glycerol dialkyl glycerol tetraethers in surface soils of the Qinghai-Tibetan Plateau: implications of brGDGTs-based proxies in cold and dry regions

NASA Astrophysics Data System (ADS)

Ding, S.; Xu, Y.; Wang, Y.; He, Y.; Hou, J.; Chen, L.; He, J.-S.

2015-06-01

The methylation index of branched tetraethers (MBT) and cyclization ratio of branched tetraethers (CBT) based on the distribution of branched glycerol dialkyl glycerol tetraethers (brGDGT) are useful proxies for the reconstruction of mean annual air temperature (MAT) and soil pH. Recently, a series of 6-methyl brGDGTs were identified which were previously co-eluted with 5-methyl brGDGTs. However, little is known about 6-methyl brGDGTs in the Qinghai-Tibetan Plateau (QTP), a critical region of the global climate system. Here, we analyze 30 surface soils covering a large area of the QTP, among which 6-methyl brGDGTs were the most abundant components (average 53 ± 17% of total brGDGT). The fractional abundance of 6-methyl brGDGTs showed a good correlation with soil pH, while the global MBT'5ME calibration overestimates MAT in the QTP. We therefore proposed a MBT5/6 index including both 5- and 6-methyl brGDGTs, presenting a strong correlation with MAT in QTP: MAT = -20.14 + 39.51 × MBT5/6 (n = 27, r2 = 0.82; RMSE = 1.3 °C). Another index, namely IBT (isomerization of branched tetraether), based on carbon skeleton isomerization of the 5-methyl to 6-methyl brGDGTs, is dependent on soil pH: pH = 6.77 - 1.56 × IBT (n = 27; r2 = 0.74, RMSE = 0.32). Our study suggests that changing the position of methyl group of brGDGTs may be another mechanism for some soil bacteria to adapt to the ambient pH change in addition to the well-known cyclization.

Construction of a novel Mo/Cu/S cluster with a closed double-cubane-like polyhedron and a chain polymer of W/Cu/S clusters.

PubMed

Li, Zhihua; Du, Shaowu; Wu, Xintao

2004-08-09

Reaction of [MoOS(3)](2)(-) and [WS(4)](2)(-) with Cudtp (dtp = diethyl dithiophosphate) gave rise to the clusters [Bu(4)N](2)[(MoOS(3))(4)Cu(12)(dtp)(6)], 1, and [Et(4)N][(WS(4)Cu(4))(dtp)(3)], 2, respectively. In cluster 1, the dtp- ligands act as both monodentate and bidentate ligands that bridge between Cu atoms and link together a closed double-cubane-like [Mo(2)O(2)S(6)Cu(6)](2+) core and two incomplete cubane-like [MoOS(3)Cu(3)]+ units. In cluster 2, the [WS(4)Cu(4)](2+) fragments were connected via bidentate and doubly bridging dtp- bridges to give a chain polymeric anion. Cluster 1 is the first example of a Mo/Cu/S cluster that contains a closed double-cubane-like structure. Compound 2 is also rare and the first W/Cu/S polymer with dtp- linkages.

In situ production of branched glycerol dialkyl glycerol tetraethers in a great basin hot spring (USA).

PubMed

Zhang, Chuanlun L; Wang, Jinxiang; Dodsworth, Jeremy A; Williams, Amanda J; Zhu, Chun; Hinrichs, Kai-Uwe; Zheng, Fengfeng; Hedlund, Brian P

2013-01-01

Branched glycerol dialkyl glycerol tetraethers (bGDGTs) are predominantly found in soils and peat bogs. In this study, we analyzed core (C)-bGDGTs after hydrolysis of polar fractions using liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry and analyzed intact P-bGDGTs using total lipid extract (TLE) without hydrolysis by liquid chromatography-electrospray ionization-multiple stage mass spectrometry. Our results show multiple lines of evidence for the production of bGDGTs in sediments and cellulolytic enrichments in a hot spring (62-86°C) in the Great Basin (USA). First, in situ cellulolytic enrichment led to an increase in the relative abundance of hydrolysis-derived P-bGDGTs over their C-bGDGT counterparts. Second, the hydrolysis-derived P- and C-bGDGT profiles in the hot spring were different from those of the surrounding soil samples; in particular, a monoglycosidic bGDGT Ib containing 13,16-dimethyloctacosane and one cyclopentane moiety was detected in the TLE but it was undetectable in surrounding soil samples even after sample enrichments. Third, previously published 16S rRNA gene pyrotag analysis from the same lignocellulose samples demonstrated the enrichment of thermophiles, rather than mesophiles, and total bGDGT abundance in cellulolytic enrichments correlated with the relative abundance of 16S rRNA gene pyrotags from thermophilic bacteria in the phyla Bacteroidetes, Dictyoglomi, EM3, and OP9 ("Atribacteria"). These observations conclusively demonstrate the production of bGDGTs in this hot spring; however, the identity of organisms that produce bGDGTs in the geothermal environment remains unclear.

Phosphonic acid: preparation and applications

PubMed Central

Sevrain, Charlotte M; Berchel, Mathieu; Couthon, Hélène

2017-01-01

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H3PO3) and that produce a phosphonic acid functional group simultaneously to the formation of the P–C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids. PMID:29114326

Fused dithienogermolodithiophene low band gap polymers for high-performance organic solar cells without processing additives.

PubMed

Zhong, Hongliang; Li, Zhe; Deledalle, Florent; Fregoso, Elisa Collado; Shahid, Munazza; Fei, Zhuping; Nielsen, Christian B; Yaacobi-Gross, Nir; Rossbauer, Stephan; Anthopoulos, Thomas D; Durrant, James R; Heeney, Martin

2013-02-13

We report the synthesis of a novel ladder-type fused ring donor, dithienogermolodithiophene, in which two thieno[3,2-b]thiophene units are held coplanar by a bridging dialkyl germanium. Polymerization of this extended monomer with N-octylthienopyrrolodione by Stille polycondensation afforded a polymer, pDTTG-TPD, with an optical band gap of 1.75 eV combined with a high ionization potential. Bulk heterojunction solar cells based upon pDTTG-TPD:PC(71)BM blends afforded efficiencies up to 7.2% without the need for thermal annealing or processing additives.

n-BuLi as a highly efficient precatalyst for hydrophosphonylation of aldehydes and unactivated ketones.

PubMed

Liu, Chengwei; Zhang, Yu; Qian, Qinqin; Yuan, Dan; Yao, Yingming

2014-12-05

It was found for the first time that organic alkali metal compounds serve as highly efficient precatalysts for the hydrophosphonylation reactions of aldehydes and unactivated ketones with dialkyl phosphite under mild conditions. For ketone substrates, a reversible reaction was observed, and the influence of catalyst loading and reaction temperature on the reaction equilibrium was studied in detail. Overall, the hydrophosphonylation reactions catalyzed by 0.1 mol % n-BuLi were completed within 5 min for a broad range of substrates and generated a series of α-hydroxy phosphonates in high yields.

The synthesis of α-aryl-α-aminophosphonates and α-aryl-α-aminophosphine oxides by the microwave-assisted Pudovik reaction

PubMed Central

Tajti, Ádám; Ádám, Anna; Csontos, István; Karaghiosoff, Konstantin; Czugler, Mátyás; Ábrányi-Balogh, Péter

2017-01-01

A family of α-aryl-α-aminophosphonates and α-aryl-α-aminophosphine oxides was synthesized by the microwave-assisted solvent-free addition of dialkyl phosphites and diphenylphosphine oxide, respectively, to imines formed from benzaldehyde derivatives and primary amines. After optimization, the reactivity was mapped, and the fine mechanism was evaluated by DFT calculations. Two α-aminophosphonates were subjected to an X-ray study revealing a racemic dimer formation made through a N–H···O=P intermolecular hydrogen bridges pair. PMID:28179951

Structural Analogues of Selfotel.

PubMed

Dziuganowska, Zofia A; Ślepokura, Katarzyna; Volle, Jean-Noël; Virieux, David; Pirat, Jean-Luc; Kafarski, Paweł

2016-06-17

A small library of phosphonopiperidylcarboxylic acids, analogues of NMDA antagonist selfotel (CGS 19755), was synthesized. First, the series of aromatic esters was obtained via a palladium-catalyzed cross-coupling reaction (Hirao coupling) of dialkyl phosphites with bromopyridinecarboxylates, followed by their hydrolysis. Then, hydrogenation of the resulting phosphonopyridylcarboxylic acids over PtO2 yielded the desired phosphonopiperidylcarboxylic acids. NMR studies indicated that the hydrogenation reaction proceeds predominantly by cis addition. Several compounds were obtained as monocrystal structures. Preliminary biological studies performed on cultures of neurons suggest that the obtained compounds possess promising activity toward NMDA receptors.

Development of a Regional Glycerol Dialkyl Glycerol Tetraether (GDGT) - Temperature Calibration for Antarctic and sub-Antarctic Lakes

NASA Astrophysics Data System (ADS)

Roberts, S. J.; Foster, L. C.; Pearson, E. J.; Steve, J.; Hodgson, D.; Saunders, K. M.; Verleyen, E.

2016-12-01

Temperature calibration models based on the relative abundances of sedimentary glycerol dialkyl glycerol tetraethers (GDGTs) have been used to reconstruct past temperatures in both marine and terrestrial environments, but have not been widely applied in high latitude environments. This is mainly because the performance of GDGT-temperature calibrations at lower temperatures and GDGT provenance in many lacustrine settings remains uncertain. To address these issues, we examined surface sediments from 32 Antarctic, sub-Antarctic and Southern Chilean lakes. First, we quantified GDGT compositions present and then investigated modern-day environmental controls on GDGT composition. GDGTs were found in all 32 lakes studied. Branched GDGTs (brGDGTs) were dominant in 31 lakes and statistical analyses showed that their composition was strongly correlated with mean summer air temperature (MSAT) rather than pH, conductivity or water depth. Second, we developed the first regional brGDGT-temperature calibration for Antarctic and sub-Antarctic lakes based on four brGDGT compounds (GDGT-Ib, GDGT-II, GDGT-III and GDGT-IIIb). Of these, GDGT-IIIb proved particularly important in cold lacustrine environments. Our brGDGT-Antarctic temperature calibration dataset has an improved statistical performance at low temperatures compared to previous global calibrations (r2=0.83, RMSE=1.45°C, RMSEP-LOO=1.68°C, n=36 samples), highlighting the importance of basing palaeotemperature reconstructions on regional GDGT-temperature calibrations, especially if specific compounds lead to improved model performance. Finally, we applied the new Antarctic brGDGT-temperature calibration to two key lake records from the Antarctic Peninsula and South Georgia. In both, downcore temperature reconstructions show similarities to known Holocene warm periods, providing proof of concept for the new Antarctic calibration model.

Biological Sources of Branched Glycerol Dialkyl Glycerol Tetraethers (brGDGTs) in Terrestrial Hot Springs: A Possible Link Between Nitrogen-cycling Bacteria and brGDGT Production

NASA Astrophysics Data System (ADS)

Wang, J. X.; Xie, W.; Boyd, E. S.; Hedlund, B. P.; Zhang, C.

2014-12-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are common in peat, soil, lakes, rivers and hot springs. To seek the potential biological sources of brGDGTs in geothermal environments, we investigated 65 hot springs in the Yellowstone National Park (USA) and Tengchong (China). Together with previously published data from hot springs in the Great Basin (USA) and Tibet (China), we found that the abundance of brGDGTs tended to peak in springs with pH > 8. This contrasts with previous observations indicating an abundance of brGDGTs in acidic soils and peat bogs, suggesting a different biological source and function for lipids in these environments. In support of this hypothesis, a comparison of Cyclization ratios of Branched Tetraethers (CBT) between hot springs and surrounding soils indicated that more brGDGTs with cyclopentane moieties were produced in alkaline hot springs than in nearby low-temperature soils. Since Acidobacteria (the likely source of brGDGTs in peat bog environments) tend to have low CBT ratios, these data suggest a different source for brGDGTs in hot spring environments. RDA and regression analysis integrating brGDGT compounds and nitrogen species indicate that Bacteria involved in the nitrogen biogeochemical cycle (ammonia oxidation and nitrite reduction) may be related to the production of brGDGTs in terrestrial hot springs. However, direct evidence showing the link between nitrogen-cycling bacteria and brGDGT production has yet to be demonstrated under laboratory conditions. Nevertheless, our study expands the possibility of brGDGT sources into bacterial communities in terrestrial geothermal systems where Acidobacteria are absent or only a minor component.

Branched glycerol dialkyl glycerol tetraethers in Arctic lake sediments: Sources and implications for paleothermometry at high latitudes

NASA Astrophysics Data System (ADS)

Peterse, Francien; Vonk, Jorien E.; Holmes, R. Max; Giosan, Liviu; Zimov, Nikita; Eglinton, Timothy I.

2014-08-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are analyzed in different lakes of the Mackenzie (Canadian Arctic) and Kolyma (Siberian Arctic) River basins to evaluate their sources and the implications for brGDGT-based paleothermometry in high-latitude lakes. The comparison of brGDGT distributions and concentrations in the lakes with those in river suspended particulate matter, riverbank sediments, and permafrost material indicates that brGDGTs in Arctic lake sediments have mixed sources. In contrast to global observations, distributional offsets between brGDGTs in Arctic lakes and elsewhere in the catchment are minor, likely due to the extreme seasonality and short window of biological production at high latitudes. Consequently, both soil- and lake-calibrated brGDGT-based temperature proxies return sensible temperature estimates, even though the mean air temperature (MAT) in the Arctic is below the calibration range. The original soil-calibrated MBT-CBT (methylation of branched tetraethers-cyclisation of branched tetraethers) proxy generates MATs similar to those in the studied river basins, whereas using the recently revised MBT'-CBT calibration overestimates MAT. The application of the two global lake calibrations, generating summer air temperatures (SAT) and MAT, respectively, illustrates the influence of seasonality on the production of brGDGTs in lakes, as the latter overestimates actual MAT, whereas the SAT-based lake calibration accounts for this influence and consequently returns more accurate temperatures. Our results in principle support the application of brGDGT-based temperature proxies in high-latitude lakes in order to obtain long-term paleotemperature records for the Arctic, although the calibration and associated transfer function have to be selected with care.

Disulfide oil hazard assessment using categorical analysis and a mode of action determination.

PubMed

Morgott, David; Lewis, Christopher; Bootman, James; Banton, Marcy

2014-01-01

Diethyl and diphenyl disulfides, naphtha sweetening (Chemical Abstracts Service [CAS] # 68955-96-4), are primarily composed of low-molecular-weight dialkyl disulfides extracted from C4 to C5 light hydrocarbon streams during the refining of crude oil. The substance, commonly known as disulfide oil (DSO), can be composed of up to 17 different disulfides and trisulfides with monoalkyl chain lengths no greater than C4. The disulfides in DSO constitute a homologous series of chemical constituents that are perfectly suited for a hazard evaluation using a read-across/worst-case approach. The DSO constituents exhibit a common mode of action that is operable at all trophic levels. The observed oxidative stress response is mediated by reactive oxygen species and free radical intermediates generated after disulfide bond cleavage and subsequent redox cycling of the resulting mercaptan. Evidence indicates that the lowest series member, dimethyl disulfide (DMDS), can operate as a worst-case surrogate for other members of the series, since it displays the highest toxicity. Increasing the alkyl chain length or degree of substitution has been shown to serially reduce disulfide toxicity through resonance stabilization of the radical intermediate or steric inhibition of the initial enzymatic step. The following case study examines the mode of action for dialkyl disulfide toxicity and documents the use of read-across information from DMDS to assess the hazards of DSO. The results indicate that DSO possesses high aquatic toxicity, moderate environmental persistence, low to moderate acute toxicity, high repeated dose toxicity, and a low potential for genotoxicity, carcinogenicity, and reproductive/developmental effects.

Photoinduced electron transfer from nucleotides to DNA intercalating viologens. A study by laser-flash photolysis and spectroelectrochemistry.

PubMed

Knapp, C; Lecomte, J P; Mesmaeker, A K; Orellana, G

1996-10-01

Fluorescent DNA-binding N,N'-dialkyl 6-(2-pyridinium)phenanthridinium dications (where dialkyl stands for -(CH2)2-or-(CH2)3-, abbreviated dq2pyp and dq3pyp, respectively) associate with GMP (guanosine-5'-monophosphate) in 0.1-mol l-1, pH 3.5-5.5, phosphate buffer solution to yield 1:1 and 1:2 non-emissive complexes, the formation constants of which range from 197-63 and 19-11 l mol-1, respectively. In addition to the strong static quenching, dynamic deactivation of their excited state occurs at diffusion-controlled rate ki = 5.2 x 10(9) l mol-1 s-1). Illumination of the GMP-containing solutions of the dyes with a 355 nm laser pulse produces a transient, with strong absorbance at 510 and 720 nm for dq2pyp, and 420 and 560 nm for dq3pyp. An identical transient is produced in the presence of ascorbic acid instead of the mononucleotide. By comparison to the electrochemically generated absorption spectra of the monoreduced dyes, the photogenerated transients have been assigned unequivocally to their corresponding radical-cations, formed by electron transfer to the anglet excited state. The back redox reaction between the oxidized quencher and dq2pyp+ proceeds at a rate of 1-2 x 10(9) l mol-1 s-1. The same transient has been observed also for the DNA intercalated viologens; this result, together with the little ability of these dyes to sensitize the formation of singlet dioxygen or to produce superoxide anion, demonstrate that their DNA photocleavaging activity is initiated by an efficient light-induced electron transfer from the nucleobases.

Epoxidation of Geraniol: An Advanced Organic Experiment that Illustrates Asymmetric Synthesis

NASA Astrophysics Data System (ADS)

Bradley, Lynn M.; Springer, Joseph W.; Delate, Gregory M.; Goodman, Andrew

1997-11-01

The Sharpless epoxidation reaction is considered one of the most powerful advances in asymmetric organic synthesis (1). It is a classic example of the use of an asymmetric catalyst to provide an enantiomerically enriched mixture of epoxy alcohols. The procedure typically uses titanium(IV) tetraisopropoxide (Ti(OiPr)4) as a catalyst, a peroxide, and dialkyl tartrates to induce asymmetry in the epoxidation reaction of allylic alcohols. The experiment described in this paper illustrates the principle of asymmetric epoxidation and enables students to determine enantiomeric product ratios using chiral shift reagents and NMR spectroscopy.

Rapid isolation of biomarkers for compound specific radiocarbon dating using high-performance liquid chromatography and flow injection analysis-atmospheric pressure chemical ionisation mass spectrometry.

PubMed

Smittenberg, Rienk H; Hopmans, Ellen C; Schouten, Stefan; Sinninghe Damsté, Jaap S

2002-11-29

Repeated semi-preparative normal-phase HPLC was performed to isolate selected biomarkers from sediment extracts for radiocarbon analysis. Flow injection analysis-mass spectrometry was used for rapid analysis of collected fractions to evaluate the separation procedure, taking only 1 min per fraction. In this way 100-1000 microg of glycerol dialkyl glycerol tetraethers, sterol fractions and chlorophyll-derived phytol were isolated from typically 100 g of marine sediment, i.e., in sufficient quantities for radiocarbon analysis, without significant carbon isotopic fractionation or contamination.

Thermodynamic analysis of vapor-phase epitaxy of CdTe using a metallic Cd source

NASA Astrophysics Data System (ADS)

Iso, Kenji; Murakami, Hisashi; Koukitu, Akinori

2017-07-01

Thermodynamic analysis of CdTe growth using cost-effective metallic Cd and dialkyl telluride was performed. The major vapor species at source zone in equilibrium were gaseous Cd for the group-II precursor, and Te2 and H2Te for the group-VI precursors. The driving force for the CdTe deposition was still positive even at 650 °C. This indicates that CdTe formation from gaseous Cd can proceed thermodynamically. Furthermore, the calculations showed that CdTe decomposes at higher temperature and increasing the II/VI ratio increases the limit of the growth temperature, which coincides with the experimental results.

Asymmetric Additions to Dienes Catalyzed by a Dithiophosphoric Acid

PubMed Central

Shapiro, Nathan D.; Rauniyar, Vivek; Hamilton, Gregory L.; Wu, Jeffrey; Toste, F. Dean

2011-01-01

Chiral Brønsted acids have become an invaluable tool for achieving a variety of asymmetric chemical transformations under catalytic conditions while avoiding the use of toxic and expensive metals1–8. While the catalysts developed so far are remarkably effective at activating polarized functional groups, chemists have not yet been able to use organic Brønsted acids to catalyze highly enantioselective transformations of unactivated carbon-carbon multiple bonds. This deficiency persists despite the fact that racemic acid-catalyzed “Markovnikov” additions to olefins are a well-established part of the chemist’s toolbox. Here we show that chiral dithiophosphoric acids catalyze the intramolecular hydroamination and hydroarylation of dienes and allenes to generate heterocyclic products in exceptional yield and enantiomeric excess. To help rationalize the unique success of this catalytic system, we present a mechanistic hypothesis that involves the addition of the acid catalyst to the diene followed by SN2′ displacement of the resulting dithiophosphate intermediate. Mass spectrometry and deuterium labelling studies are presented in support of the proposed mechanism. The catalysts and concepts revealed in this study should prove applicable to other asymmetric functionalizations of unsaturated systems. PMID:21307938

The Impact of Prenatal Organophosphate Pesticide Exposures on Thai Infant Neurodevelopment

PubMed Central

Kongtip, Pornpimol; Techasaensiri, Benyachalee; Nankongnab, Noppanun; Adams, Jane; Phamonphon, Akkarat; Surach, Anu; Sangprasert, Supha; Thongsuksai, Aree; Srikumpol, Prayoon; Woskie, Susan

2017-01-01

A birth cohort was begun to investigate the levels and sources of pesticide exposure in pregnant women living in Thailand, and to examine the effects of pesticide exposure on infant neurodevelopment at five months of age. Subjects were interviewed using questionnaires regarding their demographic characteristics, educational background, and work and home activities related to pesticide exposures. Spot urine samples were collected at 28 weeks gestation and analyzed by gas chromatography-mass spectrometry to determine maternal metabolite levels of organophosphate pesticides including dimethyl phosphate (DMP); total DEP (diethyl phosphate (DEP), diethyl thiophosphate (DETP), and diethyl dithiophosphate (DEDTP), and total DAP (the sum of all metabolite levels). At five months of age, infant development was evaluated using the Bayley Scales of Infant and Toddler Development-III (Bayley-III). Higher total DEP and total DAP metabolite levels from the mother at 28 weeks’ gestation were significantly associated with reduced motor composite scores on the Bayley-III at five months of age. The total DEP levels were also significantly associated with reduced cognitive composite scores. Prenatal concentrations of maternal urinary metabolites were associated with infant cognitive and motor development. The results of several studies now suggest the need for public health intervention to reduce prenatal pesticide exposures from both agricultural and domestic use. PMID:28554999

Synthesis, spectral and antifungal analysis of diaryldithiophosphates of mono- and dibutyltin(IV): x-ray structure of [{(3,5-CH3)2C6H3O)2PS2}2Sn(nBu)2].

PubMed

Syed, Atiya; Khajuria, Ruchi; Kumar, Sandeep; Jassal, Amanpreet Kaur; Hundal, Maninder S; Pandey, Sushil K

2014-01-01

Diaryldithiophosphate complexes of mono- and dibutyltin(IV) corresponding to [(ArO)(2)PS(2)(n)Sn(nBu)xCl(4-x-n)] (Ar = o-CH(3)C(6)H(4), m-CH(3)C(6)H(4), p-CH(3)C(6)H(4), 4-Cl-3-CH(3)C(6)H(3), (3,5-CH(3))(2)C(6)H(3); n = 1, 2 for x = 1 and n = 2 for x = 2) were successfully isolated and characterized by elemental analyses, IR, multinuclear NMR ((1)H, (13)C, (31)P and (119)Sn) spectroscopy and X-ray analysis. The thermal properties of the complex [(3,5-CH(3))(2)C(6)H(3)O(2)PS(2)](2)Sn(nBu)(2) (12) have been examined by combined DTA/ DTG thermal analyses. Single crystal X-ray analysis of [(3,5-CH(3))(2)C(6)H(3)O(2)PS(2)](2)S(n)(nBu)(2) (12) revealed that two diaryldithiophosphate ions are coordinated to tin atom in an anisobidentate fashion through the sulfur atoms of each dithiophosphate moiety leading to distorted skew-trapezoidal bipyramidal geometry. The antifungal activity depicts that these complexes are active against fungus Penicillium chrysogenium.

Changes in the ratio of tetraether to diether lipids in cattle feces in response to altered dietary ratio of grass silage and concentrates.

PubMed

McCartney, C A; Dewhurst, R J; Bull, I D

2014-09-01

The distinctive membrane lipids of the archaea can contain a wide range of chemical structures. The membrane lipid composition of ruminal methanogenic archaea has not yet been characterized. In this study, we analyzed proportions of the core archaeal membrane lipids dialkyl glycerol diethers (DGDG) and glycerol dialkyl glycerol tetraether (GDGT). We analyzed the feces of beef steers consuming diets that promoted differences in ruminal conditions that were either favorable (i.e., grass silage) or challenging (i.e., concentrates) for the methanogenic archaea. There was significantly less total ether lipid in the feces of cattle consuming the concentrate diet in comparison to the grass silage diet (97 vs. 218 mg/kg DM, respectively), reflecting the inhibitory effect of dietary concentrate on methanogens. Additionally, the proportion of fecal ether lipids as GDGT was much greater in feces from cattle consuming the concentrate diet than in feces from cattle fed grass silage (90% vs. 67% GDGT). A possible explanation for this adaptation is that membrane lipids composited of GDGT lipids are less permeable to protons, thereby protecting the methanogens against low ruminal pH and helping to maintain the chemiosmotic potential (which is important for ATP production, methanogenesis, and growth). The greater proportion of fecal ether lipids as GDGT may reflect adaptation of membrane lipids within the same species, a shift toward methanogens that have a greater proportion of GDGT (e.g., Thermoplasmata), or both. The effect of ruminal environment on membrane composition means that it will be important to consider the production of both DGDG and GDGT lipids when developing a proxy for methanogenesis.

Influence of water availability in the distributions of branched glycerol dialkyl glycerol tetraether in soils of the Iberian Peninsula

NASA Astrophysics Data System (ADS)

Menges, J.; Huguet, C.; Alcañiz, J. M.; Fietz, S.; Sachse, D.; Rosell-Melé, A.

2014-05-01

The combined application of the MBT (degree of methylation) and CBT (degree of cyclization) indices, based on the distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in soils, has been proposed as a paleoproxy to estimate mean annual temperature (MAT). CBT quantifies the degree of cyclization of brGDGTs and relates to soil pH. MBT and the simplified version MBT' quantify the degree of methylation of brGDGTs and relate to MAT and soil pH. However, other factors such as soil water availability have also been suggested to influence MBT' and possibly restrict the combined application of the MBT' and CBT indices as a paleotemperature proxy. To assess the effect of hydrological conditions on MBT' and CBT, a set of 23 Iberian Peninsula soil samples, covering a MAT range from 10 to 18 °C and a mean annual precipitation (MAP) range of 405 mm to 1455 mm, was analyzed. We found that the CBT was indeed significantly correlated with soil pH in our sample set. In contrast, MBT' was not correlated with MAT but had a significant correlation with the aridity index (AI), a parameter related to water availability in soils. The AI can explain 50% of the variation of the MBT', and 70% of the residuals of MAT estimated with the MBT/CBT proxy as compared to instrumentally measured MAT. We propose that, in arid settings, where water may be an ecologically limiting factor, MBT' is influenced by hydrological conditions rather than temperature. Thus, our results suggest that the combination of MBT' and CBT indices should be applied with caution in paleotemperature reconstructions in soils from dry subhumid to hyperarid environments.

Evidence of moisture control on the methylation of branched glycerol dialkyl glycerol tetraethers in semi-arid and arid soils

NASA Astrophysics Data System (ADS)

Dang, Xinyue; Yang, Huan; Naafs, B. David A.; Pancost, Richard D.; Xie, Shucheng

2016-09-01

The distribution of bacterial branched glycerol dialkyl glycerol tetraethers (brGDGTs) is influenced by growth temperature and pH. This results in the widespread application of the brGDGT-based MBT(‧)/CBT proxy (MBT - methylation of branched tetraethers, CBT - cyclization of branched tetraethers) in terrestrial paleo-environmental reconstructions. Recently, it was shown that the amount of precipitation could also have an impact on CBT, as well as the abundance of brGDGTs relative to that of archaeal isoprenoidal (iso)GDGTs (Ri/b) and the absolute abundance of brGDGTs, potentially complicating the use of MBT/CBT as paleothermometer. However, the full influence of hydrology, and in particular soil water content (SWC), on GDGT distributions remains unclear. Here we investigated variations in the GDGT distribution across a SWC gradient (0-61%) around Qinghai Lake in the Tibetan Plateau, an arid to semiarid region in China. Our results demonstrate that SWC affects the brGDGT distribution. In particular, we show that SWC has a clear impact on the degree of methylation of C6-methylated brGDGTs, whereas C5-methylated brGDGTs are more impacted by temperature. This results in a combined SWC and temperature control on MBT‧. In this context we propose a diagnostic parameter, the IR6ME (relative abundance of C6-methylated GDGTs) index, to evaluate the applicability of brGDGT-based paleotemperature reconstructions. Using the global dataset, expanded with our own data, MBT‧ has a significant correlation with mean annual air temperature when IR6ME < 0.5, allowing for the use of MBT‧/CBT as temperature proxy. However, MBT‧ has a significant correlation with mean annual precipitation (i.e., a substantial reflection of SWC impact) when IR6ME > 0.5, implying that MBT‧ may respond to hydrological change in these regions and can be used as a proxy for MAP.

Aib and iva in the biosphere: neither rare nor necessarily extraterrestrial.

PubMed

Brückner, Hans; Becker, Dieter; Gams, Walter; Degenkolb, Thomas

2009-01-01

Fourty-nine species and strains of filamentous fungi of the genera Acremonium, Bionectria, Clonostachys, Emericellopsis, Hypocrea/Trichoderma, Lecythophora, Monocillium, Nectriopsis, Niesslia, Tolypocladium, and Wardomyces, deposited with the culture collection of the Centraalbureau voor Schimmelcultures (CBS) in Utrecht, The Netherlands, were grown on nutrient agar plates. Organic extracts of mycelia were analyzed after acidic total hydrolysis and derivatization by GC/SIM-MS on Chirasil-L-Val for the presence of Aib (=alpha-aminoisobutyric acid, 2-methylalanine) and DL-Iva (=isovaline, 2-ethylalanine). In 37 of the hydrolysates, Aib was detected, and in several of them D-Iva or mixtures of D- and L-Iva. Non-proteinogenic Aib, in particular, is a highly specific marker for a distinctive group of fungal polypeptides named peptaibols or, comprehensively, peptaibiotics, i.e., peptides containing Aib and displaying (anti)biotic activities. The biotic synthesis of these amino acids by filamentous fungi contradicts the still widespread belief that alpha,alpha-dialkyl-alpha-amino acids do not or rarely occur in the biosphere and, if detected, are of extraterrestrial origin. The abundant production of peptaibiotics by cosmopolitan species of microfungi has also to be considered in the discussion on the occurrence of Aib and Iva in ancient and recent sediments. The detection of trace amounts of Aib in ice samples of Antarctica that are devoid of meteorites might also be related to the presence of Aib-producing microorganisms, being either indigenous psychrophiles, or being transported and localized by mechanisms related to bioaerosols and cryoconites. The presence of microfungi being capable of producing alpha,alpha-dialkyl alpha-amino acids in terrestrial samples, and possible contamination of extraterrestrial materials are pointed out to be of relevance for the reliable interpretation of cosmogeochemical data.

The partition and transport behavior of cytotoxic ionic liquids (ILs) through the DPPC bilayer: Insights from molecular dynamics simulation.

PubMed

Ganjali Koli, Mokhtar; Azizi, Khaled

A molecular dynamics (MD) simulation with atomistic details was performed to examine the partitioning and transport behavior of moderately cytotoxic ionic liquids (ILs), namely choline bis(2-ethylhexyl) phosphate (CBEH), choline bis(2,4,4-trimethylpentyl) phosphinate (CTMP) and choline O,O-diethyl dithiophosphate (CDEP) in a fully hydrated dipalmitoylphosphatidylcholine (DPPC) bilayer in the fluid phase at 323 K. The structure of ILs was so selected to understand if the role of dipole and dispersion forces in the ILs distribution in the membrane can be possible. Several analyses including mass density, electrostatic potential, order parameter, diffusion coefficients and hydrogen bond formation, was carried out to determine the precise location of the anionic species inside the membrane. Moreover, the potential of the mean force (PMF) method was used to calculate free energy profile for transferring anionic species from the DPPC membrane into the bulk water. While less cytotoxic DEP is located within the bulk water, more cytotoxic TMP and BEH ILs were found to remain in the membrane and the energy barrier for crossing through the bilayer center of BEH was higher. Various ILs have no significant effect on P-N vector. The thickness of lipid bilayer decreased in all systems comprising ILs, while area per lipid increased.

Investigation of isovaline enantiomeric excesses in CM meteorites using liquid chromatography time of flight mass spectrometry

NASA Technical Reports Server (NTRS)

Glavin, Daniel P.; Dworkin, Jason P.

2003-01-01

The enantiomeric abundances of the alpha-dialkyl amino acid isovaline were measured in the CM2 meteorites Murchison and LEW 90500 using a new liquid chromatography-time of flight-mass spectrometry (LC-ToF-MS) technique coupled with OPA/NAC derivatization and UV fluorescence detection. Previous analyses of Murchison have shown that L-enantiomeric excesses of isovaline range from 0 to 15.2% with significant variation between meteorite fragments [1]. For this study, hot water extracts of interior fragments (> 2 cm from fusion crust) of the Murchison (USNM 6650.2, mass 6 g) and LEW 90500 (split 69, parent 1, mass 5 g) carbonaceous meteorites were analyzed. Enantiomeric excesses were measured using the single ion LC-ToF-MS trace for the OPA/NAC derivative of isovaline at d z 393.15 (Fig. 1). L-isovaline excesses in these meteorite samples ranged from 18.9 to 20.5% for Murchison and -0.5 to 3.0% for LEW 90500. The measured values for Murchison are the largest enantiomeric excesses for isovaline reported to date. The enantiomeric excesses of L-isovaline cannot be the result of interference from other C5 amino acid isomers present in the meteorites or terrestrial contamination from the landing site environments. The L-isovaline excesses in Murchison are inconsistent with the synthesis of all of the isovaline by the Strecker-cyanohydrin pathway on the CM meteorite parent body. The mechanism(s) for the formation of the enantiomeric asymmetry in isovaline in Murchison are currently unknown and it is not clear how the asymmetry of alpha-dialkyl amino acids could be transferred to the a-hydrogen protein amino acids common in all life on Earth today.

Distributions of glycerol dialkyl glycerol tetraethers in surface soils of Qinghai-Tibetan Plateau: implications of GDGT-based proxies in cold and dry regions

NASA Astrophysics Data System (ADS)

Ding, S.; Xu, Y.; Wang, Y.; He, Y.; Hou, J.; Chen, L.; He, J.-S.

2015-01-01

The methylation index of branched tetraethers (MBT) and cyclization ratio of branched tetraethers (CBT) based on the distribution of bacteria-derived branched glycerol dialkyl glycerol tetraethers (bGDGTs) are useful proxies for the reconstruction of continental paleotemperature and soil pH. Several calibrations of the MBT-CBT index have been proposed based on global and regional soils and lake sediments. However, little is known about the distribution and applicability of GDGTs proxies in the Qinghai-Tibet Plateau (QTP), a critical region of the global climate system. Here, we investigated 33 surface soils covering a large area of the QTP. Redundancy analysis showed that soil pH was the most important factor affecting GDGT distributions, followed by mean annual precipitation (MAP) and mean annual air temperature (MAT). The branched-isoprenoid tetraether (BIT) index, an indicator for estimation of soil organic matter in aquatic environments, varied from 0.48 to 1 and negatively correlated with soil pH (r2 = 0.38), suggesting that the BIT index should be used with caution in the QTP. A transfer function of the CBT index-soil pH was established to estimate paleo-soil pH in the QTP: pH = 8.33-1.43 × CBT (r2 = 0.80, RMSE = 0.27 pH unit). The local calibration of MBT-CBT index presented a weak, still significant correlation with MAT (r2 = 0.36) mainly owing to the additional influence of MAP (r2 = 0.50). Combining our data with previously reported GDGTs for Chinese soils resulted in a new calibration of MBT/CBT-MAT: MAT = 2.68+26.14 × MBT-3.37 × CBT (r2 = 0.73; RMSE = 4.2 °C, n = 164). The correlation coefficient and residual error of this new transfer function is comparable with global calibrations, suggesting that MBT-CBT paleotemperature proxy is still valid in the QTP.

Potent antiprotozoal activity of a novel semi-synthetic berberine derivative.

PubMed

Bahar, Mark; Deng, Ye; Zhu, Xiaohua; He, Shanshan; Pandharkar, Trupti; Drew, Mark E; Navarro-Vázquez, Armando; Anklin, Clemens; Gil, Roberto R; Doskotch, Raymond W; Werbovetz, Karl A; Kinghorn, A Douglas

2011-05-01

Treatment of diseases such as African sleeping sickness and leishmaniasis often depends on relatively expensive or toxic drugs, and resistance to current chemotherapeutics is an issue in treating these diseases and malaria. In this study, a new semi-synthetic berberine analogue, 5,6-didehydro-8,8-diethyl-13-oxodihydroberberine chloride (1), showed nanomolar level potency against in vitro models of leishmaniasis, malaria, and trypanosomiasis as well as activity in an in vivo visceral leishmaniasis model. Since the synthetic starting material, berberine hemisulfate, is inexpensive, 8,8-dialkyl-substituted analogues of berberine may lead to a new class of affordable antiprotozoal compounds. Copyright © 2011. Published by Elsevier Ltd.

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

PubMed Central

Perosa, Alvise; Guidi, Sandro; Cattelan, Lisa

2016-01-01

Summary The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, specifically for the conversion of nontoxic compounds such as dialkyl carbonates to both linear mono-transesterification products or alkylene carbonates. An introductory survey compares pros and cons of classic catalysts based on both acidic and basic systems, to ionic liquids. Then, innovative green syntheses of task-specific ILs and their representative applications are introduced to detail the efficiency and highly selective outcome of ILs-catalyzed transesterification reactions. A mechanistic hypothesis is discussed by the concept of cooperative catalysis based on the dual (electrophilic/nucleophilic) activation of reactants. PMID:27829898

Enantiomeric Recognition of Organic Ammonium Salts by Chiral Dialkyl-, Dialkenyl-, and Tetramethyl-Substituted Pyridino-18-Crown-6 and Tetramethyl- Substituted Bis-Pyridino-18-Crown-6 Ligands: Comparison of Temperature-Dependent 1H NMR and Empirical Force Field Techniques

DTIC Science & Technology

1990-04-18

COVERED 14, DATE OF REPORT (Year. Month, Day) 15. PAGE COUNT Interim FROM _ _ TO April 18, 1990 16. SUPPLEMENTARY NOTATION 17 , COSATI CODES 18. SUBJECT...to epoxide 17 was carried out ,o by using the method of Koppenhoefer and Schurig.241-2 Our epoxides 17 where R was isopropyl, isobutyl, and Scheme i... 17 with diethylene glycol and a catalytic amount of sodium was carried out as reported for the preparation of the chiral dimethyl- tetraethylene glycol

Enzyme activity in dialkyl phosphate ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, M.F.; Dunn, J.; Li, L.-L.

2011-12-01

The activity of four metagenomic enzymes and an enzyme cloned from the straw mushroom, Volvariellavolvacea were studied in the following ionic liquids, 1,3-dimethylimidazolium dimethyl phosphate, [mmim][dmp], 1-ethyl-3-methylimidazolium dimethyl phosphate, [emim][dmp], 1-ethyl-3-methylimidazolium diethyl phosphate, [emim][dep] and 1-ethyl-3-methylimidazolium acetate, [emim][OAc]. Activity was determined by analyzing the hydrolysis of para-nitrobenzene carbohydrate derivatives. In general, the enzymes were most active in the dimethyl phosphate ionic liquids, followed by acetate. Generally speaking, activity decreased sharply for concentrations of [emim][dep] above 10% v/v, while the other ionic liquids showed less impact on activity up to 20% v/v.

Preparation of 4-amino-2,4-dioxobutanoic acid

DOEpatents

Unkefer, Pat J.; Martinez, Rodolfo A.; Glass, David R.

2016-03-22

A process for synthesizing 4-amino-2,4-dioxobutanoate involves reacting a dialkyl oxalate with an alkoxide in ethanol to form a reaction mixture, and afterward adding an alkyl cyano acetate to the reaction mixture and allowing a reaction to proceed under conditions suitable to form a first reaction product of the formula diethyl 2-cyano-3-hydroxy-butenedioate, and then isolating the diethyl 2-cyano-3-hydroxy-butenedioate, and afterward reacting the diethyl-2-cyano-3-hydroxy-butenedioate with an aqueous hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoate. The 4-amino-2,4-dioxobutanoate may be acidified into 4-amino-2,4-dioxobutanoic acid.

Spatial distributions of core and intact glycerol dialkyl glycerol tetraethers (GDGTs) in the Columbia River basin, Washington: Insights into origin and implications for the BIT index

NASA Astrophysics Data System (ADS)

French, David W.; Huguet, Carme; Wakeham, Stuart; Turich, Courtney; Carlson, Laura T.; Ingalls, Anitra E.

2015-04-01

Branched and isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs) are used to reconstruct carbon flow from terrestrial landscapes to the ocean in a proxy called the branched vs isoprenoid tetraether index, or BIT Index. The index is based on analysis of core GDGTs from non-living material that originate from the cell membranes of bacteria living in soils and archaea living primarily in the marine environment. However, uncertainty in the identity and location of branched GDGTs (BrGDGTs) producing organisms and the likely production of isoprenoid GDGTs (IsoGDGTs) in terrestrial environments hinders interpretation of the BIT Index. Since BrGDGTs remain our only tool to study BrGDGT producing organisms, it is particularly important to use the intact form of BrGDGTs, present in living cells, to infer organism distributions. In situ production within riverine, lacustrine, and marine environments is currently thought to be possible, yet few measures of intact BrGDGTs (I-BrGDGTs) are available to confirm this. Here we assess the spatial distribution of both core and intact GDGTs throughout the Columbia River basin and nearby areas in Washington and Oregon in order to elucidate source environments for these lipids. The presence of I-BrGDGTs throughout the studied soils, rivers and estuaries suggests in situ production across the continuum from soil to marine environments. Likewise, intact crenarchaeol, the marine endmember isoprenoidal GDGT used in the BIT index, was present in all samples. Widespread production of each GDGT class along terrestrial carbon transport paths likely alters the BIT Index along this continuum. The core to intact GDGT ratios and the weak correlation between I-GDGT derived BIT values and carbon isotope signatures suggest a mixture of allocthonous and autochthonous sources of GDGTs in riverine and marine environments. Our findings highlight the need for further work into the provenance of GDGTs to improve the BIT index and other environmental proxies that rely on these compounds.

Regioselective Formation of (E)-β-Vinylstannanes with a Topologically Controlled Molybdenum-Based Alkyne Hydrostannation Catalyst.

PubMed

Mandla, Kyle A; Moore, Curtis E; Rheingold, Arnold L; Figueroa, Joshua S

2018-06-04

The regioselective formation of (E)-β-vinylstannanes has been a long-standing challenge in transition-metal-catalyzed alkyne hydrostannation. Herein, we report a well-defined molybdenum-based system featuring two encumbering m-terphenyl isocyanides that reliably and efficiently delivers (E)-β-vinylstannanes from a range of terminal and internal alkynes with high regioselectivity. The system is particularly effective for aryl alkynes and can discriminate between alkyl chains of low steric hindrance in unsymmetrically substituted dialkyl alkynes. Catalytic hydrostannation with this system is also characterized by an electronic effect that leads to a decrease in regioselectivity when electron-withdrawing groups are present on the alkyne substrate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactivities of some thiol collectors and their interactions with Ag (+1) ion by molecular modeling

NASA Astrophysics Data System (ADS)

Yekeler, Hulya; Yekeler, Meftuni

2004-09-01

The most commonly used collectors for sulfide minerals in the mining industry are the thiol collectors for the recovery of these minerals from their associated gangues by froth flotation. For this reason, a great deal of attention has been paid to understand the attachment mechanism of thiol collectors to metal sulfide surfaces. The density functional theory (DFT) calculations at the B3LYP/3-21G* and B3LYP/6-31++G** levels were employed to propose the flotation responses of these thiol collectors, namely, diethyl dithiocarbamate, ethyl dithiocarbamate, ethyl dithiocarbonate, ethyl trithiocarbonate and ethyl dithiophosphate ions, and to study the interaction energies of these collectors with Ag (+1) ion in connection to acanthite (Ag 2S) mineral. The calculated interaction energies, Δ E, were interpreted in terms of the highest occupied molecular orbital (HOMO) energies of the isolated collector ions. The results show that the HOMOs are strongly localized to the sulfur atoms and the HOMO energies can be used as a reactivity descriptor for the flotation ability of the thiol collectors. Using the HOMO and Δ E energies, the reactivity order of the collectors is found to be (C 2H 5) 2NCS 2- > C 2H 5NHCS 2- > C 2H 5OCS 2- > C 2H 5SCS 2- > (C 2H 5O)(OH)PS 2-. The theoretically obtained results are in good agreement with the experimental data reported.

Carbodithioic acid esters of fluoxetine, a novel class of dual-function spermicides.

PubMed

Kiran Kumar, S T V S; Kumar, Lalit; Sharma, Vishnu L; Jain, Ashish; Jain, Rajeev K; Maikhuri, Jagdamba P; Kumar, Manish; Shukla, Praveen K; Gupta, Gopal

2008-10-01

Carbodithioic acid esters of fluoxetine have been prepared by replacing the methylamino function in aminopropane chain with carbodithioic acid ester group and by adding various S-2-hydroxypropyl ester of dialkyl carbodithioic acid at 3-methylamino group. Some of these compounds showed spermicidal, antifungal and anti-Trichomonas activities. The study revealed that incorporation of carbodithioic acid residue directly into fluoxetine structure leads to compounds with better antifungal and anti-Trichomonas activities, and N-methyl-[3-phenyl-3-(4-trifluoromethyl-phenoxy)-propyl]carbodithioic acid S-(2-pyrrolidino-ethyl) ester (14) has shown better profile than both fluoxetine and nonoxynol-9. Further lead optimization may yield a potent dual-function spermicide.

Origin of lipid biomarkers in mud volcanoes from the Alboran Sea, western Mediterranean

NASA Astrophysics Data System (ADS)

López-Rodríguez, C.; Stadnitskaia, A.; De Lange, G. J.; Martínez-Ruíz, F.; Comas, M.

2014-06-01

Mud volcanoes (MVs) are the most prominent indicators of active methane/hydrocarbon venting at the seafloor on both passive and active continental margins. Their occurrence in the western Mediterranean is patent at the West Alboran Basin, where numerous MVs develop overlaying a major sedimentary depocentre containing overpressured shales. Although some of these MVs have been studied, the detailed biogeochemistry of expelled mud so far has not been examined in detail. This work provides the first results on the composition and origin of organic matter, anaerobic oxidation of methane (AOM) processes and general characteristics on MV dynamics using lipid biomarkers as the main tool. Lipid biomarker analysis was performed on MV expelled material (mud breccias) and interbedded hemipelagic sediments from Perejil, Kalinin and Schneider's Heart MVs located in the northwest margin of the Alboran Sea. The n alkane distributions and n alkane-derived indices (CPI and ACL), in combination with the epimerization degree of hopanes (22S/(22S+22R)) indicate that all studied mud breccia have a similar biomarker composition consisting of mainly thermally immature organic matter with an admixture of petroleum-derived compounds. This concordant composition indicates that common source strata must feed all three studied MVs. The past or present AOM activity was established using lipid biomarkers specific for anaerobic methanotrophic archaea (irregular isoprenoids and dialkyl glycerol diethers) and the depleted carbon isotope composition (δ13C) of crocetane/phytane. The presence of these lipid biomarkers, together with the low amounts of detected glycerol dialkyl glycerol tetraethers, is consistent with the dominance of anaerobic methanotrophs of the ANME-2 over ANME-1, at least in mud breccia from Perejil MVs. In contrast, the scarce presence or lack of these AOM-related lipid biomarkers in sediments from Kalinin and Schneider's Heart MVs, suggests that no recent active methane seepage has occurred at these sites. Moreover, the observed methane concentrations support the current activity of Perejil MV, and the very low methane seepage activity in Kalinin and Schneider's Heart MVs.

Evaluating Spatial Heterogeneity and Environmental Variability Inferred from Branched Glycerol Dialkyl Glycerol Tetraethers (GDGTs) Distribution in Soils from Valles Caldera, New Mexic

NASA Astrophysics Data System (ADS)

Contreras Quintana, S. H.; Werne, J. P.; Brown, E. T.; Halbur, J.; Sinninghe Damsté, , J.; Schouten, S.; Correa-Metrio, A.; Fawcett, P. J.

2014-12-01

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are recently discovered bacterial membrane lipids, ubiquitously present in peat bogs and soils, as well as in rivers, lakes and lake sediments. Their distribution appears to be controlled mainly by soil pH and annual mean air temperature (MAT) and they have been increasingly used as paleoclimate proxies in sedimentary records. In order to validate their application as paleoclimate proxies, it is essential evaluate the influence of small scale environmental variability on their distribution. Initial application of the original soil-based branched GDGT distribution proxy to lacustrine sediments from Valles Caldera, New Mexico (NM) was promising, producing a viable temperature record spanning two glacial/interglacial cycles. In this study, we assess the influence of analytical and spatial soil heterogeneity on the concentration and distribution of 9 branched GDGTs in soils from Valles Caldera, and show how this variability is propagated to MAT and pH estimates using multiple soil-based branched GDGT transfer functions. Our results show that significant differences in the abundance and distribution of branched GDGTs in soil can be observed even within a small area such as Valles Caldera. Although the original MBT-CBT calibration appears to give robust MAT estimates and the newest calibration provides pH estimates in better agreement with modern local soils in Valles Caldera, the environmental heterogeneity (e.g. vegetation type and soil moisture) appears to affect the precision of MAT and pH estimates. Furthermore, the heterogeneity of soils leads to significant variability among samples taken even from within a square meter. While such soil heterogeneity is not unknown (and is typically controlled for by combining multiple samples), this study quantifies heterogeneity relative to branched GDGT-based proxies for the first time, indicating that care must be taken with samples from heterogeneous soils in MAT and pH reconstructions.

Plio-Pleistocene Temperature Variability in the Terrestrial Arctic: Insights from Branched Glycerol Dialkyl Glycerol Tetraethers

NASA Astrophysics Data System (ADS)

Castañeda, I. S.; Salacup, J.; de Wet, G.; Habicht, M. H.; Keisling, B. A.; Phu, V.; Johnson, J.; Lukas, S.; Lyons, N.; Brigham-Grette, J.

2014-12-01

Drill coring at Lake El'gygytgyn (Far East Russia) in 2009 retrieved a 3.6 Ma long sediment core, which is presently the oldest continuous sedimentary record available from the terrestrial Arctic. This unique Plio-Pleistocene record allows for the response of the Arctic to global climate events under a variety of different boundary conditions to be examined. Here we present results of ongoing organic geochemical analyses of Lake El'gygytgyn sediments focusing on the mid-Pliocene warm period, the Plio-Pleistocene transition, the mid-Brunhes transition, and warm Pleistocene interglacial periods including Marine Isotope Stages (MIS) 5, 9, 11, 19 and 31. Despite the ultra-oligotrophic nature of Lake El'gygytgyn and the generally low sedimentary total organic carbon (TOC) content, we find abundant branched glycerol dialkyl glycerol tetraethers (brGDGTs) throughout the entire record and use the methylation and cyclization indices of branched tetraethers (MBT and CBT, respectively) to reconstruct past temperature (Weijers et al., 2007). We hypothesize that the majority of brGDGTs are produced in the lake during the brief summer period of ice free conditions and that MBT/CBT likely reflects a warm season temperature. Trends noted in the MBT/CBT record are in close agreement with pollen-based temperature estimates throughout the entire core. For example, we note a dramatic ~6°C cooling associated with the mid-Pliocene M2 event and thus far MIS 31 has emerged as the warmest period at Lake El'gygytgyn during the past ~ 1 Ma, corroborating the pollen data. Interestingly, a number of abrupt and relatively short-lived cooling events of 2 to 4°C are noted within several of the particularly warm interglacial periods (e.g. MIS 5e, MIS 11 and MIS 31) and are the subject of ongoing investigation. Overall, application of the MBT/CBT paleothermometer to Lake El'gygytgyn sediments is a highly promising technique for generating a Plio-Pleistocene temperature record from the continental Arctic although a site specific calibration is required before absolute temperature can be reconstructed with confidence from brGDGTs.

Lipidic Carbo-benzenes: Molecular Probes of Magnetic Anisotropy and Stacking Properties of α-Graphyne.

PubMed

Zhu, Chongwei; Rives, Arnaud; Duhayon, Carine; Maraval, Valérie; Chauvin, Remi

2017-01-20

Solubilization of the C 18 fundamental circuit of α-graphyne has been envisaged by decoration with aliphatic chains R = n-C n H 2n+1 . The synthesis and characterization of p-dialkyl-tetraphenyl-carbo-benzenes (n = 2, 8, 14, 20) are thus presented and compared to the monoalkyl series produced concomitantly. In both series, a dramatic enhancement of solubility in organic solvents (CH 2 Cl 2 , CHCl 3 ) is observed for n ≥ 8, and in the dialkyl series, the melting-decomposition temperature of the solid products is shown to decrease linearly from 208 °C for n = 2 to 149 °C for n = 20. Fluoroalkyl analogues with R = n-C 8 H 4 F 13 are also described. The products display classical UV-vis electronic spectra of carbo-benzenes in solution (λ max = 445.5 ± 1 nm, ε ≈ 200 000 L·mol -1 ·cm -1 ). They are also characterized by UV-vis absorption in the solid state, which is found to be correlated with the color and crystal packing. The methylene groups of R provide an experimental probe of the magnetic anisotropy and aromaticity of the C 18 ring through the progressive NMR shielding of the 1 H nuclei from ca. 4.70 to 1.25 ppm going away from the border of the ring (as far as 8 Å away). All alkyl-carbo-benzenes were also found to be highly crystalline. Seven of them have been characterized by X-ray diffraction analysis and the C 18 columnar packing compared in a systematic manner. Crystals of the diethyl and bistetradecyl derivatives, containing no solvent molecule, provided the first examples of direct π-stacking of carbo-benzene rings, with inter-ring distances very close to calculated interlayer distances in AB and ABC α-graphityne (3.255 and 3.206 Å vs 3.266 and 3.201 Å, respectively).

Wide distribution of autochthonous branched glycerol dialkyl glycerol tetraethers (bGDGTs) in U.S. Great Basin hot springs

PubMed Central

Hedlund, Brian P.; Paraiso, Julienne J.; Williams, Amanda J.; Huang, Qiuyuan; Wei, Yuli; Dijkstra, Paul; Hungate, Bruce A.; Dong, Hailiang; Zhang, Chuanlun L.

2013-01-01

Branched glycerol dialkyl glycerol tetraethers (bGDGTs) are membrane-spanning lipids that likely stabilize membranes of some bacteria. Although bGDGTs have been reported previously in certain geothermal environments, it has been suggested that they may derive from surrounding soils since bGDGTs are known to be produced by soil bacteria. To test the hypothesis that bGDGTs can be produced by thermophiles in geothermal environments, we examined the distribution and abundance of bGDGTs, along with extensive geochemical data, in 40 sediment and mat samples collected from geothermal systems in the U.S. Great Basin (temperature: 31–95°C; pH: 6.8–10.7). bGDGTs were found in 38 out of 40 samples at concentrations up to 824 ng/g sample dry mass and comprised up to 99.5% of total GDGTs (branched plus isoprenoidal). The wide distribution of bGDGTs in hot springs, strong correlation between core and polar lipid abundances, distinctness of bGDGT profiles compared to nearby soils, and higher concentration of bGDGTs in hot springs compared to nearby soils provided evidence of in situ production, particularly for the minimally methylated bGDGTs I, Ib, and Ic. Polar bGDGTs were found almost exclusively in samples ≤70°C and the absolute abundance of polar bGDGTs correlated negatively with properties of chemically reduced, high temperature spring sources (temperature, H2S/HS−) and positively with properties of oxygenated, low temperature sites (O2, NO−3). Two-way cluster analysis and nonmetric multidimensional scaling based on relative abundance of polar bGDGTs supported these relationships and showed a negative relationship between the degree of methylation and temperature, suggesting a higher abundance for minimally methylated bGDGTs at high temperature. This study presents evidence of the widespread production of bGDGTs in mats and sediments of natural geothermal springs in the U.S. Great Basin, especially in oxygenated, low-temperature sites (≤70°C). PMID:23964271

Reconstructing Late Pleistocene air temperature variability based on branched GDGTs in the sedimentary record of Llangorse Lake (Wales)

NASA Astrophysics Data System (ADS)

Maas, David; Hoek, Wim; Peterse, Francien; Akkerman, Keechy; Macleod, Alison; Palmer, Adrian; Lowe, John

2015-04-01

This study aims to provide a temperature reconstruction of the Lateglacial sediments of Llangorse Lake. A new temperature proxy is used, based on the occurrence of different membrane lipids of soil bacteria (de Jonge et al., 2014). Application of this proxy on lacustrine environments is difficult because of in situ (water column) production and co-elution of isomers. Pollen analysis provides a palynological record that can be used for biostratigraphical correlation to other records. Llangorse Lake lies in a glacial basin just northeast of the Brecon Beacons in Powys, South Wales. The lake is located upstream in the Afon Llynfi valley, at the edge of the watershed of the River Wye. The lake consists of two semi-separated basins with a maximum water depth of 7.5 m, arranged in an L-shape with a surface area of roughly 1.5 km2. Previous studies have focused on the Holocene development of the lake and its surrounding environment (Jones et al., 1985). This study focuses on the deglacial record that appeared to be present in the basal part of the sequence. The lake was cored in the September, 2014 with a manual operated 3 m piston corer from a small coring platform. Overlapping cores were taken to form a continuous 12 m core, spanning the Holocene and the Lateglacial sediments. Six adjacent Lateglacial core segments from the southern basin of Llangorse lake were scanned for their major element composition using XRF scanning at 5 mm resolution to discern changes in sediment origin. Furthermore, loss on ignition (LOI) analysis was used to determine the changes in organic content of the sediments. Subsamples of the Lateglacial sedimentary record were analyzed for the occurrence of different bacterial membrane lipids (brGDGTs: branched glycerol dialkyl glycerol tetraethers) by means of HPLC-MS (high performance liquid chromatography and mass spectrometry) using two silica columns to achieve proper separation of isomers (de Jonge et al., 2013). Air temperatures are reconstructed using a multiple linear regression index based on the relative abundance of the brGDGTs. This allows for the quantification of the temperature fluctuation in the events leading up to the Holocene warming, especially the Interstadial (GI-1) warming, subsequent Stadial (GS-1) cooling and eventual transition into the Interglacial period. References: Jones, R., Benson-Evans, K. and Chambers, F.M. (1985) Human influence upon sedimentation in Llangorse Lake, Wales, Earth Surface Processes and Landforms, Vol 10, p 227-235 De Jonge, C., Hopmans, E., Zell, C.I., Kim, J-H., Schouten, S. and Sinninghe-Damsté, J. (2014) Occurrence and abundance of 6-methyl branched glycerol dialkyl glycerol tetraethers in soils: Implications for palaeoclimate reconstruction, Geochimica et Cosmochimica Acta, Vol 141, p 97-112 De Jonge C., Hopmans E. C., Stadnitskaia A., Rijpstra W. I. C., Hofland R., Tegelaar E. and Sinninghe-Damste, J.S. (2013) Identification of novel penta- and hexamethylated branched glycerol dialkyl glycerol tetraethers in peat using HPLC-MS2, GC-MS and GC-SMB-MS. Organic Geochemistry, Vol 54, p 78-82.

Feasibility study for a secondary Na/S battery

NASA Technical Reports Server (NTRS)

Abraham, K. M.; Schiff, R.; Brummer, S. B.

1979-01-01

The feasibility of a moderate temperature Na battery was studied. This battery is to operate at a temperature in the range of 100-150 C. Two kinds of cathode were investigated: (1) a soluble S cathode consisting of a solution of Na2Sn in an organic solvent and (2) an insoluble S cathode consisting of a transition metal dichalcogenide in contact with a Na(+)ion conducting electrolyte. Four amide solvents, dimethyl acetamide, diethyl acetamide, N-methyl acetamide and acetamide, were investigated as possible solvents for the soluble S cathode. Results of stability and electrochemical studies using these solvents are presented. The dialkyl substituted amides were found to be superior. Although the alcohol 1,3-cyclohexanediol was found to be stable in the presence of Na2Sn at 130 C, its Na2Sn solutions did not appear to have suitable electrochemical properties.

High-temperature resins

NASA Technical Reports Server (NTRS)

Serafini, T. T.

1982-01-01

The basic chemistry, cure processes, properties, and applications of high temperature resins known as polyimides are surveyed. Condensation aromatic polymides are prepared by reacting aromatic diamines with aromatic dianhydrides, aromatic tetracarboxylic acids, or with dialkyl esters of aromatic tetracarboxylic acids, depending on the intended end use. The first is for coatings or films while the latter two are more suitable for polyimide matrix resins. Prepreg solutions are made by dissolving reactants in an aprotic solvent, and advances in the addition of a diamine on the double bond and radical polymerization of the double bond are noted to have yielded a final cure product with void-free characteristics. Attention is given to properties of the Skybond, Pyralin, and NR-150B polyimide prepreg materials and characteristics of aging in the NP-150 polyimides. Finally, features of the NASA-developed PMR polyimides are reviewed.

Protocol for Future Amino Acid Analyses of Samples Returned by the Stardust Mission

NASA Technical Reports Server (NTRS)

Glavin, D. P.; Doty, J. H., III; Matrajt, G.; Dworkin, J. P.

2006-01-01

We have demonstrated that LC-ToF-MS coupled with UV fluorescence detection is a powerful tool for the detection of amino acids in meteorite extracts. Using this new analytical technique we were able to identify the extraterrestrial amino acid AIB extracted from fifteen 20 micron sized Murchison meteorite grains. We found that the amino acid contamination levels in Stardust aerogels was much lower than the levels observed in the Murchison meteorite. In addition, the alpha-dialkyl amino acids AIB and isovaline which are the most abundant amino acids in Murchison were not detected in the aerogel above blank levels. We are currently integrating LIF detection capability to our existing nanoflow LC-ToF-MS for enhanced sensitivity required for the analysis of amino acids in Stardust samples.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olofinjana, Bolutife; Lorenzo-Martin, Cinta; Ajayi, Oyelayo O.

Surface texturing or topographical design is one of the primary techniques to control friction and wear performance of surfaces in tribological contact. Laser surface texturing (LST), whereby a laser beam is used to produce regular arrays of dimples on a surface, has been demonstrated to reduce friction in conformal lubricated contacts. Friction and wear behavior under boundary lubrication is also known to be dependent on the formation and durability of the tribochemical film formed from lubricant additives. In this paper, the effects of LST on the formation and durability of tribochemical films and its consequent impacts on friction and wearmore » behavior in various lubrication regimes were evaluated. Friction and wear tests that cycled through different lubrication regimes were conducted with both polished and LST treated surfaces using a synthetic lubricant with and without model additives of ZDDP and MoDTC mixture. In the base oil without additives, LST produced noticeable reduction in friction in all lubrication regimes. However, with low-friction model additives, friction was higher in tests with LST due to significant differences in the tribochemical film formation in the polished and LST surfaces, as well as the sliding counterface. Continuous tribo-films were formed on ball conterface rubbed against polished surfaces while the films were streaky and discontinuous in ball rubbed against LST surfaces. LST produced more wear on the ball counterface in both base and additized oils. Lastly, no measurable wear was observed in both the polished and LST flat specimens.« less

Lube oil-dependent ash chemistry on soot oxidation reactivity in a gasoline direct-injection engine

DOE PAGES

Choi, Seungmok; Seong, Heeje

2016-09-30

Gasoline particulate filters (GPF) are considered an enabling technology to meet stringent particulate matter (PM) regulations for gasoline direct-injection (GDI) engines, which are known to produce significant PM emissions. While ash loading in filters has been recognized to be detrimental in filter performance by increasing back pressure, increased ash fractions in soot were observed to enhance soot oxidation. In this study, GDI soot samples derived from different gasoline/lube oil blends were evaluated to identify potential promoting factors when formulated lube oils were dosed into gasoline fuel. Ca-derived ash enhanced soot oxidation remarkably, while P- and ZDDP-derived ash deteriorated soot oxidation.more » It is apparent that the promoting effect of lube oil-derived ash is due mainly to the Ca component that is the most abundant among additive components in lube oil. Bulk and surface analyses of these ash compounds indicate that Ca-derived ash would be complex compounds, while the contribution of CaSO 4, which is one of the most abundant ash compounds from diesel engines, is almost negligible. For the validation of the ash promoting impact in filters, the regeneration experiments were compared for a TWC-coated GPF in a GDI engine before and after ash loading was performed. The pressure drop of the ash-loaded GPF decreased noticeably in the initial regeneration stage and it increased gradually, whereas that of no ash-loaded GPF increased gradually without any reduction. So, it is concluded that the ash layer in the GPF assisted soot oxidation in the early regeneration stage when it was in close contact with soot.« less

Efficient synthesis of novel dialkyl-3-cyanopropylphosphate derivatives and evaluation of their anticholinesterase activity.

PubMed

Aouani, Iyadh; Sellami, Badreddine; Lahbib, Karima; Cavalier, Jean-François; Touil, Soufiane

2017-06-01

Based on the broad spectrum of biological activities associated with organophosphates, a novel type of this class of compounds was synthesized, bearing a nitrile group, from the sodium alkoxide-catalyzed reaction of dialkylphosphites with γ-ketonitriles at 80°C under solvent-free conditions. A reaction mechanism involving a phospha-Brook type rearrangement is proposed. Eight title compounds were investigated for their in vitro inhibitory potency and selectivity against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) using Ellman's spectrophotometric method. The synthesized derivatives exhibited mostly a moderate activity against both cholinesterases. The IC 50 values for BChE were in a smaller concentration range (5.96-23.35µM) compared to those for AChE inhibition (9.61-53.74µM). The diethyl-3-cyano-1-p-tolylpropylphosphate which displayed the higher dual inhibitory potency towards both cholinesterases could be considered as a potential candidate for developing new drugs to treat Alzheimer's disease. Copyright © 2017 Elsevier Inc. All rights reserved.

Dithiocarbamate Self-Assembled Monolayers as Efficient Surface Modifiers for Low Work Function Noble Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, Dominik; Schäfer, Tobias; Schulz, Philip

2016-09-06

Tuning the work function of the electrode is one of the crucial steps to improve charge extraction in organic electronic devices. Here, we show that N,N-dialkyl dithiocarbamates (DTC) can be effectively employed to produce low work function noble metal electrodes. Work functions between 3.1 and 3.5 eV are observed for all metals investigated (Cu, Ag, and Au). Ultraviolet photoemission spectroscopy (UPS) reveals a maximum decrease in work function by 2.1 eV as compared to the bare metal surface. Electronic structure calculations elucidate how the complex interplay between intrinsic dipoles and dipoles induced by bond formation generates such large work functionmore » shifts. Subsequently, we quantify the improvement in contact resistance of organic thin film transistor devices with DTC coated source and drain electrodes. These findings demonstrate that DTC molecules can be employed as universal surface modifiers to produce stable electrodes for electron injection in high performance hybrid organic optoelectronics.« less

Cyclopropylamines from N,N-dialkylcarboxamides and Grignard reagents in the presence of titanium tetraisopropoxide or methyltitanium triisopropoxide.

PubMed

de Meijere, Armin; Chaplinski, Vladimir; Winsel, Harald; Kordes, Markus; Stecker, Björn; Gazizova, Vesta; Savchenko, Andrei I; Boese, Roland; Schill, Farina

2010-12-10

Thirty-three different N,N-dialkyl- and N-alkyl-N-phosphorylalkyl-substituted carboxamides 9-17 were treated with unsubstituted as well as with 2-alkyl-, 2,2-dialkyl-, and 3-alkenyl-substituted ethylmagnesium bromides 6 in the presence of stoichiometric amounts of titanium tetraisopropoxide or methyltitanium triisopropoxide to furnish substituted cyclopropylamines 20-25 in 20-98% yield, depending on the substituents with no (1:1) to excellent (>25:1) diastereoselectivities. Generally higher yields (up to 98%) of the cyclopropylamines 20-28 without loss of the diastereoselectivity were obtained with methyltitanium triisopropoxide as the titanium mediator. Under these conditions, even dioxolane-protected ketones and halogen-substituted and chiral as well as achiral alkyloxyalkyl-substituted carboxamides could be converted to the correspondingly substituted cyclopropylamines with unsubstituted as well as phenyl- and a variety of alkyl-substituted ethylmagnesium bromides in addition to numerous heteroatom-containing (e.g., halogen-, trityloxy-, tetrahydropyranyloxy-substituted) Grignard reagents (62 examples altogether). The transformation of N,N-diformylalkylamines 54 with ethylmagnesium bromide in the presence of methyltitanium triisopropoxide to N,N-dicyclopropyl-N-alkylamines 55 can be brought about in up to 82% yield (6 examples). An asymmetric variant of the titanium-mediated cyclopropanation of N,N-dialkylcarboxamides has been developed by applying chiral titanium mediators generated from stoichiometric amounts of titanium tetraisopropoxide and chiral diamino or diol ligands, respectively. The most efficient chiral mediators turned out to be titanium bistaddolates that provided the corresponding cyclopropylamines with enantiomeric excesses (ee) of up to 84%. Evaluation of several silyl-based additives revealed that the reaction can also efficiently be carried out with substoichiometric amounts (down to 25 mol%) of the titanium reagent, as long as 2-aryl- or 2-ethenyl-substituted ethylmagnesium halides are used and a concomitant slight decrease in yields is accepted. The newly developed methodology was successfully applied for the preparation of analogues with cyclopropylamine moieties of known drugs and natural products such as the nicotine metabolite (S)-Cotinine as well as the insecticides Dinotefuran and Imidacloprid.

In situ produced branched glycerol dialkyl glycerol tetraethers in suspended particulate matter from the Yenisei River, Eastern Siberia

NASA Astrophysics Data System (ADS)

De Jonge, Cindy; Stadnitskaia, Alina; Hopmans, Ellen C.; Cherkashov, Georgy; Fedotov, Andrey; Sinninghe Damsté, Jaap S.

2014-01-01

Soil-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs) in marine river fan sediments have a potential use for determining changes in the mean annual temperature (MAT) and pH of the river watershed soils. Prior to their incorporation in marine sediments, the compounds are transported to the marine system by rivers. However, emerging evidence suggests that the brGDGTs in freshwater systems can be derived from both soil run-off and in situ production. The production of brGDGTs in the river system can complicate the interpretation of the brGDGT signal delivered to the marine system. Therefore, we studied the distribution of brGDGT lipids in suspended particulate matter (SPM) of the Yenisei River. Chromatographic improvements allowed quantification of the recently described hexamethylated brGDGT isomer, characterized by having two methyl groups at the 6/6‧ instead of the 5/5‧ positions, in an environmental dataset for the first time. This novel compound was the most abundant brGDGT in SPM from the Yenisei. Its fractional abundance correlated well with that of the 6-methyl isomer of the hexamethylated brGDGT that contains one cyclopentane moiety. The Yenisei River watershed is characterized by large differences in MAT (>11 °C) as it spans a large latitudinal range (46-73°N), which would be expected to be reflected in brGDGT distributions of its soils. However, the brGDGT distributions in its SPM show little variation. Furthermore, the reconstructed pH values are high compared to the watershed soil pH. We, therefore, hypothesize that the brGDGTs in the Yenisei River SPM are predominantly produced in situ and not primarily derived from erosion of soil. This accounts for the absence of a change in the temperature signal, as the river water temperature is more stable. Using a lake calibration, the reconstructed temperature values agree with the mean summer temperatures (MST) recorded. The brGDGTs delivered to the sea by the Yenisei River during this season are thus not soil-derived, possibly complicating the use of brGDGTs in marine sediments for palaeoclimate reconstructions.

Dialkyl phosphate urinary metabolites and chromosomal abnormalities in human sperm.

PubMed

Figueroa, Zaida I; Young, Heather A; Meeker, John D; Martenies, Sheena E; Barr, Dana Boyd; Gray, George; Perry, Melissa J

2015-11-01

The past decade has seen numerous human health studies seeking to characterize the impacts of environmental exposures, such as organophosphate (OP) insecticides, on male reproduction. Despite an extensive literature on OP toxicology, many hormone-mediated effects on the testes are not well understood. This study investigated environmental exposures to OPs and their association with the frequency of sperm chromosomal abnormalities (i.e., disomy) among adult men. Men (n=159) from a study assessing the impact of environmental exposures on male reproductive health were included in this investigation. Multi-probe fluorescence in situ hybridization (FISH) for chromosomes X, Y, and 18 was used to determine XX18, YY18, XY18 and total disomy in sperm nuclei. Urine was analyzed using gas chromatography coupled with mass spectrometry for concentrations of dialkyl phosphate (DAP) metabolites of OPs [dimethylphosphate (DMP); dimethylthiophosphate (DMTP); dimethyldithiophosphate (DMDTP); diethylphosphate (DEP); diethylthiophosphate (DETP); and diethyldithiophosphate (DEDTP)]. Poisson regression was used to model the association between OP exposures and disomy measures. Incidence rate ratios (IRRs) were calculated for each disomy type by exposure quartiles for most metabolites, controlling for age, race, BMI, smoking, specific gravity, total sperm concentration, motility, and morphology. A significant positive trend was seen for increasing IRRs by exposure quartiles of DMTP, DMDTP, DEP and DETP in XX18, YY18, XY18 and total disomy. A significant inverse association was observed between DMP and total disomy. Findings for total sum of DAP metabolites concealed individual associations as those results differed from the patterns observed for each individual metabolite. Dose-response relationships appeared nonmonotonic, with most of the increase in disomy rates occurring between the second and third exposure quartiles and without additional increases between the third and fourth exposure quartiles. This is the first epidemiologic study of this size to examine the relationship between environmental OP exposures and human sperm disomy outcomes. Our findings suggest that increased disomy rates were associated with specific DAP metabolites, suggesting that the impacts of OPs on testis function need further characterization in epidemiologic studies. Copyright © 2015 Elsevier Inc. All rights reserved.

Targeting hypoxia in tumors using 2-nitroimidazoles with peptidic chelators for technetium-99m: effect of lipophilicity.

PubMed

Zhang, X; Su, Z F; Ballinger, J R; Rauth, A M; Pollak, A; Thornback, J R

2000-01-01

Tumor hypoxia is an important prognostic factor for response to therapy. Radiolabeled 2-nitroimidazoles have been used for imaging hypoxia, and the octanol/water partition coefficient (P) of these compounds appears to play a crucial role in their suitability for imaging. A series of 11 2-nitroimidazoles coupled to peptidic chelators for (99m)Tc with divergent P was developed and evaluated in an in vitro system. Two classes of N(3)S chelators were used: dialkyl-Gly-Ser-Cys-linker-2-nitroimidazole (Class I) and dialkyl-Gly-Lys(2-nitroimidazole)-Cys (Class II). The chelators were prepared by automated solid-phase peptide synthesis. Xanthine oxidase was able to reduce the 2-nitroimidiazole moiety on the ligands, but the rate of reduction varied 5-fold among the different chelators. The chelators were labeled by transchelation from [(99m)Tc]gluconate at temperatures between 22 and 100 degrees C. The reaction mixtures were analyzed by HPLC and their P values determined. The accumulation of each complex in suspension cultures of Chinese hamster ovary cells incubated under aerobic or extremely hypoxic conditions was determined. Radiochemical yields ranged from 5 to 80% for the 11 compounds. HPLC showed that some of the compounds formed two complexes with (99m)Tc, possibly syn and anti conformations with respect to the Tc=O bond. In general, the Class I chelators labeled more readily than the class II chelators. The P values of the (99m)Tc complexes varied from 0.0002 to 5 and were generally in accordance with predictions based on structure. There were also differences in P as a function of pH; the free acids had a lower P at pH 7.4 than at pH 2.0 due to ionization, whereas the amides did not show this effect. Accumulation levels in aerobic cells were related to P but varied over a narrow range. Four of the 11 compounds showed selective accumulation in hypoxic cells. The peptidic class of 2-nitroimidazoles, with flexible design and convenient solid-phase synthesis, deserves further study as agents for imaging hypoxia in tumors.

New Unsymmetrically Benzene-Fused Bis (Tetrathiafulvalene): Synthesis, Characterization, Electrochemical Properties and Electrical Conductivity of Their Materials

PubMed Central

Abbaz, Tahar; Bendjeddou, Amel; Gouasmia, Abdelkrim; Villemin, Didier; Shirahata, Takashi

2014-01-01

The synthesis of new unsymmetrically benzene-fused bis (tetrathiafulvalene) has been carried out by a cross-coupling reaction of the respective 4,5-dialkyl-1,3-dithiole- 2-selenone 6–9 with 2-(4-(p-nitrophenyl)-1,3-dithiole-2-ylidene)-1,3,5,7-tetrathia-s-indacene- 6-one 5 prepared by olefination of 4-(p-nitrophenyl)-1,3-dithiole-2-selenone 3 and 1,3,5,7-tetrathia-s-indacene-2,6-dione 4. The conversion of the nitro moiety 10a–d to amino 11a–d then dibenzylamine 12a–d groups respectively used reduction and alkylation methods. The electron donor ability of these new compounds has been measured by cyclic voltammetry (CV) technique. Charge transfer complexes with tetracyanoquino-dimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials. PMID:24642878

Fungal Peptaibiotics: Assessing Potential Meteoritic Amino Acid Contamination

NASA Technical Reports Server (NTRS)

Elsila, J. E.; Callahan, M. P.; Glavin, D. P.; Dworkin, J. P.; Bruckner, H.

2010-01-01

The presence of non-protein alpha-dialkyl-amino acids such as alpha-aminoisobutyric acid (alpha-A1B) and isovaline (Iva), which are relatively rare in the terrestrial biosphere, has long been used as an indication of the indigeneity of meteoritic amino acids, however, the discovery of alpha-AIB in peptides producers by a widespread group of filamentous fungi indicates the possibility of a terrestrial biotic source for the alpha-AIB observed in some meteorites. The alpha-AIB-containing peptides produced by these fungi are dubbed peptaibiotics. We measured the molecular distribution and stable carbon and nitrogen isotopic ratios for amino acids found in the total hydrolysates of four biologically synthesized peptaibiotics. We compared these aneasurenetts with those from the CM2 carbonaceous chondrite Murchison and from three Antarctic CR2 carbonaceous chondrites in order to understand the peptaibiotics as a potential source of meteoritic contamination.

Effect of laser surface texturing (LST) on tribochemical films dynamics and friction and wear performance

DOE PAGES

Olofinjana, Bolutife; Lorenzo-Martin, Cinta; Ajayi, Oyelayo O.; ...

2015-06-06

Surface texturing or topographical design is one of the primary techniques to control friction and wear performance of surfaces in tribological contact. Laser surface texturing (LST), whereby a laser beam is used to produce regular arrays of dimples on a surface, has been demonstrated to reduce friction in conformal lubricated contacts. Friction and wear behavior under boundary lubrication is also known to be dependent on the formation and durability of the tribochemical film formed from lubricant additives. In this paper, the effects of LST on the formation and durability of tribochemical films and its consequent impacts on friction and wearmore » behavior in various lubrication regimes were evaluated. Friction and wear tests that cycled through different lubrication regimes were conducted with both polished and LST treated surfaces using a synthetic lubricant with and without model additives of ZDDP and MoDTC mixture. In the base oil without additives, LST produced noticeable reduction in friction in all lubrication regimes. However, with low-friction model additives, friction was higher in tests with LST due to significant differences in the tribochemical film formation in the polished and LST surfaces, as well as the sliding counterface. Continuous tribo-films were formed on ball conterface rubbed against polished surfaces while the films were streaky and discontinuous in ball rubbed against LST surfaces. LST produced more wear on the ball counterface in both base and additized oils. Lastly, no measurable wear was observed in both the polished and LST flat specimens.« less

Ionic Liquids as Novel Lubricants and /or Lubricant Additives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, J.; Viola, M. B.

2013-10-31

This ORNL-GM CRADA developed ionic liquids (ILs) as novel lubricants or oil additives for engine lubrication. A new group of oil-miscible ILs have been designed and synthesized with high thermal stability, non-corrosiveness, excellent wettability, and most importantly effective anti-scuffing/anti-wear and friction reduction characteristics. Mechanistic analysis attributes the superior lubricating performance of IL additives to their physical and chemical interactions with metallic surfaces. Working with a leading lubricant formulation company, the team has successfully developed a prototype low-viscosity engine oil using a phosphonium-phosphate IL as an anti-wear additive. Tribological bench tests of the IL-additized formulated oil showed 20-33% lower friction inmore » mixed and elastohydrodynamic lubrication and 38-92% lower wear in boundary lubrication when compared with commercial Mobil 1 and Mobil Clean 5W-30 engine oils. High-temperature, high load (HTHL) full-size engine tests confirmed the excellent anti-wear performance for the IL-additized engine oil. Sequence VID engine dynamometer tests demonstrated an improved fuel economy by >2% for this IL-additized engine oil benchmarked against the Mobil 1 5W-30 oil. In addition, accelerated catalyst aging tests suggest that the IL additive may potentially have less adverse impact on three-way catalysts compared to the conventional ZDDP. Follow-on research is needed for further development and optimization of IL chemistry and oil formulation to fully meet ILSAC GF-5 specifications and further enhance the automotive engine efficiency and durability.« less

Provenance of tetraether membrane lipids in a large temperate lake (Loch Lomond, UK): implications for glycerol dialkyl glycerol tetraether (GDGT)-based palaeothermometry

NASA Astrophysics Data System (ADS)

Buckles, L. K.; Weijers, J. W. H.; Tran, X.-M.; Waldron, S.; Sinninghe Damsté, J. S.

2014-10-01

The application of glycerol dialkyl glycerol tetraether (GDGT)-based palaeoenvironmental proxies, such as the branched vs. isoprenoidal tetratether (BIT) index, TEX86 and the MBT-CBT palaeothermometer, has lately been expanded to lacustrine sediments. Given recent research identifying the production of branched, bacterial GDGTs (brGDGTs) within lakes, it is necessary to ascertain the effect of this lacustrine production on GDGT-based proxies. This study profiles a temperate, monomictic lake (Loch Lomond, UK), analysing labile intact polar GDGT lipids (IPLs) and resilient core GDGT lipids (CLs) in catchment soils, small tributary rivers, lake water and lake sediments. Loch Lomond consists of two basins bisected by the Highland Boundary Fault, resulting in a mesotrophic to oligotrophic gradient from south to north. The north basin is fjord-like, while the south basin is shallow with a lowland catchment. Besides abundant influxes of allochthonous soil- and peat-derived (CL) brGDGTs, brGDGTs are produced in a variety of settings in Loch Lomond. Rather than integrating a scattered soil signal, there is some evidence that small rivers may contribute to the brGDGT pool through addition of brGDGTs produced in situ in these streams. Three hundred days of settling particles and water column profiles of suspended particulate matter (SPM; March and September 2011) reveal brGDGT production throughout the water column, with (IPL and CL) brGDGT distributions varying by basin. In lake sediments, in situ brGDGT production affects the distributions of sedimentary brGDGTs despite high soil- and peat-derived organic matter influxes from the catchment. MBT-CBT-derived mean annual air temperature (MAAT) estimates from soil, river and lake sediments vary widely. A strong bias towards higher MAATs in the south and lower MAATs in the north basin further complicates the application of the proxy. These results emphasise that caution must be exercised when applying the MBT-CBT palaeothermometer to individual lakes in which the use of the proxy has not been validated and therefore the factors affecting its application are not well understood. Despite elevated BIT indices, (partly) due to in situ brGDGT production, reliable TEX86 lake surface temperature (LST) estimates were obtained from SPM with BIT indices up to 0.9. Lower north basin sediments yielded accurate LST estimates but require further evaluation to properly constrain the application of the TEX86 proxy.

A Simple and Mild Synthesis of 1H-Isochromenes and (Z)-1-Alkylidene-1,3-dihydroisobenzofurans by the Iodocyclization of 2-(1-Alkynyl)benzylic Alcohols

PubMed Central

Mancuso, Raffaella; Mehta, Saurabh; Gabriele, Bartolo; Salerno, Giuseppe; Jenks, William S.; Larock, Richard C.

2010-01-01

A variety of iodo-substituted isochromenes, dihydroisobenzofurans, and pyranopyridines are readily prepared in good to excellent yields under mild conditions by the iodocyclization of readily available 2-(1-alkynyl)benzylic alcohols or 2-(1-alkynyl)-3-(hydroxymethyl)pyridines. Reactions are carried out in MeCN at 15 °C using 3 equiv of I2 as the iodine source and NaHCO3 (3 equiv) as the base. The regiochemical outcome of the reaction strongly depends on the substitution pattern of the starting material. In particular, the 5-exo-dig cyclization mode, leading to dihydroisobenzofurans, is observed in the case of substrates bearing a tertiary alcoholic group, owing to the gem-dialkyl effect, while the 6-endo-dig cyclization mode, leading to isochromene or pyranopyridines, is the usually preferred pathway in the case of substrates bearing a primary or secondary alcoholic group PMID:20043652

In vitro evaluation of the schistosomicidal effect of the extracts, fractions and major 3-hydroxy-2,6-dialkyl-substituted piperidine alkaloids from the flowers of Senna spectabilis (Fabaceae).

PubMed

de Castro, Andreísa Teixeira; Castro, Aline Pereira; Silva, Matheus Siqueira; de Souza, Isabella Maria Monteiro; Martins-Souza, Raquel Lopes; Chagas-Paula, Daniela Aparecida; Coelho, Luiz Felipe Leomil; da Silva Bolzani, Vanderlan; Pivatto, Marcos; Viegas, Claudio; Marques, Marcos José

2016-09-01

In this work, we present the in vitro schistosomicidal activity evaluation of the most active dichloromethane fraction (FDm) (ED50=83.5μg/mL) and of a mixture of the major alkaloids ((-)-cassine/(-)-spectaline, C/E) (ED50=37.4μg/mL) from the flowers of Senna spectabilis against adult worms and cercariae. We also demonstrate other toxic effects including paralysis of the adult worms, inhibition of the secretory activity, tegument lesions and cercaricidal activity. In the association test of Praziquantel (PZQ)-C/E, we observed up to 80% mortality of Schistosoma mansoni in comparison to PZQ monotherapy. Due to the diversity of the toxic effects, the schistosomicidal activity of C/E is likely a result of a multitarget mechanism involving the tegument, secretory system and neuromotor action. Copyright © 2016 Elsevier Ltd. All rights reserved.

Distinct molecular structures and hydrogen bond patterns of α,α-diethyl-substituted cyclic imide, lactam, and acetamide derivatives in the crystalline phase

NASA Astrophysics Data System (ADS)

Krivoshein, Arcadius V.; Ordonez, Carlos; Khrustalev, Victor N.; Timofeeva, Tatiana V.

2016-10-01

α,α-Dialkyl- and α-alkyl-α-aryl-substituted cyclic imides, lactams, and acetamides show promising anticonvulsant, anxiolytic, and anesthetic activities. While a number of crystal structures of various α-substituted cyclic imides, lactams, and acetamides were reported, no in-depth comparison of crystal structures and solid-state properties of structurally matched compounds have been carried out so far. In this paper, we report molecular structure and intermolecular interactions of three α,α-diethyl-substituted compounds - 3,3-diethylpyrrolidine-2,5-dione, 3,3-diethylpyrrolidin-2-one, and 2,2-diethylacetamide - in the crystalline phase, as studied using single-crystal X-ray diffraction and IR spectroscopy. We found considerable differences in the patterns of H-bonding and packing of the molecules in crystals. These differences correlate with the compounds' melting points and are of significance to physical pharmacy and formulation development of neuroactive drugs.

Synthesis, electronic structure and spectral fluorescent properties of vinylogous merocyanines derived from 1,3-dialkyl-benzimidazole and malononitrile

NASA Astrophysics Data System (ADS)

Kulinich, Andrii V.; Mikitenko, Elena K.; Ishchenko, Alexander A.

2017-01-01

A vinylogous series of merocyanines were synthesized with 1,3-dibutyl-benzimidazole and malononitrile residues as the donor and acceptor terminal groups. These dyes do not comprise carbonyl groups, which are prone to the strong specific solvation by polar solvents up to hydrogen bond formation, and nevertheless they possess distinct reversed solvatochromism, i.e. their molecules have very high dipolarity. At that, they are soluble in a wide range of solvents from n-hexane to ethanol and do not aggregate readily. They were studied thoroughly by UV/Vis, fluorescence, IR, and NMR spectroscopy methods. Their structure and spectral properties in the ground and excited fluorescent states were modelled at the DFT level both in vacuum and in solvents of various polarities by using the PCM solvent field simulation. The calculations were performed using several hybrid functionals (B3LYP, CAM-B3LYP, and wB97XD) and the split-valence 6-31G (d,p) basis set.

A facile route to ketene-functionalized polymers for general materials applications

NASA Astrophysics Data System (ADS)

Leibfarth, Frank A.; Kang, Minhyuk; Ham, Myungsoo; Kim, Joohee; Campos, Luis M.; Gupta, Nalini; Moon, Bongjin; Hawker, Craig J.

2010-03-01

Function matters in materials science, and methodologies that provide paths to multiple functionality in a single step are to be prized. Therefore, we introduce a robust and efficient strategy for exploiting the versatile reactivity of ketenes in polymer chemistry. New monomers for both radical and ring-opening metathesis polymerization have been developed, which take advantage of Meldrum's acid as both a synthetic building block and a thermolytic precursor to dialkyl ketenes. The ketene-functionalized polymers are directly detected by their characteristic infrared absorption and are found to be stable under ambient conditions. The inherent ability of ketenes to provide crosslinking via dimerization and to act as reactive chemical handles via addition, provides simple methodology for application in complex materials challenges. Such versatile characteristics are illustrated by covalently attaching and patterning a dye through microcontact printing. The strategy highlights the significant opportunities afforded by the traditionally neglected ketene functional group in polymer chemistry.

Polymer Architecture Effects in Confined Geometry: Molecular Dynamics Simulation Study

NASA Astrophysics Data System (ADS)

Wijesinghe, Sidath; Perahia, Dvora; Grest, Gary

Luminescent rigid polymers confined into nanoparticles, or polydots, are emerging as a promising tool for nano medicine. The constrained architecture of a rigid backbone trapped in nano-dimensions results in photophysics that differs from that of spontaneously assembled rigid polymers. Incorporating ionizable functionalities in the polymers, often required for therapeutics, impacts the polymer conformation in solution. Here we report fully atomistic molecular dynamics simulations on the structure of dialkyl p-phenylene ethynylene confined into polydots. We find that the structure and thermal stability of polydots are sensitive to both the molecular weight n and the carboxylation fraction f. At room temperature , polydots remain confined regardless of n and f . However, as temperature is increased, polydots with lower n or f rearrange whereas polydots with higher n or fremain confined, though no direct clustering of the ionic groups was observed. NSF CHE 1308298 is acknowledged.

Lubricant additive concentrate containing isomerized jojoba oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arndt, G.

1987-05-12

This patent describes a crankcase motor oil additive concentrate intended to be added to a conventional crankcase motor oil to improve its ability to lubricate and protect the engine. The additive concentrate comprises the following components: A petroleum base stock of lubricating quality and viscosity. The base stock comprises from about 13.5 to 90 weight percent of the additive concentrate; a detergent-inhibitor package. The package is present at from about 7 to about 40 weight percent of the concentrate; a supplemental antiwear additive selected from the salts of dialkyl dithiophosporic acids. The additive is present at a level of frommore » about 1 to about 10 weight percent of the concentrate; and a supplemental antiwear additive selected from the class of sulfurized olefins. The additive is present at a level of from about 1 to about 10 weight percent of the concentrate.« less

Synthesis of a Simplified Version of Stable Bulky and Rigid Cyclic (Alkyl)(Amino)Carbenes (CAACs), and Catalytic Activity of the Ensuing Gold(I) Complex in the Three-Component Preparation of 1,2-Dihydroquinoline Derivatives

PubMed Central

Zeng, Xiaoming; Frey, Guido D.; Kinjo, Rei; Donnadieu, Bruno; Bertrand, Guy

2009-01-01

A 95/5 mixture of cis and trans 2,4-dimethyl-3-cyclohexenecarboxaldehyde (trivertal), a common fragrance and flavor material produced in bulk quantities, serves as the precursor for the synthesis of a stable spirocyclic (alkyl)(amino)carbene, in which the 2-methyl-substituted cyclohexenyl group provides steric protection to an ensuing metal. The efficiency of this carbene as ligand for transition metal based catalysts is first illustrated by the gold(I) catalyzed hydroamination of internal alkynes with secondary dialkyl amines, a process with little precedent. The feasibility of this reaction allows for significantly enlarging the scope of the one-pot three-component synthesis of 1,2-dihydroquinoline derivatives, and related nitrogen-containing heterocycles. Indeed, two different alkynes were used, which include an internal alkyne for the first step. PMID:19456108

An efficient preparation of isosteric phosphonate analogues of sphingolipids by opening of oxirane and cyclic sulfamidate intermediates with alpha-lithiated alkylphosphonic esters.

PubMed

Sun, Chaode; Bittman, Robert

2004-10-29

D-erythro-(2S,3R,4E)-Sphingosine-1-phosphonate (1), the isosteric phosphonate analogue of naturally occurring sphingosine 1-phosphate (1a), and D-ribo-phytosphingosine 1-phosphonate (2), the isosteric phosphonate analogue of D-ribo-phytosphingosine-1-phosphate (2a), were synthesized starting with methyl 2,3-O-isopropylidene-d-glycerate (4) and D-ribo-phytosphingosine (3), respectively. Oxirane 12 was formed in eight steps from 4, and cyclic sulfamidate 22 was formed in five steps from 3. The phosphonate group was introduced via regioselective ring-opening reactions of oxirane 12 and cyclic sulfamidate 22 with lithium dialkyl methylphosphonate, affording 13 and 23, respectively. The synthesis of 1 was completed by S(N)2 displacement of chloromesylate intermediate 14b with azide ion, followed by conversion of the resulting azido group to a NHBoc group and deprotection. The synthesis of 2 was completed by cleavage of the acetal, N-benzyl, and alkyl phosphonate ester groups.

Lube oil-dependent ash chemistry on soot oxidation reactivity in a gasoline direct-injection engine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Seungmok; Seong, Heeje

Gasoline particulate filters (GPF) are considered an enabling technology to meet stringent particulate matter (PM) regulations for gasoline direct-injection (GDI) engines, which are known to produce significant PM emissions. While ash loading in filters has been recognized to be detrimental in filter performance by increasing back pressure, increased ash fractions in soot were observed to enhance soot oxidation. In this study, GDI soot samples derived from different gasoline/lube oil blends were evaluated to identify potential promoting factors when formulated lube oils were dosed into gasoline fuel. Ca-derived ash enhanced soot oxidation remarkably, while P- and ZDDP-derived ash deteriorated soot oxidation.more » It is apparent that the promoting effect of lube oil-derived ash is due mainly to the Ca component that is the most abundant among additive components in lube oil. Bulk and surface analyses of these ash compounds indicate that Ca-derived ash would be complex compounds, while the contribution of CaSO 4, which is one of the most abundant ash compounds from diesel engines, is almost negligible. For the validation of the ash promoting impact in filters, the regeneration experiments were compared for a TWC-coated GPF in a GDI engine before and after ash loading was performed. The pressure drop of the ash-loaded GPF decreased noticeably in the initial regeneration stage and it increased gradually, whereas that of no ash-loaded GPF increased gradually without any reduction. So, it is concluded that the ash layer in the GPF assisted soot oxidation in the early regeneration stage when it was in close contact with soot.« less

What Happens when Sea Ice Retreats, Peatlands Form, and a Landbridge Drowns? A Molecular View of the Last Deglacial from the Pacific-Arctic Gateway

NASA Astrophysics Data System (ADS)

Kocis, J. J.; Petsch, S.; Castañeda, I. S.; Brigham-Grette, J.

2014-12-01

Arctic peatlands and thermokarst lakes (TK) are thought to play a significant role in changing atmospheric methane concentration (AMC) during the last deglacial. However, there is debate concerning timing of their initiation and extent they drove variations in AMC. Models show sea ice cover (SIC) and sea surface temperatures (SSTs) can also play a significant role. Yet, changes in peatland/TK lake areal extent in response to those dynamics as continental shelves were submerged are often not considered. To examine such connections, we report on molecular proxies in marine records that reveal change in terrestrial organic matter (TOM) export, SIC, and SSTs as sea levels rose during the last 18 ka in the Pacific-Arctic Gateway. Here, TOM input to the ocean was tracked by measuring the flux of branched glycerol dialkyl glycerol tetraethers, n-alkyl lipids, and pentacyclic triterpenoids. SIC and SSTs were reconstructed using modern calibrations of highly branched isoprenoid alkene abundances in surface sediments from the Bering and Chukchi Seas. SSTs were also reconstructed based on the relative abundance of isoprenoid glycerol dialkyl glycerol tetraethers. Our sediment records reveal increased flux of TOM coincides with peatland/TK lake initiation, reduced SIC (~20%), and warmer SSTs (~4°C) as AMC increased during the Bølling-Allerød (BA). Terrestrial flux dramatically reduced as SIC increased (~50%) and SSTs cooled as AMC fell during the Younger Dryas. Most notably, TOM export rapidly rebounds as AMC abruptly rose throughout the Holocene Thermal Maximum (HTM), when SSTs warmed by ~3°C and SIC diminished and peatland areal extent increased. Using multi-proxy evidence in combination with a simple model that accounts for submergence of peatland/TK lake area, we estimate that the exposed Beringian shelf emitted an amount of CH4 comparable to previously reported peatland emissions in Alaska during the BA and HTM. The GDGT-based methane index (MI) was <0.3 throughout our sediment records, suggesting destabilized marine gas hydrates were not the principal source of methane. Results of our study provide novel marine-based evidence for the timing of peatland and TK lake initiation and the role sea ice played in contributing to variations in AMC during deglacial sea level rise in the Arctic.

Investigation of synthesized new vanadium(III) complexes of ditolyldithiophosphate ligands by spectroscopic, cyclic voltammetric, DFT, antimicrobial and cytotoxic studies

NASA Astrophysics Data System (ADS)

Kumar, Sandeep; Syed, Atiya; Andotra, Savit; Kaur, Ramanpreet; Vikas; Pandey, Sushil K.

2018-02-01

Vanadium(III) complexes with sulfur donor dithiophosphate ligands corresponding to [{(ArO)2PS2}3V] and [{(ArO)2PS2}2VCl.L] (Ar = o-, m-, p-CH3C6H4 and p-Cl-m-CH3C6H3; L = NC5H5, P(C6H5)3, have been synthesized and characterized by various physico-chemical techniques like elemental analyses, magnetic studies, ESI-Mass, IR, UV and heteronuclear NMR (1H, 13C and 31P) spectral studies. These analyses have contributed to the prediction of structure: by exhibiting significant v(P-S) and v(Pdbnd S) band shifting in comparative IR spectra; shifting of resonance signal in comparative 31P NMR spectra of ligands and complexes and stability of V(III) ion in the complexed state is confirmed by magnetic and UV studies. Therefore, the six coordinated geometry stabilizing the trivalent vanadium atom in the complexes and adducts, respectively has been confirmed. The cyclic voltammetric analyses presented the redox aptitude of the complex under analysis which can be utilized as catalyst in organic synthesis. The geometry of ligands and complexes has been optimized using density functional theory (DFT). The structural parameters, vibrational bands and energy gaps of frontier orbitals (HOMO-LUMO) have also been calculated. The calculated geometric and spectral results reproduced the experimental data with well agreement. The DFT computed frontier molecular orbitals (HOMO-LUMO) and their energies suggest charge transfer occurs within the complexes. Antimicrobial screening of the complexes against two bacterial strains: Gram-positive, Enterrococcus faecalis and Gram-negative, Eischerichia coli and fungus Fusarium oxysporum have shown potential bioactivity. A preliminary cytotoxic analysis has been carried out using the cultivated human cell lines: lung adeno carcinoma cell line A-549, leukemia cell line THP-1, prostate cancer cell line PC3 and colorectal cancer cell line HCT-116.

Simultaneous determination of phthalates, their metabolites, alkylphenols and bisphenol A using GC-MS in urine of men with fertility problems.

PubMed

Kranvogl, Roman; Knez, Jure; Miuc, Alen; Vončina, Ernest; Vončina, Darinka Brodnjak; Vlaisavljević, Veljko

2014-01-01

A GC-MS method was successfully applied to measure simultaneously the concentrations of endocrine disrupting compounds (5 dialkyl phthalates, 9 phthalate monoesters, 3 alkylphenols and bisphenol A) in 136 male urine samples. In the present study the method was validated and concentrations of EDCs were determined. The results were compared with results from other studies. Correlations between endocrine disrupting compounds and also correlations of endocrine disrupting compounds with two semen quality parameters are presented and evaluated. Significant positive correlations were found between almost all the endocrine disrupting compounds. The parameter sum of DEHP (SUM DEHP) was positively correlated to all the endocrine disrupting compounds but negatively to two semen quality parameters. Negative correlations between the endocrine disrupting compounds and the semen quality parameters could indicate that endocrine disrupting compounds could cause reproductive problems by decreasing the semen count and quality. This research will have helped to evaluate human exposure to endocrine disrupting compounds.

Deepening the Topology of the Translocator Protein Binding Site by Novel N,N-Dialkyl-2-arylindol-3-ylglyoxylamides.

PubMed

Barresi, Elisabetta; Bruno, Agostino; Taliani, Sabrina; Cosconati, Sandro; Da Pozzo, Eleonora; Salerno, Silvia; Simorini, Francesca; Daniele, Simona; Giacomelli, Chiara; Marini, Anna Maria; La Motta, Concettina; Marinelli, Luciana; Cosimelli, Barbara; Novellino, Ettore; Greco, Giovanni; Da Settimo, Federico; Martini, Claudia

2015-08-13

As a continuation of our studies on 2-phenylindol-3-ylglyoxylamides as potent and selective translocator protein (TSPO) ligands, two subsets of novel derivatives, featuring hydrophilic group (OH, NH2, COOH) at the para-position of the pendent 2-phenyl ring (8-16) or different 2-aryl moieties, namely, 3-thienyl, p-biphenyl, 2-naphthyl (23-35), were synthesized and biologically evaluated, some of them showing Ki values in the subnanomolar range and the 2-naphthyl group performance being the best. The resulting SARs confirmed the key role played by interactions taking place between ligands and the lipophilic L1 pocket of the TSPO binding site. Docking simulations were performed on the most potent compound of the present series (29) exploiting the recently available 3D structures of TSPO bound to its standard ligand (PK11195). Our theoretical model was fully consistent with SARs of the newly investigated as well of the previously reported 2-phenylindol-3-ylglyoxylamide derivatives.

New cationic vesicles prepared with double chain surfactants from arginine: Role of the hydrophobic group on the antimicrobial activity and cytotoxicity.

PubMed

Pinazo, A; Petrizelli, V; Bustelo, M; Pons, R; Vinardell, M P; Mitjans, M; Manresa, A; Perez, L

2016-05-01

Cationic double chain surfactants have attracted much interest because they can give rise to cationic vesicles that can be used in biomedical applications. Using a simple and economical synthetic approach, we have synthesized four double-chain surfactants with different alkyl chain lengths (LANHCx). The critical aggregation concentration of the double chain surfactants is at least one order of magnitude lower than the CMC of their corresponding single-chain LAM and the solutions prepared with the LANHCx contain stable cationic vesicles. Encouragingly, these new arginine derivatives show very low haemolytic activity and weaker cytotoxic effects than conventional dialkyl dimethyl ammonium surfactants. In addition, the surfactant with the shortest alkyl chain exhibits good antimicrobial activity against Gram-positive bacteria. The results show that a rational design applied to cationic double chain surfactants might serve as a promising strategy for the development of safe cationic vesicular systems. Copyright © 2016 Elsevier B.V. All rights reserved.

Exposure to organophosphorus pesticides in Norwegian mothers and their children: Diurnal variability in concentrations of their biomarkers and associations with food consumption.

PubMed

Cequier, Enrique; Sakhi, Amrit Kaur; Haug, Line Småstuen; Thomsen, Cathrine

2017-07-15

Several studies have suggested that exposure to organophosphorus (OP) pesticides is detrimental for health, and in particular for children where moderate doses may have a negative impact on the neurodevelopment. This study surveys levels of the 6 non-specific urinary metabolites (dialkyl phosphates (DAPs)) of OP pesticides in Norwegian mothers (n=48) and their children (n=54), and examines the diurnal variation in concentrations as well as associations with consumption of specific food products. The highest median concentration measured in urine was found for dimethyl thiophosphate (5.3 and 5.5ng/mL SG ; specific gravity corrected) for both children and mothers, respectively, followed by diethyl phosphate (3.8 and 5.3ng/mL SG , respectively). The intra-class correlation coefficients of DAPs among mothers were moderate (0.49-0.68), and consumption of fruit explained between 8% and 55% of the variations in the mothers' and their children's urinary DAP concentrations. Copyright © 2017 Elsevier B.V. All rights reserved.

Atherton–Todd reaction: mechanism, scope and applications

PubMed Central

Le Corre, Stéphanie S; Berchel, Mathieu; Couthon-Gourvès, Hélène; Haelters, Jean-Pierre

2014-01-01

Summary Initially, the Atherton–Todd (AT) reaction was applied for the synthesis of phosphoramidates by reacting dialkyl phosphite with a primary amine in the presence of carbon tetrachloride. These reaction conditions were subsequently modified with the aim to optimize them and the reaction was extended to different nucleophiles. The mechanism of this reaction led to controversial reports over the past years and is adequately discussed. We also present the scope of the AT reaction. Finally, we investigate the AT reaction by means of exemplary applications, which mainly concern three topics. First, we discuss the activation of a phenol group as a phosphate which allows for subsequent transformations such as cross coupling and reduction. Next, we examine the AT reaction applied to produce fire retardant compounds. In the last section, we investigate the use of the AT reaction for the production of compounds employed for biological applications. The selected examples to illustrate the applications of the Atherton–Todd reaction mainly cover the past 15 years. PMID:24991268

Dynamics of polydots: Soft luminescent polymeric nanoparticles

DOE PAGES

Maskey, Sabina; Osti, Naresh C.; Grest, Gary S.; ...

2016-03-04

The conformation and dynamics of luminescent polymers collapsed into nanoparticles or polydots were studied using fully atomistic molecular dynamics (MD) simulations, providing a first insight into their internal dynamics. Controlling the conformation and dynamics of confined polymers is essential for realization of the full potential of polydots in nanomedicine and biotechnology. Specifically, the shape and internal dynamics of polydots that consist of highly rigid dialkyl p-phenylene ethynylene (PPE) are probed as a function of temperature. At room temperature, the polydots are spherical without any correlations between the aromatic rings on the PPE backbone. With increasing temperature, they expand and becomemore » slightly aspherical; however, the polymers remain confined. The coherent dynamic structure factor reveals that the internal motion of the polymer backbone is arrested, and the side chains dominate the internal dynamics of the polydots. Lastly, these new soft nanoparticles retain their overall shape and dynamics over an extended temperature range, and their conformation is tunable via their degree of expansion.« less

Dynamics of polydots: Soft luminescent polymeric nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maskey, Sabina; Osti, Naresh C.; Grest, Gary S.

The conformation and dynamics of luminescent polymers collapsed into nanoparticles or polydots were studied using fully atomistic molecular dynamics (MD) simulations, providing a first insight into their internal dynamics. Controlling the conformation and dynamics of confined polymers is essential for realization of the full potential of polydots in nanomedicine and biotechnology. Specifically, the shape and internal dynamics of polydots that consist of highly rigid dialkyl p-phenylene ethynylene (PPE) are probed as a function of temperature. At room temperature, the polydots are spherical without any correlations between the aromatic rings on the PPE backbone. With increasing temperature, they expand and becomemore » slightly aspherical; however, the polymers remain confined. The coherent dynamic structure factor reveals that the internal motion of the polymer backbone is arrested, and the side chains dominate the internal dynamics of the polydots. Lastly, these new soft nanoparticles retain their overall shape and dynamics over an extended temperature range, and their conformation is tunable via their degree of expansion.« less

A TEX86 surface sediment database and extended Bayesian calibration

NASA Astrophysics Data System (ADS)

Tierney, Jessica E.; Tingley, Martin P.

2015-06-01

Quantitative estimates of past temperature changes are a cornerstone of paleoclimatology. For a number of marine sediment-based proxies, the accuracy and precision of past temperature reconstructions depends on a spatial calibration of modern surface sediment measurements to overlying water temperatures. Here, we present a database of 1095 surface sediment measurements of TEX86, a temperature proxy based on the relative cyclization of marine archaeal glycerol dialkyl glycerol tetraether (GDGT) lipids. The dataset is archived in a machine-readable format with geospatial information, fractional abundances of lipids (if available), and metadata. We use this new database to update surface and subsurface temperature calibration models for TEX86 and demonstrate the applicability of the TEX86 proxy to past temperature prediction. The TEX86 database confirms that surface sediment GDGT distribution has a strong relationship to temperature, which accounts for over 70% of the variance in the data. Future efforts, made possible by the data presented here, will seek to identify variables with secondary relationships to GDGT distributions, such as archaeal community composition.

Effect of Dialkyl Ammonium Cationic Surfactants on the Microfluidity of Membranes Containing Raft Domains.

PubMed

Uyama, Makoto; Inoue, Kaori; Kinoshita, Koichi; Miyahara, Reiji; Yokoyama, Hirokazu; Nakano, Minoru

2018-01-01

It has been reported that a lot of receptors localize in lipid raft domains and that the microfluidity of these domains regulates the activation of these receptors. In this study, we focused on the lipid raft and in order to evaluate the physicochemical effects of surfactants on microfluidity of lipid membranes, we used liposomes comprising of egg-yolk L-α-phosphatidylcholine, egg-yolk sphingomyelin, and cholesterol as a model of cell membranes containing raft domains. The microfluidity of the domains was characterized by fluorescence spectrometry using 1,6-diphenyl-1,3,5-hexatriene and 2-dimethylamino-6-lauroylnaphthalene. Among several surfactants, dialkylammonium-type cationic surfactants most efficiently increased the microfluidity. It is therefore concluded that (1) the electrostatic interaction between the cationic surfactant and eggPC/eggSM/cholesterol liposome could be important, (2) surfactants with alkyl chains more effectively inserted into membranes than those with acyl chains, and (3) cationic surfactants with lower T m values have a greater ability to increase the fluidity.

Biodegradable poly(amine-co-ester) terpolymers for targeted gene delivery

PubMed Central

Zhou, Jiangbing; Liu, Jie; Cheng, Christopher J.; Patel, Toral R.; Weller, Caroline E.; Piepmeier, Joseph M.; Jiang, Zhaozhong; Saltzman, W. Mark

2014-01-01

Many synthetic polycationic vectors for non-viral gene delivery show high efficiency in vitro, but their usually excessive charge density makes them toxic for in vivo applications. Here we describe the synthesis of a series of high molecular weight terpolymers with low charge density, and show that they exhibit efficient gene delivery, some surpassing the efficiency of the commercial transfection reagents Polyethylenimine and Lipofectamine 2000. The terpolymers were synthesized via enzyme-catalyzed copolymerization of lactone with dialkyl diester and amino diol, and their hydrophobicity adjusted by varying the lactone content and by selecting a lactone comonomer of specific ring size. Targeted delivery of the pro-apoptotic TRAIL gene to tumour xenografts by one of the terpolymers results in significant inhibition of tumour growth, with minimal toxicity both in vitro and in vivo. Our findings suggest that the gene delivery ability of the terpolymers stems from their high molecular weight and increased hydrophobicity, which compensates for their low charge density. PMID:22138789

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salomon, G.; Park, E.J.; Quock, R.M.

This study was conducted to identify the opioid receptor subtype(s) responsible for RFR-induced analgesia. Male Swiss Webster mice, 20-25 g, were exposed to 20 mW/cm{sup 2} RFR in a 2,450-MHz waveguide system for 10 min, then tested 15 min later in the abdominal constriction paradigm which detects {mu}- and {kappa}-opioid activity. Immediately following RFR exposure, different groups of mice were pretreated intracerebroventricularly with different opioid receptor blockers with selectivity for {mu}- or {kappa}-opioid receptors. Results show that RFR-induced analgesia was attenuated by higher but not lower doses of the non-selective antagonist naloxone, but the selective {mu}-opioid antagonist {beta}-funaltrexamine and bymore » the selective {kappa}-opioid antagonist norbinaltorphimine. RFR-induced analgesia was also reduced by subcutaneous pretreatment with 5.0 mg/kg of the {mu}-/{kappa}-opioid antagonist({minus})-5,9-diethyl-{alpha}-5,9-dialkyl-2{prime}-hydroxy-6,7-benzomorphan(MR-2266). These findings suggest that RFR-induced analgesia may be mediated by both {mu}- and {kappa}-opioid mechanisms.« less

Synthesis, DNA interaction, and cytotoxic activity of a novel proflavine-dithiazolidinone pharmacophore.

PubMed

Janovec, Ladislav; Sabolova, Danica; Kozurkova, Maria; Paulíkova, Helena; Kristian, Pavol; Ungvarský, Jan; Moravcíkova, Erika; Bajdichova, Maria; Podhradský, Dusan; Imrich, Jan

2007-01-01

Five novel proflavine-dithiazolidinone derivatives 4a-4e have been designed and synthesized by the reaction of dialkyl acridin-3,6-diyl dithioureas 3a-3e with methyl bromoacetate. The binding affinity of dithiazolidinone hydrochlorides 5a-5e with calf thymus DNA and plasmid (pUC19) DNA was investigated by a variety of spectroscopic techniques including UV-vis, fluorescence, and CD spectroscopy. The effects of 5a-5e on the thermal denaturation profiles of calf thymus DNA were also studied. From spectrophotometric and spectrofluorimetric titrations, the binding constants for the pUC19 DNA-drug complexes were determined (K = 6.2-2.2 x 104 M-1). In vitro cytotoxic activities of compounds 5a-5e toward murine leukemia cell line L1210 and human uterus carcinoma HeLa cells were also examined. 2',2' '-[(Acridin-3,6-diyl)diimino]-3',3' '-dipropyl-1,3-dithiazolidin-4-one hydrochloride (5b) showed the highest activity against these cells with IC50 values of 6.3 microM and 12.9 microM over the course of 72 h.

Alchemy in the underworld - recent progress and future potential of organic geochemistry applied to speleothems.

NASA Astrophysics Data System (ADS)

Blyth, Alison

2016-04-01

Speleothems are well used archives for chemical records of terrestrial environmental change, and the integration of records from a range of isotopic, inorganic, and organic geochemical techniques offers significant power in reconstructing both changes in past climates and identifying the resultant response in the overlying terrestrial ecosystems. The use of organic geochemistry in this field offers the opportunity to recover new records of vegetation change (via biomarkers and compound specific isotopes), temperature change (via analysis of glycerol dialkyl glycerol tetraethers, a compound group derived from microbes and varying in structure in response to temperature and pH), and changes in soil microbial behaviour (via combined carbon isotope analysis). However, to date the use of organic geochemical techniques has been relatively limited, due to issues relating to sample size, concerns about contamination, and unanswered questions about the origins of the preserved organic matter and rates of transport. Here I will briefly review recent progress in the field, and present a framework for the future research needed to establish organic geochemical analysis in speleothems as a robust palaeo-proxy approach.

Structure of rigid polymers confined to nanoparticles: Molecular dynamics simulations insight

DOE PAGES

Maskey, Sabina; Lane, J. Matthew D.; Perahia, Dvora; ...

2016-02-04

Nanoparticles (NPs) grafted with organic layers form hybrids able to retain their unique properties through integration into the mesoscopic scale. The organic layer structure and response often determine the functionality of the hybrids on the mesoscopic length scale. Using molecular dynamics (MD) simulations, we probe the conformation of luminescent rigid polymers, dialkyl poly(p-phenylene ethynylene)s (PPE), end-grafted onto a silica nanoparticle in different solvents as the molecular weights and polymer coverages are varied. We find that, in contrast to NP-grafted flexible polymers, the chains are fully extended independent of the solvent. In toluene and decane, which are good solvents, the graftedmore » PPEs chains assume a similar conformation to that observed in dilute solutions. In water, which is a poor solvent for the PPEs, the polymer chains form one large cluster but remain extended. The radial distribution of the chains around the core of the nanoparticle is homogeneous in good solvents, whereas in poor solvents clusters are formed independent of molecular weights and coverages. As a result, the clustering is distinctively different from the response of grafted flexible and semiflexible polymers.« less

Occurrence and abundance of 6-methyl branched glycerol dialkyl glycerol tetraethers in soils: Implications for palaeoclimate reconstruction

NASA Astrophysics Data System (ADS)

De Jonge, Cindy; Hopmans, Ellen C.; Zell, Claudia I.; Kim, Jung-Hyun; Schouten, Stefan; Sinninghe Damsté, Jaap S.

2014-09-01

The distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in soils has been shown to correlate with the soil pH and the mean annual air temperature (MAT). This has been used to perform palaeoclimate reconstructions based on brGDGTs recovered from palaeosoils, freshwater, and marine sedimentary archives. Recently described 6-methyl brGDGTs were shown to co-elute with the 5-methyl brGDGTs that are used to calculate the CBT and MBT‧ indices used as palaeoclimate proxies. The impact of these 6-methyl brGDGTs on the established palaeoclimate proxies is unknown and will depend on their abundance in soils. Using improved chromatography, we quantified the fractional abundance of 6-methyl brGDGTs in globally distributed soils and show that they are abundant components, comprising on average 24% of the total amount of brGDGTs. All penta- and hexa-methylated brGDGTs (i.e. with zero to two cyclopentane moieties) were shown to comprise both 5- and 6-methyl isomers. The fractional abundances of the six 6-methyl brGDGTs correlate positively with each other, suggesting a common biological source in most soils, and correlate strongly with soil pH. The presence of the 6-methyl brGDGTs introduced scatter in the original MBT‧/CBT-MAT calibration and caused a dependence on soil pH of the MBT‧. Exclusion of the 6-methyl brGDGTs from the MBT‧, i.e. the newly defined MBT‧5ME, shows that it is no longer related to soil pH. The correlation with MAT is improved, reducing the residual mean error (RMSE) from 6.2 to 4.8 °C. Also, the correlation of the CBT after the exclusion of the 6-methyl brGDGTs (defined as CBT5ME) with soil pH slightly improved. Furthermore, the separate quantification of the 6-methyl brGDGTs allows the definition of new indices. The CBT‧, which comprises the 6-methyl brGDGTs, is a substantially improved alternative to the CBT5ME, reducing the RMSE from 0.8 to 0.5 pH units. Also, the accuracy of MAT reconstructions can be improved using a multiple linear regression, the MATmr, decreasing the RMSE further to 4.6 °C. Furthermore, we introduce an index that allows the reconstruction of MAT in sites where only the ubiquitous brGDGT Ia, IIa and IIIa are present, the MATmrs. Our results imply that separate quantification of the 6- and 5-methyl brGDGT is essential for accurately quantifying brGDGTs in environmental samples and results in substantially improved MAT and soil pH reconstructions.

Versatile reactivities of rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized β-diketiminato ligand.

PubMed

Zhu, Xiancui; Li, Yang; Guo, Dianjun; Wang, Shaowu; Wei, Yun; Zhou, Shuangliu

2018-03-12

Herein, rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized β-diketiminato ligand with the formula LRE(CH 2 SiMe 3 ) 2 (thf) (RE = Y (1a), Dy (1b), Er (1c), Yb (1d); L = MeC(NDipp)CHC(Me)NCH 2 CH 2 NC 4 H 2 -2,5-Me 2 , Dipp = 2,6- i Pr 2 C 6 H 3 ) were synthesized via the reactions of the β-diketimine HL with the rare-earth metal trialkyl complexes RE(CH 2 SiMe 3 ) 3 (thf) 2 in high yields. The reactivities of 1 with pyridine derivatives, unsaturated substrates, and elemental sulfur were investigated, and some interesting chemical transformations were observed. Ligand exchange and activation of sp 2 and sp 3 C-H bonds occurred during the reactions with pyridine derivatives to afford different types of mononuclear rare-earth metal pyridyl complexes, namely, LEr(CH 2 SiMe 3 ) 2 (η 1 -NC 5 H 4 ) (2c), LRE(η 3 -CH 2 -2-NC 5 H 2 -4,6-Me 2 ) 2 (RE = Y (3a), Er (3c)), and LRE(CH 2 SiMe 3 )(η 2 -(C,N)-2-(2-C 6 H 4 NC 5 H 4 )) (RE = Er (4c), Yb = (4d)). Similarly, activation of the sp C-H bond occurred during the reaction of phenylacetylene with 1c to produce the dinuclear erbium alkynyl complex [LEr(CH 2 SiMe 3 )(μ-C[triple bond, length as m-dash]CPh)] 2 (5c). The mixed amidinate-β-diketiminato ytterbium complex LYb[(Dipp)NC(CH 2 SiMe 3 )N(Dipp)](CH 2 SiMe 3 ) (6d) was obtained by the insertion of bis(2,6-diisopropylphenyl)carbodiimide into a Yb-alkyl bond, as well as via the direct alkane elimination of a CH 2 SiMe 3 moiety with bis(2,6-diisopropylphenyl)formamidine to afford the erbium complex LEr(DippNCHNDipp)(CH 2 SiMe 3 ) (7c). A rare sp 2 C-H bond oxidation of the β-diketiminato backbone with elemental sulfur insertion was detected to provide the unprecedented dinuclear rare-earth metal thiolate complexes (LRE) 2 (μ-SCH 2 SiMe 3 ) 2 (μ-SCC(Me)(NDipp)C(Me)NCH 2 CH 2 NC 4 H 2 Me 2 -2,5) (RE = Y (8a), Er (8c)) in the reactions of S 8 with 1a and 1c, respectively. The molecular structures of the complexes 1-8 were determined by single-crystal X-ray diffraction analyses.

Novel fluconazole derivatives with promising antifungal activity.

PubMed

Thamban Chandrika, Nishad; Shrestha, Sanjib K; Ngo, Huy X; Howard, Kaitlind C; Garneau-Tsodikova, Sylvie

2018-02-01

The fungistatic nature and toxicity concern associated with the azole drugs currently on the market have resulted in an increased demand for new azole antifungal agents for which these problematic characteristics do not exist. The extensive use of azoles has resulted in fungal strains capable of resisting the action of these drugs. Herein, we report the synthesis and antifungal activity of novel fluconazole (FLC) analogues with alkyl-, aryl-, cycloalkyl-, and dialkyl-amino substituents. We evaluated their antifungal activity by MIC determination and time-kill assay as well as their safety profile by hemolytic activity against murine erythrocytes as well as cytotoxicity against mammalian cells. The best compounds from our study exhibited broad-spectrum activity against most of the fungal strains tested, with excellent MIC values against a number of clinical isolates. The most promising compounds were found to be less hemolytic than the least hemolytic FDA-approved azole antifungal agent voriconazole (VOR). Finally, we demonstrated that the synthetic alkyl-amino FLC analogues displayed chain-dependent fungal membrane disruption as well as inhibition of ergosterol biosynthesis as possible mechanisms of action. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemical Properties of Dialkyl Halonium Ions (R2Hal+) and Their Neutral Analogues, Methyl Carboranes, CH3-(CHB11Hal11), Where Hal = F, Cl.

PubMed

Stoyanov, Evgenii S

2017-04-20

Chloronium cations in their salts (C n H 2n+1 ) 2 Cl + {CHB 11 Cl 11 - }, with n = 1 to 3 and exceptionally stable carborane anions, are stable at ambient and elevated temperatures. The temperature at which they decompose to carbocations with HCl elimination (below 150 °C) decreases with the increasing n from 1 to 3 because of increasing ionicity of C-Cl bonds in the C-Cl + -C bridge. At room temperature, the salts of cations with n ≥ 4 [starting from t-Bu 2 Cl + or (cyclo-C 5 H 11 ) 2 Cl + ] are unstable and decompose. With decreasing chloronium ion stability, their ability to interact with chloroalkanes to form oligomeric cations increases. It was shown indirectly that unstable salt of fluoronium ions (CH 3 ) 2 F + (CHB 11 F 11 - ) must exist at low temperatures. The proposed (CH 3 ) 2 F + cation is much more reactive than the corresponding chloronium, showing at room temperature chemical properties expected of (CH 3 ) 2 Cl + at elevated temperatures.

Preservation of Microbial Lipids in Geothermal Sinters

NASA Astrophysics Data System (ADS)

Kaur, Gurpreet; Mountain, Bruce W.; Hopmans, Ellen C.; Pancost, Richard D.

2011-04-01

Lipid biomarkers are widely used to study the earliest life on Earth and have been invoked as potential astrobiological markers, but few studies have assessed their survival and persistence in geothermal settings. Here, we investigate lipid preservation in active and inactive geothermal silica sinters, with ages of up to 900 years, from Champagne Pool, Waiotapu, New Zealand. Analyses revealed a wide range of bacterial biomarkers, including free and bound fatty acids, 1,2-di-O-alkylglycerols (diethers), and various hopanoids. Dominant archaeal lipids include archaeol and glycerol dialkyl glycerol tetraethers (GDGTs). The predominance of generally similar biomarker groups in all sinters suggests a stable microbial community throughout Champagne Pool's history and indicates that incorporated lipids can be well preserved. Moreover, subtle differences in lipid distributions suggest that past changes in environmental conditions can be elucidated. In this case, higher archaeol abundances relative to the bacterial diethers, a greater proportion of cyclic GDGTs, the high average chain length of the bacterial diethers, and greater concentrations of hopanoic acids in the older sinters all suggest hotter conditions at Champagne Pool in the past.

Decarbonylative Phosphorylation of Amides by Palladium and Nickel Catalysis: The Hirao Cross-Coupling of Amide Derivatives.

PubMed

Liu, Chengwei; Szostak, Michal

2017-10-02

Considering the ubiquity of organophosphorus compounds in organic synthesis, pharmaceutical discovery agrochemical crop protection and materials chemistry, new methods for their construction hold particular significance. A conventional method for the synthesis of C-P bonds involves cross-coupling of aryl halides and dialkyl phosphites (the Hirao reaction). We report a catalytic deamidative phosphorylation of a wide range of amides using a palladium or nickel catalyst giving aryl phosphonates in good to excellent yields. The present method tolerates a wide range of functional groups. The reaction constitutes the first example of a transition-metal-catalyzed generation of C-P bonds from amides. This redox-neutral protocol can be combined with site-selective conventional cross-coupling for the regioselective synthesis of potential pharmacophores. Mechanistic studies suggest an oxidative addition/transmetallation pathway. In light of the importance of amides and phosphonates as synthetic intermediates, we envision that this Pd and Ni-catalyzed C-P bond forming method will find broad application. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inter-decadal changes in the intensity of the Oxygen Minimum Zone off Concepción, Chile (~ 36° S) over the last century

NASA Astrophysics Data System (ADS)

Srain, B.; Pantoja, S.; Sepúlveda, J.; Lange, C. B.; Muñoz, P.; Summons, R. E.; McKay, J.; Salamanca, M.

2015-04-01

We reconstructed oxygenation changes in the Oxygen Minimum Zone of the upwelling ecosystem off Concepción (36° S), Chile, using inorganic and organic proxies in a sediment core covering the last ca. 110 years of sedimentation in this area. Authigenic enrichments of Mo, U and Cd were observed between ca. 1935-1971 CE indicating a prolonged period of more reduced conditions in bottom waters and surface sediments. Significant positive correlations (p < 0.05; Spearman) between redox sensitive metals, algal sterols, biomarkers of anaerobic microorganisms, and archaeal glycerol dialkyl glycerol tetraether indicated a coupling among bottom water oxygen depletion, and increased primary and export production, suggesting that the period with low O2 of ca. 35 years, follows low frequency inter-decadal variation of the Pacific Decadal Oscillation, which may have resulted in O2 depletion over the entire continental shelf off Concepción. Taken together with the concurrent increase in sedimentary molecular indicators of anaerobic microbes allow us to suggest that the prokaryote community has been influenced by changes in oxygenation of the water column.

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part II. Application to sediment and sludge samples in Austria.

PubMed

Martínez-Carballo, Elena; González-Barreiro, Carmen; Sitka, Andrea; Kreuzinger, Norbert; Scharf, Sigrid; Gans, Oliver

2007-03-01

Soxhlet extraction and high-performance liquid chromatography (HPLC) coupled to tandem mass spectrometry detection (MS/MS) was used for the determination of selected quaternary ammonium compounds (QACs) in solid samples. The method was applied for the determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds in sediment and sludge samples in Austria. The overall method quantification limits range from 0.6 to 3 microg/kg for sediments and from 2 to 5 microg/kg for sewage sludges. Mean recoveries between 67% and 95% are achieved. In general sediments were especially contaminated by C12 chain benzalkonium chloride (BAC-C12) as well as by the long C-chain dialkyldimethylammonium chloride (DDAC-C18) with a maximum concentration of 3.6 mg/kg and 2.1mg/kg, respectively. Maxima of 27 mg/kg for DDAC-C10, 25 mg/kg for BAC-C12 and 23 mg/kg for BAC-C14 were determined for sludge samples. The sums of the 12 selected target compounds range from 22 mg/kg to 103 mg/kg in the sludge samples.

Regenerable antioxidants-introduction of chalcogen substituents into tocopherols.

PubMed

Poon, Jia-Fei; Singh, Vijay P; Yan, Jiajie; Engman, Lars

2015-02-02

To improve the radical-trapping capacity of the natural antioxidants, alkylthio-, alkylseleno-, and alkyltelluro groups were introduced into all vacant aromatic positions in β-, γ- and δ-tocopherol. Reaction of the tocopherols with electrophilic chalcogen reagents generated by persulfate oxidation of dialkyl dichalcogenides provided convenient but low-yielding access to many sulfur and selenium derivatives, but failed in the case of tellurium. An approach based on lithiation of the appropriate bromo-tocopherol, insertion of chalcogen into the carbon-lithium bond, air-oxidation to a dichalcogenide, and final borohydride reduction/alkylation turned out to be generally applicable to the synthesis of all chalcogen derivatives. Whereas alkylthio- and alkylseleno analogues were generally poorer quenchers of lipid peroxyl radicals than the corresponding parents, all tellurium compounds showed a substantially improved radical-trapping activity. Introduction of alkyltelluro groups into the tocopherol scaffold also caused a dramatic increase in the regenerability of the antioxidant. In a two-phase lipid peroxidation system containing N-acetylcysteine as a water-soluble co-antioxidant the inhibition time was up to six-fold higher than that recorded for the natural antioxidants. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biological evaluation of omega-(dialkylamino)alkyl derivatives of 6H-indolo[2,3-b]quinoline--novel cytotoxic DNA topoisomerase II inhibitors.

PubMed

Godlewska, Joanna; Luniewski, Wojciech; Zagrodzki, Bogdan; Kaczmarek, Lukasz; Bielawska-Pohl, Aleksandra; Dus, Danuta; Wietrzyk, Joanna; Opolski, Adam; Siwko, Magdalena; Jaromin, Anna; Jakubiak, Anna; Kozubek, Arkadiusz; Peczyñska-Czoch, Wanda

2005-01-01

A series of novel 6H-indolo[2,3-b]quinoline derivatives, substituted at C-2, C-9 or N-6 position with dialkyl(alkylamino)alkyl chains differing in the number of methylene groups, was prepared. These compounds were evaluated in vitro for their antimicrobial and cytotoxic activity against several cell lines of different origin and tested for their ability to influence the cell cycle and inhibit topoisomerase II activity. Liphophilic and calf thymus DNA-binding properties of these compounds were also investigated. All the compounds tested inhibited the growth of Gram-positive bacteria and fungi at MIC values ranging between 0.25 and 1 mM. They also showed cytotoxic activity against KB (human cervix carcinoma) cells (ID50 varied from 2.1 to 9.0 microM) and were able to overcome multidrug resistance in colorectal adenocarcinoma LoVo/DX, uterine sarcoma MES-SA/DX5 and promyelocytic leukemia HL-60/MX2 cells (the values of the resistance index RI fell between 0.54 and 2.4). The compounds induced G2M-phase cell cycle arrest in Jurkat T-cell leukemia cells, revealed DNA-binding properties and inhibited topoisomerase II activity.

From biomass to chemicals: synthesis of precursors of biodegradable surfactants from 5-hydroxymethylfurfural.

PubMed

Arias, K S; Al-Resayes, Saud I; Climent, Maria J; Corma, Avelino; Iborra, Sara

2013-01-01

The selective acetalization of 5-hydroxymethylfurfural (HMF) with long-chain alkyl alcohols has been performed to obtain precursors of molecules with surfactant properties. If direct acetalization of HMF with n-octanol is performed in the presence of strong acids (homogeneous and heterogeneous catalysts), an increase in etherification versus acetalization occurs. Beta zeolite catalyzes both reactions. However, if the acidity of a zeolite (Beta) was controlled by partial exchange of H(+) with Na(+), the dioctyl acetal of HMF can be achieved in 95% yield by transacetalization. It is possible to achieve a high yield in a very short reaction time through a two-step one-pot process, which includes the synthesis of the dimethyl acetal of HMF followed by transacetalization with n-octanol. The one-pot process could be extended to other alcohols that contain 6-12 carbon atoms to afford 87-98% yield of the corresponding dialkyl acetal with a selectivity higher than 96%. The optimized catalyst with an adequate Na content (1.5NaBeta) could be recycled without loss of activity or selectivity. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cl⋯N weak interactions. Conformational analysis of imidazol-2-ylum heterocycles bearing N-β-chloroethyl and N-vinyl pendant groups

NASA Astrophysics Data System (ADS)

Rodríguez-López, Germán; Montes-Tolentino, Pedro; Sánchez-Ruiz, Sonia; Villaseñor-Granados, Tayde Osvaldo; Flores-Parra, Angelina

2017-11-01

Enantiomerically pure and racemic mixtures of β-chloroethylamines hydrochlorides with one and two stereogenic centres were used to synthesise 1,4-dialkyl-1,3-diimines, which in turn gave place to a series of imidazolium chlorides and tetraphenylborates bearing pendant N-β-chloroethyl substituents (sbnd CHEt-CH2Cl; sbnd CHMe-CHPhCl). Stereoselective dehydrochlorination of imidazolium compounds afforded in good yield the corresponding heterocycles bearing N-vinyl groups (-CEt=CH2; -CMe=CHPh). The volume of the N-substituents provides a steric screening of the cationic ring. The structure of the new compounds was determined by IR, mass spectra, NMR and X-ray diffraction analyses as well as DFT calculations of the optimized geometries. Uncommon stabilising intramolecular Cl⋯N weak interactions are described, together with H⋯Cl and H···π hydrogen bonds. The existence of the non-covalent weak intramolecular bonds was deduced from the X-ray diffraction analysis and confirmed by calculations of the electrostatic potential, electronic density distributions and the maps of the Laplacian functions of the electronic density.

Impact of water depth on the distribution of iGDGTs in the surface sediments from the northern South China Sea: applicability of TEX86 in marginal seas

NASA Astrophysics Data System (ADS)

Chen, Jiali; Hu, Pengju; Li, Xing; Yang, Yang; Song, Jinming; Li, Xuegang; Yuan, Huamao; Li, Ning; Lü, Xiaoxia

2018-03-01

The TEX 86 H paleothermometer on the base of isoprenoid glycerol dialkyl glycerol tetraethers (iGDGTs) has been widely applied to various marine settings to reconstruct past sea surface temperatures (SSTs). However, it remains uncertain how well this proxy reconstructs SSTs in marginal seas. In this study, we analyze the environmental factors governing distribution of iGDGTs in surface sediments to assess the applicability of TEX 86 H paleothermometer in the South China Sea (SCS). Individual iGDGT concentrations increase gradually eastwards. Redundancy analysis based on the relative abundance of an individual iGDGT compound and environmental parameters suggests that water depth is the most influential factor to the distribution of iGDGTs, because thaumarchaeota communities are water-depth dependent. Interestingly, the SST difference (Δ T) between TEX 86 H derived temperature and remote-sensing SST is less than 1°C in sediments with water depth>200 m, indicating that TEX 86 H was the robust proxy to trace the paleo-SST in the region if water depth is greater than 200 m.

Simple hollow fiber renewal liquid membrane extraction method for pre-concentration of Cd(II) in environmental samples and detection by flame atomic absorption spectrometry.

PubMed

Carletto, Jeferson Schneider; Luciano, Raquel Medeiros; Bedendo, Gizelle Cristina; Carasek, Eduardo

2009-04-06

A hollow fiber renewal liquid membrane (HFRLM) extraction method to determine cadmium (II) in water samples using Flame Atomic Absorption Spectrometry (FAAS) was developed. Ammonium O,O-diethyl dithiophosphate (DDTP) was used to complex cadmium (II) in an acid medium to obtain a neutral hydrophobic complex (ML(2)). The organic solvent introduced to the sample extracts this complex from the aqueous solution and carries it over the poly(dimethylsiloxane) (PDMS) membrane, that had their walls previously filled with the same organic solvent. The organic solvent is solubilized inside the PDMS membrane, leading to a homogeneous phase. The complex strips the lumen of the membrane where, at higher pH, the complex Cd-DDTP is broken down and cadmium (II) is released into the stripping phase. EDTA was used to complex the cadmium (II), helping to trap the analyte in the stripping phase. A multivariate procedure was used to optimize the studied variables. The optimized variables were: sample (donor phase) pH 3.25, DDTP concentration 0.05% (m/v), stripping (acceptor phase) pH 8.75, EDTA concentration 1.5x10(-2) mol L(-1), extraction temperature 40 degrees C, extraction time 40 min, a solvent mixture N-butyl acetate and hexane (60/40%, v/v) with a volume of 100 microL, and addition of ammonium sulfate to saturate the sample. The sample volume used was 20 mL and the stripping volume was 165 microL. The analyte enrichment factor was 120, limit of detection (LOD) 1.3 microg L(-1), relative standard deviation (RSD) 5.5% and the working linear range 2-30 microg L(-1).

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light-emitting diodes

NASA Astrophysics Data System (ADS)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-07-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90 %). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize product yields and to identify side products. The present work demonstrates that UV-LED arrays are a viable alternative to current Hg lamp setups.

Processes of Fatigue Destruction in Nanopolymer-Hydrophobised Ceramic Bricks.

PubMed

Fic, Stanisław; Szewczak, Andrzej; Barnat-Hunek, Danuta; Łagód, Grzegorz

2017-01-06

The article presents a proposal of a model of fatigue destruction of hydrophobised ceramic brick, i.e., a basic masonry material. The brick surface was hydrophobised with two inorganic polymers: a nanopolymer preparation based on dialkyl siloxanes (series 1-5) and an aqueous silicon solution (series 6-10). Nanosilica was added to the polymers to enhance the stability of the film formed on the brick surface. To achieve an appropriate blend of the polymer liquid phase and the nano silica solid phase, the mixture was disintegrated by sonication. The effect of the addition of nano silica and sonication on changes in the rheological parameters, i.e., viscosity and surface tension, was determined. Material fatigue was induced by cyclic immersion of the samples in water and drying at a temperature of 100 °C, which caused rapid and relatively dynamic movement of water. The moisture and temperature effect was determined by measurement of changes in surface hardness performed with the Vickers method and assessment of sample absorbability. The results provided an approximate picture of fatigue destruction of brick and hydrophobic coatings in relation to changes in their temporal stability. Additionally, SEM images of hydrophobic coatings in are shown.

Metal alkyls programmed to generate metal alkylidenes by α-H abstraction: prognosis from NMR chemical shift† †Electronic supplementary information (ESI) available: Experimental and computational details, NMR spectra, results of NMR calculations and NCS analysis, graphical representation of shielding tensors, molecular orbital diagrams of selected compounds, optimized structures for all calculated species. See DOI: 10.1039/c7sc05039a

PubMed Central

Gordon, Christopher P.; Yamamoto, Keishi; Searles, Keith; Shirase, Satoru

2018-01-01

Metal alkylidenes, which are key organometallic intermediates in reactions such as olefination or alkene and alkane metathesis, are typically generated from metal dialkyl compounds [M](CH2R)2 that show distinctively deshielded chemical shifts for their α-carbons. Experimental solid-state NMR measurements combined with DFT/ZORA calculations and a chemical shift tensor analysis reveal that this remarkable deshielding originates from an empty metal d-orbital oriented in the M–Cα–Cα′ plane, interacting with the Cα p-orbital lying in the same plane. This π-type interaction inscribes some alkylidene character into Cα that favors alkylidene generation via α-H abstraction. The extent of the deshielding and the anisotropy of the alkyl chemical shift tensors distinguishes [M](CH2R)2 compounds that form alkylidenes from those that do not, relating the reactivity to molecular orbitals of the respective molecules. The α-carbon chemical shifts and tensor orientations thus predict the reactivity of metal alkyl compounds towards alkylidene generation. PMID:29675237

Late Pliocene and Early Pleistocene Temperature Reconstructions from Paleolakes of the West Turkana and North Awash Basins, East Africa

NASA Astrophysics Data System (ADS)

Castañeda, I. S.; Thompson-Munson, M.; Lupien, R.; Russell, J. M.

2015-12-01

The Hominin Sites and Paleolakes Drilling Project (HSPDP) aims to reconstruct past environments of the East African Rift Valley from locations in close proximity to some of the world's most important fossil hominin and artifact sites. In this study, we investigate sediments from the West Turkana and North Awash Basins, which were recently drilled as part of the HSPDP. The North Awash Basin contains abundant early hominin fossils and the lakebeds of the Hadar Formation (~3.6 to ~2.9 Ma) will provide a record of climate variability during the Pliocene, prior to the intensification of Northern Hemisphere glaciation at ~2.7 Ma. The lakebeds of the Turkana Basin are Early Pleistocene in age (~1.9 to ~1.45 Ma) and span the interval that includes some the earliest fossils of Homo rudolfensis and H. ergaster/erectus. Here we examine the organic geochemistry of West Turkana and North Awash Basin sediments and investigate the use of proxies based on isoprenoid and branched glycerol dialkyl glycerol tetraethers (GDGTs) to reconstruct temperature, including TEX86 and the methylation and cyclization (MBT and CBT) ratios and relative abundances of branched GDGTs. We also examine variability in the abundances and ratios of plant leaf waxes (n-alkanes) to provide insight into past vegetation changes on the East African landscape.

Modification of aniline containing proteins using an oxidative coupling strategy.

PubMed

Hooker, Jacob M; Esser-Kahn, Aaron P; Francis, Matthew B

2006-12-13

A new bioconjugation reaction has been developed based on the chemoselective modification of anilines through an oxidative coupling pathway. Aryl amines were installed on the surface of protein substrates through lysine acylation reactions or through the use of native chemical ligation techniques. Upon exposure to NaIO4 in aqueous buffer, the anilines coupled rapidly to the aromatic rings of N,N-dialkyl-N'-acyl-p-phenylenediamines. The identities of the reaction products were confirmed using ESI-MS and through comparison to small molecule analogs. Control experiments indicated that none of the native amino acids participated in the reaction. The resulting bioconjugates were found to be stable toward hydrolysis from pH 4 to pH 11 and in the presence of many commonly used oxidants, reductants, and nucleophiles. A fluorescent phenylenediamine reagent was synthesized for the selective detection of aniline labeled proteins in mixtures, and the reaction was used to append the C-terminus of the green fluorescent protein with a single PEG chain. When combined with techniques for the incorporation of unnatural amino acids into proteins, this bioorthogonal coupling method should prove useful for a number of applications requiring a high degree of labeling specificity.

Pentafluorobenzyl bromide-A versatile derivatization agent in chromatography and mass spectrometry: I. Analysis of inorganic anions and organophosphates.

PubMed

Tsikas, Dimitrios

2017-02-01

Pentafluorobenzyl bromide (PFB-Br) is a versatile derivatization agent. It is widely used in chromatography and mass spectrometry since several decades. The bromide atom is largely the single leaving group of PFB-Br. It is substituted by wide a spectrum of nucleophiles in aqueous and non-aqueous systems to form electrically neutral, in most organic solvents soluble, generally thermally stable, volatile, strongly electron-capturing and ultraviolet light-absorbing derivatives. Because of these greatly favoured physicochemical properties, PFB-Br emerged an ideal derivatization agent for highly sensitive analysis of endogenous and exogenous substances including various inorganic and organic anions by electron capture detection or after electron-capture negative-ion chemical ionization in GC-MS. The present article attempts an appraisal of the utility of PFB-Br in analytical chemistry. It reviews and discusses papers dealing with the use of PFB-Br as the derivatization reagent in the qualitative and quantitative analysis of endogenous and exogenous inorganic anions in various biological samples, notably plasma, urine and saliva. These analytes include nitrite, nitrate, cyanide and dialkyl organophosphates. Special emphasis is given to mass spectrometry-based approaches and stable-isotope dilution techniques. Copyright © 2016 Elsevier B.V. All rights reserved.

Processes of Fatigue Destruction in Nanopolymer-Hydrophobised Ceramic Bricks

PubMed Central

Fic, Stanisław; Szewczak, Andrzej; Barnat-Hunek, Danuta; Łagód, Grzegorz

2017-01-01

The article presents a proposal of a model of fatigue destruction of hydrophobised ceramic brick, i.e., a basic masonry material. The brick surface was hydrophobised with two inorganic polymers: a nanopolymer preparation based on dialkyl siloxanes (series 1–5) and an aqueous silicon solution (series 6–10). Nanosilica was added to the polymers to enhance the stability of the film formed on the brick surface. To achieve an appropriate blend of the polymer liquid phase and the nano silica solid phase, the mixture was disintegrated by sonication. The effect of the addition of nano silica and sonication on changes in the rheological parameters, i.e., viscosity and surface tension, was determined. Material fatigue was induced by cyclic immersion of the samples in water and drying at a temperature of 100 °C, which caused rapid and relatively dynamic movement of water. The moisture and temperature effect was determined by measurement of changes in surface hardness performed with the Vickers method and assessment of sample absorbability. The results provided an approximate picture of fatigue destruction of brick and hydrophobic coatings in relation to changes in their temporal stability. Additionally, SEM images of hydrophobic coatings in are shown. PMID:28772404

Influence of Polyethylene Glycol Lipid Desorption Rates on Pharmacokinetics and Pharmacodynamics of siRNA Lipid Nanoparticles

PubMed Central

Mui, Barbara L; Tam, Ying K; Jayaraman, Muthusamy; Ansell, Steven M; Du, Xinyao; Tam, Yuen Yi C; Lin, Paulo JC; Chen, Sam; Narayanannair, Jayaprakash K; Rajeev, Kallanthottathil G; Manoharan, Muthiah; Akinc, Akin; Maier, Martin A; Cullis, Pieter; Madden, Thomas D; Hope, Michael J

2013-01-01

Lipid nanoparticles (LNPs) encapsulating short interfering RNAs that target hepatic genes are advancing through clinical trials, and early results indicate the excellent gene silencing observed in rodents and nonhuman primates also translates to humans. This success has motivated research to identify ways to further advance this delivery platform. Here, we characterize the polyethylene glycol lipid (PEG-lipid) components, which are required to control the self-assembly process during formation of lipid particles, but can negatively affect delivery to hepatocytes and hepatic gene silencing in vivo. The rate of transfer from LNPs to plasma lipoproteins in vivo is measured for three PEG-lipids with dialkyl chains 14, 16, and 18 carbons long. We show that 1.5 mol % PEG-lipid represents a threshold concentration at which the chain length exerts a minimal effect on hepatic gene silencing but can still modify LNPs pharmacokinetics and biodistribution. Increasing the concentration to 2.5 and 3.5 mol % substantially compromises hepatocyte gene knockdown for PEG-lipids with distearyl (C18) chains but has little impact for shorter dimyristyl (C14) chains. These data are discussed with respect to RNA delivery and the different rates at which the steric barrier disassociates from LNPs in vivo. PMID:24345865

Computing UV/vis spectra using a combined molecular dynamics and quantum chemistry approach: bis-triazin-pyridine (BTP) ligands studied in solution.

PubMed

Höfener, Sebastian; Trumm, Michael; Koke, Carsten; Heuser, Johannes; Ekström, Ulf; Skerencak-Frech, Andrej; Schimmelpfennig, Bernd; Panak, Petra J

2016-03-21

We report a combined computational and experimental study to investigate the UV/vis spectra of 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine (BTP) ligands in solution. In order to study molecules in solution using theoretical methods, force-field parameters for the ligand-water interaction are adjusted to ab initio quantum chemical calculations. Based on these parameters, molecular dynamics (MD) simulations are carried out from which snapshots are extracted as input to quantum chemical excitation-energy calculations to obtain UV/vis spectra of BTP ligands in solution using time-dependent density functional theory (TDDFT) employing the Tamm-Dancoff approximation (TDA). The range-separated CAM-B3LYP functional is used to avoid large errors for charge-transfer states occurring in the electronic spectra. In order to study environment effects with theoretical methods, the frozen-density embedding scheme is applied. This computational procedure allows to obtain electronic spectra calculated at the (range-separated) DFT level of theory in solution, revealing solvatochromic shifts upon solvation of up to about 0.6 eV. Comparison to experimental data shows a significantly improved agreement compared to vacuum calculations and enables the analysis of relevant excitations for the line shape in solution.

Interdecadal changes in intensity of the oxygen minimum zone off Concepción, Chile (~ 36° S), over the last century

NASA Astrophysics Data System (ADS)

Srain, B.; Pantoja, S.; Sepúlveda, J.; Lange, C. B.; Muñoz, P.; Summons, R. E.; McKay, J.; Salamanca, M.

2015-10-01

We reconstructed oxygenation changes in the upwelling ecosystem off Concepción (36° S), Chile, using inorganic and organic proxies in a sediment core covering the last ca. 110 years of sedimentation in this area. Authigenic enrichments of Mo, U and Cd were observed between ca. 1935 and 1971 CE, implying a prolonged period with predominantly more reduced conditions in bottom waters and surface sediments. Significant positive correlations between redox-sensitive metals, algal sterols, biomarkers of micro-aerophilic and anaerobic microorganisms, and archaeal glycerol dialkyl glycerol tetraethers point to a tight coupling among bottom water O2 depletion and increased primary and export production. The time interval with low O2 of ca. 35 years seems to follow low-frequency interdecadal variation of the Pacific Decadal Oscillation, and it may have resulted in O2 depletion over the entire continental shelf off Concepción. Taking this together with the concurrent increase in sedimentary molecular indicators of micro-aerophilic and anaerobic microbes, we can suggest that changes in oxygenation of the water column are reflected by changes in microbial community. This study can inform our understanding of ecological consequences to projected trends in ocean deoxygenation.

Novel bright-emission small-molecule NIR-II fluorophores for in vivo tumor imaging and image-guided surgery† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc00251c Click here for additional data file.

PubMed Central

Sun, Yao; Ding, Mingmin; Zeng, Xiaodong; Xiao, Yuling; Wu, Huaping; Zhou, Hui; Ding, Bingbing; Qu, Chunrong; Hou, Wei; Er-bu, AGA; Zhang, Yejun; Cheng, Zhen

2017-01-01

Though high brightness and biocompatible small NIR-II dyes are highly desirable in clinical or translational cancer research, their fluorescent cores are relatively limited and their synthetic processes are somewhat complicated. Herein, we have explored the design and synthesis of novel NIR-II fluorescent materials (H1) without tedious chromatographic isolation with improved fluorescence performance (QY ≈ 2%) by introducing 2-amino 9,9-dialkyl-substituted fluorene as a donor into the backbone. Several types of water-soluble and biocompatible NIR-II probes: SXH, SDH, and H1 NPs were constructed via different chemical strategies based on H1, and then their potential to be used in in vivo tumor imaging and image-guided surgery in the NIR-II region was explored. High levels of uptake were obtained for both passive and active tumor targeting probes SXH and SDH. Furthermore, high resolution imaging of blood vessels on tumors and the whole body of living mice using H1 NPs for the first time has demonstrated precise NIR-II image-guided sentinel lymph node (SLN) surgery. PMID:28507722

[Study on the kinetics of organo-clay removing red tide organisms].

PubMed

Wu, Ping; Yu, Zhi-ming

2007-07-01

The kinetics of red tide organisms (Heterosigma akashiwo and Scrippsiella trochoidea) coagulation with clays modified by dialkyl-polyoxyethenyl quaternary ammonium compound (DPQAC) was studied using spectrophotometer and fluorometry, and the effects of different kinds and concentrations of clays, the second component DPQAC added in clays and pH on the coagulation rate were examined. When using spectrophotometer, the coagulation kinetics of red tide organism coagulation with organo-clays is well fit for the bimolecular reaction model; while using fluorometry, it is fit for the hyperbola model much better. Moreover, the results also prove that using fluorometry can avoid the great change of permeance efficiency caused by clays' sedimentation when using spectrophotometer, which has availably avoided the influence of clays' sedimentation and reflected the essential of algal coagulation and sedimentation well and truly. The results of two studying methods show that the coagulation rate is more rapid in the system of kaolin than in that of bentonite; increasing the concentration of clays and DPQAC and increasing pH all can accelerate coagulation, and among those increasing the concentration of DPQAC is the most efficient way of increasing the removal efficiency and coagulation rate.

Effect of oxygen concentration in ZDP containing oils on surface composition and wear

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Ferrante, J.

1983-01-01

A pin-on-disk wear study was performed with the lubricants dibutyl sebacate (DBS) and mineral oil (MO) with and without 1 weight percent zinc-dialkyl-dithiophospatee (ZDP) as an additive. The pin was annealed pure iron and the disk was M-2 tool steel. The selected load and speed guaranteed boundary lubrication. The ambient atmospheric oxygen concentration in an oxygen-nitrogen mixture was varied from 0 percent to 20 percent in order to examine its relationship to ZDP effectiveness. Auger electron spectroscopy combined with argon ion bombardment (depth profiling) was used to determine surface elemental composition on the pin when tested in DBS with and without ZDP. The ambient atmosphere was found to cause large variations in wear rate and surface composition. With MO, ZDP reduced wear under all conditions, but had little advantage over oxides formed at 20 percent oxygen atmosphere. With DBS, ZDP reduced wear at 0 percent oxygen, but gave varied results at other oxygen concentrations. Depth profiling revealed sulfuide formation at 0 percent oxygen and probably sulfates at 20 percent oxygen. The results are significant because varied oxygen concentrations can occur under actual lubricating conditions in practical machinery.

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light emitting diodes

NASA Astrophysics Data System (ADS)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-01-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90%). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize products yields and to identify side products. The use of UV-LED arrays offers many advantages over conventional Hg lamp setups, including greater light output over a narrower wavelength range, lower power consumption, and minimal generation of heat.

Cu-Fe-S Nanocrystals Exhibiting Tunable Localized Surface Plasmon Resonance in the Visible to NIR Spectral Ranges.

PubMed

Gabka, Grzegorz; Bujak, Piotr; Ostrowski, Andrzej; Tomaszewski, Waldemar; Lisowski, Wojciech; Sobczak, Janusz W; Pron, Adam

2016-07-05

Cu-Fe-S nanocrystals exhibiting a strong localized surface plasmon resonance (LSPR) effect were synthesized for the first time. The elaborated reproducible preparation procedure involved copper(II) oleate, iron(III) stearate, and sulfur powder dissolved in oleylamine (OLA) as precursors. The wavelength of the plasmonic resonance maximum could be tuned by changing the Cu/Fe ratio in the resulting nanocrystals, being the most energetic for the 1:1 ratio (486 nm) and undergoing a bathochromic shift to ca. 1200 nm with an increase to 6:1. LSPR could also be observed in nanocrystals prepared from the same metal precursors and sulfur powder dissolved in 1-octadecene (ODE), provided that the sulfur precursor was taken in excess. Detailed analysis of the reaction mixture by chromatographic techniques, supplemented by mass spectrometry and (1)H NMR spectroscopy enabled the identification of the true chemical nature of the sulfur precursor in S/OLA, namely, (C18H35NH3(+))(C18H35NH-S8(-)), a reactive product of the reduction of elemental sulfur by the amine groups of OLA. In the case of the S/ODE precursor, the true precursors are much less reactive primary or secondary thioethers and dialkyl polysulfides.

P alpha-chiral phosphorothioate analogues of bis(5'-adenosyl)tetraphosphate (Ap4A); their enzymatic synthesis and degradation.

PubMed Central

Lazewska, D; Guranowski, A

1990-01-01

Synthesis of Sp and Rp diastereomers of Ap4A alpha S has been characterized in two enzymatic systems, the lysyl-tRNA synthetase from Escherichia coli and the Ap4A alpha, beta-phosphorylase from Saccharomyces cerevisiae. The synthetase was able to use both (Sp)ATP alpha S and (Rp)ATP alpha S as acceptors of adenylate thus yielding corresponding monothioanalogues of Ap4A,(Sp) Ap4A alpha S and (Rp)Ap4A alpha S. No dithiophosphate analogue was formed. Relative synthetase velocities of the formation of Ap4A,(Sp) Ap4A alpha S and (Rp)Ap4A alpha S were 1:0.38:0.15, and the computed Km values for (Sp)ATP alpha S and (Rp)ATP alpha S were 0.48 and 1.34 mM, respectively. The yeast Ap4A phosphorylase synthesized (Sp)Ap4A alpha S and (Rp)Ap4A alpha S using adenosine 5'-phosphosulfate (APS) as source of adenylate. The adenylate was accepted by corresponding thioanalogues of ATP. In that system, relative velocities of Ap4A, (Sp)Ap4A alpha S and (Rp)Ap4A alpha S formation were 1:0.15:0.60. The two isomeric phosphorothioate analogues of Ap4A were tested as substrates for the following specific Ap4A-degrading enzymes: (asymmetrical) Ap4A hydrolase (EC 3.6.1.17) from yellow lupin (Lupinus luteus) seeds hydrolyzed each of the analogues to AMP and the corresponding isomer of ATP alpha S; (symmetrical) Ap4A hydrolase (EC 3.6.1.41) from E. coli produced ADP and the corresponding diastereomer of ADP alpha S; and Ap4A phosphorylase (EC 2.7.7.53) from S. cerevisiae cleaved the Rp isomer only at the unmodified end yielding ADP and (Rp)ATP alpha S whereas the Sp isomer was degraded non-specifically yielding a mixture of ADP, (Sp)ADP alpha S, ATP and (Sp)ATP alpha S. For all the Ap4A-degrading enzymes, the Rp isomer of Ap4A alpha S appeared to be a better substrate than its Sp counterpart; stereoselectivity of the three enzymes for the Ap4A alpha S diastereomers is 51, 6 and 2.5, respectively. Basic kinetic parameters of the degradation reactions are presented and structural requirements of the Ap4A-metabolizing enzymes with respect to the potential substrates modified at the Ap4A-P alpha are discussed. PMID:2172926

Effects of analogues of ethanolamine and choline on phospholipid metabolism in rat hepatocytes

PubMed Central

Åkesson, Björn

1977-01-01

1. Analogues of ethanolamine and choline were incubated with different labelled precursors of phospholipids and isolated hepatocytes and the effects on phospholipid synthesis were studied. 2. 2-Aminopropan-1-ol and 2-aminobutan-1-ol were the most efficient inhibitors of [14C]ethanolamine incorporation into phospholipids, whereas the incorporation of [3H]choline was inhibited most extensively by NN-diethylethanolamine and NN-dimethylethanolamine. 3. When the analogues were incubated with [3H]glycerol and hepatocytes, the appearance of 3H in unnatural phospholipids indicated that they were incorporated, at least in part, via CDP-derivatives. The distribution of [3H]glycerol among molecular species of phospholipids containing 2-aminopropan-1-ol and 1-aminopropan-2-ol was the same as in phosphatidylethanolamine. In other phospholipid analogues the distribution of 3H was more similar to that in phosphatidylcholine. 4. NN-Diethylethanolamine stimulated both the conversion of phosphatidylethanolamine into phosphatidylcholine and the incorporation of [Me-14C]methionine into phospholipids. Other N-alkyl- or NN-dialkyl-ethanolamines also stimulated [14C]methionine incorporation, but inhibited the conversion of phosphatidylethanolamine into phosphatidylcholine. This indicates that phosphatidyl-NN-diethylethanolamine is a poor methyl acceptor, in contrast with other N-alkylated phosphatidylethanolamines. 5. These results on the regulation of phospholipid metabolism in intact cells are discussed with respect to the possible control points. They also provide guidelines for future experiments on the manipulation of phospholipid polar-headgroup composition in primary cultures of hepatocytes. PMID:606244

Impact of the 2008 Wenchuan earthquake on river organic carbon provenance: Insight from biomarkers

NASA Astrophysics Data System (ADS)

Wang, Jin; Feng, Xiaojuan; Hilton, Robert; Jin, Zhangdong; Ma, Tian; Zhang, Fei; Li, Gen; Densmore, Alexander; West, A. Joshua

2017-04-01

Large earthquakes can trigger widespread landslides in active mountain belts, which can mobilize biospheric organic carbon (OC) from the soil and vegetation. Rivers can erode and export biospheric particulate organic carbon (POC), which is an export of ecosystem productivity and may result in a CO2 sink if buried in sedimentary deposits. Our previous work showed that the 2008 Mw 7.9 Wenchuan earthquake increased the discharge of biospheric OC by rivers, due to the increased supply by earthquake triggered landslides (Wang et al., 2016). However, while the OC derived from sedimentary rocks could be accounted for, the source of biospheric OC in rivers before and after the earthquake remains poorly constrained. Here we use suspended sediment samples collected from the Zagunao River before and after the Wenchuan earthquake and measured the specific compounds of OC, including fatty acids, lignin phenols and glycerol dialkyl glycerol tetraether (GDGT) lipids. In combination with the analysis of bulk elemental concentration (C and N) and carbon isotopic ratio, the new data shows differential export patterns for OC components derived from varied terrestrial sources. A high frequency sampling enabled us to explore how the biospheric OC source changes following the earthquake, helping to better understand the link between active tectonics and the carbon cycle. Our results are also important in revealing how sedimentary biomarker records may record past earthquakes.

Optimization of isotherm models for pesticide sorption on biopolymer-nanoclay composite by error analysis.

PubMed

Narayanan, Neethu; Gupta, Suman; Gajbhiye, V T; Manjaiah, K M

2017-04-01

A carboxy methyl cellulose-nano organoclay (nano montmorillonite modified with 35-45 wt % dimethyl dialkyl (C 14 -C 18 ) amine (DMDA)) composite was prepared by solution intercalation method. The prepared composite was characterized by infrared spectroscopy (FTIR), X-Ray diffraction spectroscopy (XRD) and scanning electron microscopy (SEM). The composite was utilized for its pesticide sorption efficiency for atrazine, imidacloprid and thiamethoxam. The sorption data was fitted into Langmuir and Freundlich isotherms using linear and non linear methods. The linear regression method suggested best fitting of sorption data into Type II Langmuir and Freundlich isotherms. In order to avoid the bias resulting from linearization, seven different error parameters were also analyzed by non linear regression method. The non linear error analysis suggested that the sorption data fitted well into Langmuir model rather than in Freundlich model. The maximum sorption capacity, Q 0 (μg/g) was given by imidacloprid (2000) followed by thiamethoxam (1667) and atrazine (1429). The study suggests that the degree of determination of linear regression alone cannot be used for comparing the best fitting of Langmuir and Freundlich models and non-linear error analysis needs to be done to avoid inaccurate results. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of a new family of conformationally restricted peptides as potent nucleators of beta-turns. Design, synthesis, structure, and biological evaluation of a beta-lactam peptide analogue of melanostatin.

PubMed

Palomo, Claudio; Aizpurua, Jesus M; Benito, Ana; Miranda, José Ignacio; Fratila, Raluca M; Matute, Carlos; Domercq, Maria; Gago, Federico; Martin-Santamaria, Sonsoles; Linden, Anthony

2003-12-31

Novel enantiopure (i)-(beta-lactam)-(Gly)-(i+3) peptide models, defined by the presence of a central alpha-alkyl-alpha-amino-beta-lactam ring placed as the (i+1) residue, have been synthesized in a totally stereocontrolled way by alpha-alkylation of suitable N-[bis(trimethylsilyl)methyl]-beta-lactams. The structural properties of these beta-lactam pseudopeptides have been studied by X-ray crystallography, Molecular Dynamics simulation, and NOESY-restrained NMR simulated annealing techniques, showing a strong tendency to form stable type II or type II' beta-turns either in the solid state or in highly coordinating DMSO solutions. Tetrapeptide models containing syn- or anti-alpha,beta-dialkyl-alpha-amino-beta-lactam rings have also been synthesized and their conformations analyzed, revealing that alpha-alkyl substitution is essential for beta-turn stabilization. A beta-lactam analogue of melanostatin (PLG amide) has also been prepared, characterized as a type-II beta-turn in DMSO-d6 solution, and tested by competitive binding assay as a dopaminergic D2 modulator in rat neuron cultured cells, displaying moderate agonist activity in the micromolar concentration range. On the basis of these results, a novel peptidomimetic design concept, based on the separation of constraint and recognition elements, is proposed.

Concentrations of phthalates and DINCH metabolites in pooled urine from Queensland, Australia.

PubMed

Gomez Ramos, M J; Heffernan, A L; Toms, L M L; Calafat, A M; Ye, X; Hobson, P; Broomhall, S; Mueller, J F

2016-03-01

Dialkyl phthalate esters (phthalates) are ubiquitous chemicals used extensively as plasticizers, solvents and adhesives in a range of industrial and consumer products. 1,2-Cyclohexane dicarboxylic acid, diisononyl ester (DINCH) is a phthalate alternative introduced due to a more favourable toxicological profile, but exposure is largely uncharacterised. The aim of this study was to provide the first assessment of exposure to phthalates and DINCH in the general Australian population. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n=24 pools of 100). Concentrations of free and total species were measured using online solid phase extraction isotope dilution high performance liquid chromatography tandem mass spectrometry. Concentrations ranged from 2.4 to 71.9ng/mL for metabolites of di(2-ethylhexyl)phthalate, and from <0.5 to 775ng/mL for all other metabolites. Our data suggest that phthalate metabolites concentrations in Australia were at least two times higher than in the United States and Germany; and may be related to legislative differences among countries. DINCH metabolite concentrations were comparatively low and consistent with the limited data available. Ongoing biomonitoring among the general Australian population may help assess temporal trends in exposure and assess the effectiveness of actions aimed at reducing exposures. Copyright © 2015 Elsevier Ltd. All rights reserved.

Clean thermal decomposition of tertiary-alkyl metal thiolates to metal sulfides: environmentally-benign, non-polar inks for solution-processed chalcopyrite solar cells

NASA Astrophysics Data System (ADS)

Heo, Jungwoo; Kim, Gi-Hwan; Jeong, Jaeki; Yoon, Yung Jin; Seo, Jung Hwa; Walker, Bright; Kim, Jin Young

2016-11-01

We report the preparation of Cu2S, In2S3, CuInS2 and Cu(In,Ga)S2 semiconducting films via the spin coating and annealing of soluble tertiary-alkyl thiolate complexes. The thiolate compounds are readily prepared via the reaction of metal bases and tertiary-alkyl thiols. The thiolate complexes are soluble in common organic solvents and can be solution processed by spin coating to yield thin films. Upon thermal annealing in the range of 200-400 °C, the tertiary-alkyl thiolates decompose cleanly to yield volatile dialkyl sulfides and metal sulfide films which are free of organic residue. Analysis of the reaction byproducts strongly suggests that the decomposition proceeds via an SN1 mechanism. The composition of the films can be controlled by adjusting the amount of each metal thiolate used in the precursor solution yielding bandgaps in the range of 1.2 to 3.3 eV. The films form functioning p-n junctions when deposited in contact with CdS films prepared by the same method. Functioning solar cells are observed when such p-n junctions are prepared on transparent conducting substrates and finished by depositing electrodes with appropriate work functions. This method enables the fabrication of metal chalcogenide films on a large scale via a simple and chemically clear process.

Grain size associations of branched tetraether lipids in soils and riverbank sediments: influence of hydrodynamic sorting processes

NASA Astrophysics Data System (ADS)

Peterse, Francien; Eglinton, Timothy I.

2017-06-01

We analyzed the abundance and distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in grain size fractions of 7 globally distributed river flank sediments and catchment soils in order to determine if and how the initial soil-brGDGT signature is influenced by hydrodynamic sorting upon entering a river and during subsequent transport from land to sea. BrGDGTs are hypothesized to form associations with high-surface-area fine-grained minerals in soils. Such associations, if maintained during transport, may impart resistance to degradation and promote downstream transport, reducing potential interferences by aquatic brGDGTs. We find that brGDGTs are indeed primarily associated with organic carbon (OC) bound to the clay-silt fraction (<63μm) in both soils and river sediments, and that these associations appear to be maintained during river transport. However, the relative distribution of individual brGDGTs among size fractions is relatively uniform, suggesting that brGDGTs are well mixed in river sediments and that OC-mineral associations are continuously renewed. Consequently, the brGDGT signature finally stored in continental margin sediments appears insensitive to differential particle transport processes. Nevertheless, the lower (upstream) temperature signal generally reflected by brGDGTs in river sediments may also be explained by a contribution of in situ produced brGDGTs leading to an underestimation of reconstructed air temperatures.

Exposure of aircraft maintenance technicians to organophosphates from hydraulic fluids and turbine oils: a pilot study.

PubMed

Schindler, Birgit Karin; Koslitz, Stephan; Weiss, Tobias; Broding, Horst Christoph; Brüning, Thomas; Bünger, Jürgen

2014-01-01

Hydraulic fluids and turbine oils contain organophosphates like tricresyl phosphate isomers, triphenyl phosphate and tributyl phosphate from very small up to high percentages. The aim of this pilot study was to determine if aircraft maintenance technicians are exposed to relevant amounts of organophosphates. Dialkyl and diaryl phosphate metabolites of seven organophosphates were quantified in pre- and post-shift spot urine samples of technicians (N=5) by GC-MS/MS after solid phase extraction and derivatization. Pre- and post shift values of tributyl phosphate metabolites (dibutyl phosphate (DBP): median pre-shift: 12.5 μg/L, post-shift: 23.5 μg/L) and triphenyl phosphate metabolites (diphenyl phosphate (DPP): median pre-shift: 2.9 μg/L, post-shift: 3.5 μg/L) were statistically higher than in a control group from the general population (median DBP: <0.25 μg/L, median DPP: 0.5 μg/L). No tricresyl phosphate metabolites were detected. The aircraft maintenance technicians were occupationally exposed to tributyl and triphenyl phosphate but not to tricresyl phosphate, tri-(2-chloroethyl)- and tri-(2-chloropropyl)-phosphate. Further studies are necessary to collect information on sources, routes of uptake and varying exposures during different work tasks, evaluate possible health effects and to set up appropriate protective measures. Copyright © 2013 Elsevier GmbH. All rights reserved.

Combined 3D-QSAR and molecular docking study on 7,8-dialkyl-1,3-diaminopyrrolo-[3,2-f] Quinazoline series compounds to understand the binding mechanism of DHFR inhibitors

NASA Astrophysics Data System (ADS)

Aouidate, Adnane; Ghaleb, Adib; Ghamali, Mounir; Chtita, Samir; Choukrad, M'barek; Sbai, Abdelouahid; Bouachrine, Mohammed; Lakhlifi, Tahar

2017-07-01

A series of nineteen DHFR inhibitors was studied based on the combination of two computational techniques namely, three-dimensional quantitative structure activity relationship (3D-QSAR) and molecular docking. The comparative molecular field analysis (CoMFA) and comparative molecular similarity index analysis (CoMSIA) were developed using 19 molecules having pIC50 ranging from 9.244 to 5.839. The best CoMFA and CoMSIA models show conventional determination coefficients R2 of 0.96 and 0.93 as well as the Leave One Out cross-validation determination coefficients Q2 of 0.64 and 0.72, respectively. The predictive ability of those models was evaluated by the external validation using a test set of five compounds with predicted determination coefficients R2test of 0.92 and 0.94, respectively. The binding mode between this kind of compounds and the DHFR enzyme in addition to the key amino acid residues were explored by molecular docking simulation. Contour maps and molecular docking identified that the R1 and R2 natures at the pyrazole moiety are the important features for the optimization of the binding affinity to the DHFR receptor. According to the good concordance between the CoMFA/CoMSIA contour maps and docking results, the obtained information was explored to design novel molecules.

Biomarkers in Lake Van sediments reveal dry conditions in eastern Anatolia during 110.000-10.000 years B.P.

NASA Astrophysics Data System (ADS)

Randlett, Marie-Eve; Bechtel, Achim; van der Meer, Marcel T. J.; Peterse, Francien; Litt, Thomas; Pickarski, Nadine; Kwiecien, Ola; Stockhecke, Mona; Wehrli, Bernhard; Schubert, Carsten J.

2017-02-01

Lipid biomarkers were analyzed in Lake Van sediments covering the last 600 ka, with a focus on the period between 110 and 10 ka, when a broad maximum in pore water salinity as a relict from the past suggests dry conditions. The occurrence and distribution of biomarkers indicative for terrestrial plants (long-chain n-alkane C29), haptophyte algae (methyl alkenones C37) and halophilic archaea (archaeol) all point toward a dry climate in Lake Van region during this time interval. The hydrogen isotopic composition of C29 n-alkanes (δDC29) and C37 alkenones (δDC37) is enriched between MIS 4 and MIS 2, which is interpreted as a decrease in the regional ratio of precipitation to evaporation. Similarly, the low abundance of the acyclic glycerol dialkyl glycerol tetraether GDGT-0 relative to archaeol, quantified by the Archaeol and Caldarchaeol Ecometric (ACE) is assumed to reflect the presence of halophilic euryarchaeota adapted to high salinity water. The climate around Lake Van appears in phase with the Yammouneh basin 800 km southwest and Lake Urmia 250 km southeast of Lake Van over the last two glacial periods. The results highlight the potential of combining ACE, δDC29, and δDC37 for reconstructing salinity changes and regional precipitation to evaporation ratio from lake sediments.

Influence of Polyethylene Glycol Lipid Desorption Rates on Pharmacokinetics and Pharmacodynamics of siRNA Lipid Nanoparticles.

PubMed

Mui, Barbara L; Tam, Ying K; Jayaraman, Muthusamy; Ansell, Steven M; Du, Xinyao; Tam, Yuen Yi C; Lin, Paulo Jc; Chen, Sam; Narayanannair, Jayaprakash K; Rajeev, Kallanthottathil G; Manoharan, Muthiah; Akinc, Akin; Maier, Martin A; Cullis, Pieter; Madden, Thomas D; Hope, Michael J

2013-12-17

Lipid nanoparticles (LNPs) encapsulating short interfering RNAs that target hepatic genes are advancing through clinical trials, and early results indicate the excellent gene silencing observed in rodents and nonhuman primates also translates to humans. This success has motivated research to identify ways to further advance this delivery platform. Here, we characterize the polyethylene glycol lipid (PEG-lipid) components, which are required to control the self-assembly process during formation of lipid particles, but can negatively affect delivery to hepatocytes and hepatic gene silencing in vivo. The rate of transfer from LNPs to plasma lipoproteins in vivo is measured for three PEG-lipids with dialkyl chains 14, 16, and 18 carbons long. We show that 1.5 mol % PEG-lipid represents a threshold concentration at which the chain length exerts a minimal effect on hepatic gene silencing but can still modify LNPs pharmacokinetics and biodistribution. Increasing the concentration to 2.5 and 3.5 mol % substantially compromises hepatocyte gene knockdown for PEG-lipids with distearyl (C18) chains but has little impact for shorter dimyristyl (C14) chains. These data are discussed with respect to RNA delivery and the different rates at which the steric barrier disassociates from LNPs in vivo.Molecular Therapy-Nucleic Acids (2013) 2, e139; doi:10.1038/mtna.2013.66; published online 17 December 2013.

Reliability of concentrations of organophosphate pesticide metabolites in serial urine specimens from pregnancy in the Generation R study

PubMed Central

Spaan, Suzanne; Pronk, Anjoeka; Koch, Holger M.; Jusko, Todd A.; Jaddoe, Vincent W.V.; Shaw, Pamela A.; Tiemeier, Henning M.; Hofman, Albert; Pierik, Frank H.; Longnecker, Matthew P.

2014-01-01

The widespread use of organophosphate (OP) pesticides has resulted in ubiquitous exposure in humans, primarily through their diet. Exposure to OP pesticides may have adverse health effects, including neurobehavioral deficits in children. The optimal design of new studies requires data on the reliability of urinary measures of exposure. In the present study, urinary concentrations of six dialkyl phosphate (DAP) metabolites, the main urinary metabolites of OP pesticides, were determined in 120 pregnant women participating in the Generation R Study in Rotterdam. Intra-class correlation coefficients (ICCs) across serial urine specimens taken at <18, 18–25, and >25 weeks of pregnancy were determined to assess reliability. Geometric mean total DAP metabolite concentrations were 229 (GSD 2.2), 240 (GSD 2.1), and 224 (GSD 2.2) nmol/g creatinine across the three periods of gestation. Metabolite concentrations from the serial urine specimens in general correlated moderately. The ICCs for the six DAP metabolites ranged from 0.14 to 0.38 (0.30 for total DAPs), indicating weak to moderate reliability. Although the DAP metabolite levels observed in this study are slightly higher and slightly more correlated than in previous studies, the low to moderate reliability indicates a high degree of within-person variability, which presents challenges for designing well-powered epidemiologic studies. PMID:25515376

Reliability of concentrations of organophosphate pesticide metabolites in serial urine specimens from pregnancy in the Generation R Study.

PubMed

Spaan, Suzanne; Pronk, Anjoeka; Koch, Holger M; Jusko, Todd A; Jaddoe, Vincent W V; Shaw, Pamela A; Tiemeier, Henning M; Hofman, Albert; Pierik, Frank H; Longnecker, Matthew P

2015-05-01

The widespread use of organophosphate (OP) pesticides has resulted in ubiquitous exposure in humans, primarily through their diet. Exposure to OP pesticides may have adverse health effects, including neurobehavioral deficits in children. The optimal design of new studies requires data on the reliability of urinary measures of exposure. In the present study, urinary concentrations of six dialkyl phosphate (DAP) metabolites, the main urinary metabolites of OP pesticides, were determined in 120 pregnant women participating in the Generation R Study in Rotterdam. Intra-class correlation coefficients (ICCs) across serial urine specimens taken at <18, 18-25, and >25 weeks of pregnancy were determined to assess reliability. Geometric mean total DAP metabolite concentrations were 229 (GSD 2.2), 240 (GSD 2.1), and 224 (GSD 2.2) nmol/g creatinine across the three periods of gestation. Metabolite concentrations from the serial urine specimens in general correlated moderately. The ICCs for the six DAP metabolites ranged from 0.14 to 0.38 (0.30 for total DAPs), indicating weak to moderate reliability. Although the DAP metabolite levels observed in this study are slightly higher and slightly more correlated than in previous studies, the low to moderate reliability indicates a high degree of within-person variability, which presents challenges for designing well-powered epidemiological studies.

Tracing tetraether lipids from source to sink in the Rhône River system (NW Mediterranean)

NASA Astrophysics Data System (ADS)

Kim, Jung-Hyun; Ludwig, Wolfgang; Buscail, Roselyne; Dorhout, Denise; Sinninghe Damste, Jaap

2015-06-01

In this study, we investigated soils and river suspended particulate matter (SPM) collected in the Rhône and its tributary basins as well as marine surface sediments taken in the Rhône prodelta (Gulf of Lions, NW Mediterranean). Thereby, we traced the signal of branched glycerol dialkyl glycerol tetraethers (brGDGTs) from the source to sink via the Rhône River and its tributaries and identified sources of brGDGTs in rivers and marine sediments. Soil pH rather than the mean annual air temperature (MAAT) explains most of the observed variances of the brGDGT distribution in our soil dataset. The observed changes in the distribution of brGDGTs in the river SPM indicate that brGDGTs brought by the river to the sea are primarily derived from the lower Rhône and its tributary soils, even though in situ production in the river itself cannot be excluded. In marine surface sediments, it appears that the input of riverine brGDGTs is the primary source of brGDGTs in the Rhône prodelta, although the brGDGT composition may be further modified by the in situ production in the marine environment. More work is required to assess fully whether brGDGTs can be used to reconstruct the terrestrial paleoenvironmental changes using marine sediment cores taken in the Rhône prodelta close to the river mouth.

Branched GDGT distributions in lakes from Mexico and Central America

NASA Astrophysics Data System (ADS)

Lei, A.; Werne, J. P.; Correa-Metrio, A.; Pérez, L.; Caballero, M.

2017-12-01

The potential to use bacterial derived branched glycerol dialkyl glycerol tetraethers (brGDGTs) to reconstruct mean annual air temperatures from soils sparked significant interest in the terrestrial paleoclimate community, where a high-fidelity paleotemperature proxy is desperately needed. While the source of brGDGTs remains unknown (but are potentially attributed to the highly diverse phylum Acidobacteria), much evidence points to the potential for these bacteria to live not only in the terrestrial environment but also in lake water and sediments as well. Though the application of brGDGTs to lacustrine reconstructions is promising, the initial applications of soil-based MBT/CBT proxy to lacustrine sediments typically resulted in lower temperatures than were reasonable, likely due to additions from lacustrine bacterial brGDGTs. Here, we present data from a suite of >100 lakes in Mexico and Central America, producing a regional core-top calibration different from those developed in other regions. Results indicate a significant role for regional differences in controlling the brGDGTs distribution, likely due to different brGDGT-producing microbial communities thriving under varying environmental conditions. Rigorous development of brGDGT based proxies will improve our understanding of the source and applicability of these biomarkers, and increase confidence in the accuracy of paleotemperature reconstructions to numerous lacustrine records in the region.

Effects of a garlic-derived principle (ajoene) on aggregation and arachidonic acid metabolism in human blood platelets.

PubMed

Srivastava, K C; Tyagi, O D

1993-08-01

When garlic cloves are chopped or crushed several dialkyl thiosulfinates are rapidly formed by the action of the enzyme alliin lyase or alliinase (EC 4.4.1.4) on S(+)-alkyl-L-cysteine sulfoxides. Allicin (diallyl thiosulfinate or allyl 2-propene thiosulfinate) is the dominant thiosulfinate released. A variety of sulfur containing compounds are formed from allicin and other thiosulfinates depending on the way in which garlic is handled. One such compound identified recently is ajoene which has been reported to possess antithrombotic properties. We present here data on the antiplatelet properties of ajoene together with its effects on the metabolism of arachidonic acid (AA) in intact platelets. Thus, ajoene was found to inhibit platelet aggregation induced by AA, adrenaline, collagen, adenosine diphosphate (ADP) and calcium ionophore A23187; the nature of the inhibition was irreversible. In washed platelets stimulated by labelled arachidonate, ajoene inhibited the formation of thromboxane A2; 12-lipoxygenase product(s) were reduced at higher ajoene concentrations. This garlic-derived substance inhibited the incorporation of labelled AA into platelet phospholipids at higher concentration. In labelled platelets, on stimulation with either calcium ionophore A23187 or collagen, reduced amounts of thromboxane and 12-HETE (12-hydroxyeicosatetraenoic acid) were produced in ajoene-treated platelets compared to control platelets. This substance had no effect on the deacylation of platelet phospholipids. The results suggest that at least one of the mechanisms by which ajoene shows antiplatelet effects could be related to altered metabolism of AA.

Molecules in the mud: Combining ancient DNA and lipid biomarkers to reconstruct vegetation response to climate variability during the Last Interglacial and the Holocene on Baffin Island, Arctic Canada

NASA Astrophysics Data System (ADS)

Crump, S. E.; Sepúlveda, J.; Bunce, M.; Miller, G. H.

2017-12-01

Modern ecological studies are revealing that the "greening" of the Arctic, resulting from a poleward shift in woody vegetation ranges, is already underway. The increasing abundance of shrubs in tundra ecosystems plays an important role in the global climate system through multiple positive feedbacks, yet uncertainty in future predictions of terrestrial vegetation means that climate models are likely not capturing these feedbacks accurately. Recently developed molecular techniques for reconstructing past vegetation and climate allow for a closer look at the paleo-record in order to improve our understanding of tundra community responses to climate variability; our current research focus is to apply these tools to both Last Interglacial and Holocene warm times. Here we present initial results from a small lake on southern Baffin Island spanning the last 7.2 ka. We reconstruct climate with both bulk geochemical and biomarker proxies, primarily using biogenic silica and branched glycerol dialkyl glycerol tetraethers (brGDGTs) as temperature indicators. We assess shifts in plant community using multivariate analysis of sedimentary ancient DNA (sedaDNA) metabarcoding data. This combination of approaches reveals that the vegetation community has responded sensitively to early Holocene warmth, Neoglacial cooling, and possibly modern anthropogenic warming. To our knowledge, this represents the first combination of a quantitative, biomarker-based climate reconstruction with a sedaDNA-based paleoecological reconstruction, and offers a glimpse at the potential of these molecular techniques used in tandem.

A high-resolution mid-Pleistocene temperature record from Arctic Lake El'gygytgyn: a 50 kyr super interglacial from MIS 33 to MIS 31?

NASA Astrophysics Data System (ADS)

de Wet, Gregory A.; Castañeda, Isla S.; DeConto, Robert M.; Brigham-Grette, Julie

2016-02-01

Previous periods of extreme warmth in Earth's history are of great interest in light of current and predicted anthropogenic warming. Numerous so called "super interglacial" intervals, with summer temperatures significantly warmer than today, have been identified in the 3.6 million year (Ma) sediment record from Lake El'gygytgyn, northeast Russia. To date, however, a high-resolution paleotemperature reconstruction from any of these super interglacials is lacking. Here we present a paleotemperature reconstruction based on branched glycerol dialkyl glycerol tetraethers (brGDGTs) from Marine Isotope Stages (MIS) 35 to MIS 29, including super interglacial MIS 31. To investigate this period in detail, samples were analyzed with an unprecedented average sample resolution of 500 yrs from MIS 33 to MIS 30. Our results suggest the entire period currently defined as MIS 33-31 (∼1114-1062 kyr BP) was characterized by generally warm and highly variable conditions at the lake, at times out of phase with Northern Hemisphere summer insolation, and that cold "glacial" conditions during MIS 32 lasted only a few thousand years. Close similarities are seen with coeval records from high southern latitudes, supporting the suggestion that the interval from MIS 33 to MIS 31 was an exceptionally long interglacial (Teitler et al., 2015). Based on brGDGT temperatures from Lake El'gygytgyn (this study and unpublished results), warming in the western Arctic during MIS 31 was matched only by MIS 11 during the Pleistocene.

Transfection Studies with Colloidal Systems Containing Highly Purified Bipolar Tetraether Lipids from Sulfolobus acidocaldarius.

PubMed

Engelhardt, Konrad H; Pinnapireddy, Shashank Reddy; Baghdan, Elias; Jedelská, Jarmila; Bakowsky, Udo

2017-01-01

Lipid vectors are commonly used to facilitate the transfer of nucleic acids into mammalian cells. In this study, two fractions of tetraether lipids from the archaea Sulfolobus acidocaldarius were extracted and purified using different methods. The purified lipid fractions polar lipid fraction E (PLFE) and hydrolysed glycerol-dialkyl-nonitol tetraether (hGDNT) differ in their structures, charge, size, and miscibility from conventional lipids. Liposomes were prepared by mixing tetraether lipids with cholesterol (CH) and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) resulting in stable vectors for gene delivery. Lipoplexes were prepared by complexation of liposomes with a luciferase expressing plasmid (pCMV-luc) at certain nitrogen-to-phosphorus (N/P) ratios and optimised for the transient transfection of ovarian adenocarcinoma cells (SK-OV-3). Complexation efficacy was investigated by gel-red fluorescence assay. Biophysical properties, like size, surface charge, and morphology, were investigated by differential light scattering (DLS), atomic force microscopy (AFM), and scanning electron microscopy (Cryo-SEM), respectively, revealing structural differences between liposomes and lipoplexes. A range of stable transfecting agents containing tetraether lipids were obtained by incorporating 5 mol% of tetraether lipids. Lipoplexes showed a decrease in free gel-red with increasing N/P ratios indicating efficient incorporation of plasmid DNA (pDNA) and remarkable stability. Transfection experiments of the lipoplexes revealed successful and superior transfection of SK-OV-3 cell line compared to the commercially available DOTAP and branched polyethyleneimine (25 kDa bPEI).

Vesicles from pH-regulated reversible gemini amino-acid surfactants as nanocapsules for delivery.

PubMed

Lv, Jing; Qiao, Weihong; Li, Zongshi

2016-10-01

Reversible transition from micelles to vesicles by regulating pH were realized by gemini amino-acid surfactants N,N'-dialkyl-N,N'-diacetate ethylenediamine. Measurement results of ζ-potential at different pH and DLS at varying solvents revealed that the protonation between H(+) and double NCH2COO(-) groups (generating NH(+)CH2COO(-)), expressed as pKa1 and pKa2, is the key driving force to control the aggregation behaviors of gemini surfactant molecule. Effect of pH on the bilayer structure was studied in detail by using steady-state fluorescence spectroscopy of hydrophobic pyrene and Coumarin 153 (C153) respectively and fluorescence resonance energy transfer (FRET) from C153 to Rhodamine 6G (R6G). Various pH-regulated and pH-reversible self-assemblies were obtained in one surfactant system. Vitamin D3 was encapsulated in vesicle bilayers to form nano-VD3-capsules as VD3 supplement agent for health care products. By using the electrostatic attraction between Ca(2+) and double -COO(-) groups, nano-VD3-capsules with Ca(2+) coated outermost layers were prepared as a formulation for VD3 and calcium co-supplement agent. DLS and TEM were performed to check stability and morphology of the nano-capsules. It is concluded that the pH-regulated gemini amino-acid surfactants can be used to construct colloidal systems for delivering hydrophobic drugs or nutritions without lipids at human physiological pH level. Copyright © 2016 Elsevier B.V. All rights reserved.

Flash pyrolysis of coal, coal maceral, and coal-derived pyrite with on-line characterization of volatile sulfur compounds

USGS Publications Warehouse

Chou, I.-Ming; Lake, M.A.; Griffin, R.A.

1988-01-01

A Pyroprobe flash pyrolysis-gas chromatograph equipped with a flame photometric detector was used to study volatile sulfur compounds produced during the thermal decomposition of Illinois coal, coal macerals and coal-derived pyrite. Maximum evolution of volatile organic sulfur compounds from all coal samples occurred at a temperature of approximately 700??C. At this temperature, the evolution of thiophene, its alkyl isomers, and short-chain dialkyl sulfide compounds relative to the evolution of benzothiophene and dibenzothiophene compounds was greater from coal high in organic sulfur than from coal low in organic sulfur. The variation in the evolution of sulfur compounds observed for three separate coal macerals (exinite, vitrinite, and inertinite) was similar to that observed for whole coal samples. However, the variation trend for the macerals was much more pronounced. Decomposition of coal-derived pyrite with the evolution of elemental sulfur was detected at a temperature greater than 700??C. The results of this study indicated that the gas chromotographic profile of the volatile sulfur compounds produced during flash pyrolysis of coals and coal macerals varied as a function of the amount of organic sulfur that occurred in the samples. Characterization of these volatile sulfur compounds provides a better understanding of the behavior of sulfur in coal during the thermolysis process, which could be incorporated in the design for coal cleaning using flash pyrolysis techniques. ?? 1988.

Enrichment and Characterization of an Autotrophic Ammonia-Oxidizing Archaeon of Mesophilic Crenarchaeal Group I.1a from an Agricultural Soil▿†

PubMed Central

Jung, Man-Young; Park, Soo-Je; Min, Deullae; Kim, Jin-Seog; Rijpstra, W. Irene C.; Sinninghe Damsté, Jaap S.; Kim, Geun-Joong; Madsen, Eugene L.; Rhee, Sung-Keun

2011-01-01

Soil nitrification is an important process for agricultural productivity and environmental pollution. Though one cultivated representative of ammonia-oxidizing Archaea from soil has been described, additional representatives warrant characterization. We describe an ammonia-oxidizing archaeon (strain MY1) in a highly enriched culture derived from agricultural soil. Fluorescence in situ hybridization microscopy showed that, after 2 years of enrichment, the culture was composed of >90% archaeal cells. Clone libraries of both 16S rRNA and archaeal amoA genes featured a single sequence each. No bacterial amoA genes could be detected by PCR. A [13C]bicarbonate assimilation assay showed stoichiometric incorporation of 13C into Archaea-specific glycerol dialkyl glycerol tetraethers. Strain MY1 falls phylogenetically within crenarchaeal group I.1a; sequence comparisons to “Candidatus Nitrosopumilus maritimus” revealed 96.9% 16S rRNA and 89.2% amoA gene similarities. Completed growth assays showed strain MY1 to be chemoautotrophic, mesophilic (optimum at 25°C), neutrophilic (optimum at pH 6.5 to 7.0), and nonhalophilic (optimum at 0.2 to 0.4% salinity). Kinetic respirometry assays showed that strain MY1's affinities for ammonia and oxygen were much higher than those of ammonia-oxidizing bacteria (AOB). The yield of the greenhouse gas N2O in the strain MY1 culture was lower but comparable to that of soil AOB. We propose that this new soil ammonia-oxidizing archaeon be designated “Candidatus Nitrosoarchaeum koreensis.” PMID:22003023

Bacterial tetraethers from Tibetan hot springs: Implications for nitrogen metabolism and biological sources

NASA Astrophysics Data System (ADS)

Li, F.; Zhang, C.; Wang, S.; Klotz, M. G.; Dong, H.; Li, W.

2013-12-01

Branched glycerol dialkyl glycerol tetraethers (bGDGTs) are considered to be produced by bacteria that are predominantly found in soils and peat bogs. Recently, however, in situ production of bGDGTs is reported from a terrestrial hot spring in the Great Basin. In this study, we analyzed water chemistry, bacterial lipids, and pyrosequencing data from 37 Tibetan hot springs in order to evaluate the linkage between biological sources, metabolic processes and the distribution of bGDGTs. Analyses of absolute and relative concentrations of intact polar- and core bGDGTs (IP-bGDGTs and C-bGDGTs) suggest that the bGDGTs are predominantly produced in situ in Tibetan hot springs. Cluster analysis separated the hot spring samples into three major groups, which showed significant relationships between bGDGTs and concentrations of ammonia, nitrite or nitrate. The nirS gene abundance also correlated significantly with bGDGTs. These results indicate that the bGDGT-producing organisms may be involved in nitrogen metabolism in the Tibetan hot springs. Pyrosequencing analysis identified eight phyla of Bacteria (Acidobacteria, Bacteroidetes, Chlorobi, Firmicutes, Nitrospirae, Proteobacteria, Verrucomicrobia and Spirochetes) that may be potential sources of bGDGTs based on significant correlations of these organisms with the distribution of different bGDGTs. Representatives of these phyla have been implicated in nitrogen oxide transformations in many diverse environments including hot springs. Overall, our results suggest that bacteria producing bGDGTs may play an important role in nitrogen cycle in the Tibetan hot springs.

Localized environmental control on the distribution of brGDGTs in Chinese soils: Implication for paleo-pH reconstruction

NASA Astrophysics Data System (ADS)

Zheng, F.; Chen, Y.; Li, F.; Ma, C.; Zhu, Y.; Zhang, C. L.

2014-12-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are unique bacterial lipids that commonly occur in soil and peat bog. The methylation and cyclization degrees of brGDGTs, expressed as MBT and CBT, respectively, are mainly controlled by mean annual air temperature (MAAT) and soil pH. However, the brGDGT-derived temperatures scatter widely compared to actual MAATs in both regional and global calibrations. In this study, we collected 297 soil samples from diverse regions of China (Lanzhou, Guangzhou, Shanghai, Yunnan, Dongying and Tibetan Plateau) in order to identify environmental variables that control the distribution of brGDGTs locally. The results show that MBT correlated positively with MAAT under the global calibration framework; however, large variation in MBT occurred for a given MAAT for individual regions. When confined within a specific region, MBT index positively correlated with conductivity in Dongying soils and negatively with pH in Yunnan and Guangzhou soils. Removing GDGT-II from CBT calculation resulted in a revised CBT index that provides more accurate estimation of pH (R2=0.79 vs 0.67), especially in alkaline soils. In addition, the combination of MBT and revised CBT also improves the estimation of soil pH (R2 =0.79) than the original CBT index alone (R2=0.67). Our results demonstrate that brGDGTs-derived proxies may be more reliable for estimating paleo-soil pH than paleo-continental temperature.

Clean thermal decomposition of tertiary-alkyl metal thiolates to metal sulfides: environmentally-benign, non-polar inks for solution-processed chalcopyrite solar cells.

PubMed

Heo, Jungwoo; Kim, Gi-Hwan; Jeong, Jaeki; Yoon, Yung Jin; Seo, Jung Hwa; Walker, Bright; Kim, Jin Young

2016-11-09

We report the preparation of Cu 2 S, In 2 S 3 , CuInS 2 and Cu(In,Ga)S 2 semiconducting films via the spin coating and annealing of soluble tertiary-alkyl thiolate complexes. The thiolate compounds are readily prepared via the reaction of metal bases and tertiary-alkyl thiols. The thiolate complexes are soluble in common organic solvents and can be solution processed by spin coating to yield thin films. Upon thermal annealing in the range of 200-400 °C, the tertiary-alkyl thiolates decompose cleanly to yield volatile dialkyl sulfides and metal sulfide films which are free of organic residue. Analysis of the reaction byproducts strongly suggests that the decomposition proceeds via an SN 1 mechanism. The composition of the films can be controlled by adjusting the amount of each metal thiolate used in the precursor solution yielding bandgaps in the range of 1.2 to 3.3 eV. The films form functioning p-n junctions when deposited in contact with CdS films prepared by the same method. Functioning solar cells are observed when such p-n junctions are prepared on transparent conducting substrates and finished by depositing electrodes with appropriate work functions. This method enables the fabrication of metal chalcogenide films on a large scale via a simple and chemically clear process.

Synthesis of Novel 1,4- Dihydropyridine Derivatives Bearing Biphenyl-2'-Tetrazole Substitution as Potential Dual Angiotensin II Receptors and Calcium Channel Blockers

PubMed Central

Shahbazi Mojarrad, Javid; Zamani, Zahra; Nazemiyeh, Hossein; Ghasemi, Saeed; Asgari, Davoud

2011-01-01

Introduction: We report the synthesis of novel 1,4-dihydropyridine derivatives containing biphenyl-2'-tetrazole moieties. We hypothesized that merging the key structural elements present in an AT1 receptor antagonist with key structural elements in 1,4-dihydropyridine calcium channel blockers would yield novel analogs with potential dual activity for both receptors. This strategy led to the design and synthesis of dialkyl 1,4-dihydro-2,6-dimethyl-4-[2-n-alkyl-1-[2΄-(1H-tetrazole-5-yl) biphenyl -4-yl] methyl] imidazole-4(or 5)-yl]- 3, 5-pyridinedicarboxylate analogs. Methods: These compounds were obtained by two methods starting from biphenyltetrazolyl-4-(or 5)-imidazolecarboxaldehyde intermediates employing in classical Hantzsch condensation reaction. In the first method, triphenylmethyl protecting group of 4- or 5-carboxaldehyde intermediate was first removed in acidic media and then classical Hantzsch reaction was employed in order to obtain the final products. In the second method, without further deprotection process, protected 4- or 5-carboxaldehyde intermediate directly was used in Hantzsch reaction. Results: The second method was more efficient than the first method since the deprotection and ring closure reaction occurs simultaneously in one pot. Conclusion: Eight novel dihydropridines analogs were synthesized using classic Hantzsch condensation reaction. Chemical structures of the compounds were characterized by 1H NMR, infrared and mass spectroscopy. PMID:24312750

Impacts of temperature and pH on the distribution of archaeal lipids in Yunnan hot springs, China

PubMed Central

Wu, Weiyan; Zhang, Chuanlun L.; Wang, Huanye; He, Liu; Li, Wenjun; Dong, Hailiang

2013-01-01

In culture experiments and many low temperature environments, the distribution of isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs) commonly shows a strong correlation with temperature; however, this is often not the case in hot springs. We studied 26 hot springs in Yunnan, China, in order to determine whether temperature or other factors control the distribution of GDGTs in these environments. The hot springs ranged in temperature from 39.0 to 94.0°C, and in pH from 2.35 to 9.11. Water chemistry including nitrogen-, sulfur-, and iron species was also determined. Lipids from the samples were analyzed using liquid chromatography–mass spectrometry (LC–MS). Distributions of GDGTs in these hot springs were examined using cluster analysis, which resulted in two major groups. Group 1 was characterized by the lack of dominance of any individual GDGTs, while Group 2 was defined by the dominance of GDGT-0 or thaumarchaeol. Temperature was the main control on GDGT distribution in Group 1, whereas pH played an important role in the distribution of GDGTs in Group 2. However, no correlations were found between the distribution of GDGTs and any of the nitrogen-, sulfur-, or iron species. Results of this study indicate the dominance of temperature or pH control on archaeal lipid distribution, which can be better evaluated in the context of lipid classification. PMID:24194734

Investigating the Biosynthesis of Membrane-spanning Lipids Using Model Strains of Acidobacteria

NASA Astrophysics Data System (ADS)

Bradley, A. S.; Chubiz, L. M.

2016-12-01

Glycerol dialkyl glycerol tetraethers (GDGTs), deriving from the membrane-spanning lipids of microbes, are detected in a wide range of environments including marine and lacustrine waters, sediments, and in terrestrial soils. In sediments and soils, ratios of various GDGT structures form the basis of the TEX86 proxy based on isoprenoidal GDGTs derived from archaea, and the MBT/CBT proxy based on bacterial-derived branched GDGTs (brGDGTs), which is influenced by both temperature and pH. While the relationships of the proxy values to environmental variables have been empirically calibrated, much uncertainty remains in understanding genetic and physiological factors that affect the production of these lipid structures by microbes. In this study we compare two model bacterial strains - Edaphobacter aggregans WGB-1 , which has been previously demonstrated to produce brGDGTs (Damsté et al 2011) and Edaphobacter modestus JBG-1 (a non-brGDGT producer) to gain traction into understanding brGDGT production. We have sequenced each genome, facilitating comparisons that can be used to computationally generate hypotheses for genes involved in brGDGT biosynthesis. We will also report the results of initial experiments conducted to understand how the lipid profiles of each strain vary as a function of growth phase. Through a combination of genetic approaches and physiolotical experiments, we aim to bring new understanding to brGDGTs and how proxies derived from these lipids relate to environmental variables. Damsté et al. 2011 AEM 77: 4147

Study on thermal effects & sulfurized additives, in lubricating greases

NASA Astrophysics Data System (ADS)

Shah, Ami Atul

Lithium Base grease constitutes about 50% of market. The greases are developed to be able to work in multiple working conditions and have longer working life. Greases with extreme pressure additives and anti-wear additives have been developed as a solution to many of the applications. These developed greases are tested under ASTM D2266 testing conditions to meet the requirements. The actual working conditions, although, differ than the real testing conditions. The loading, speed and temperature conditions can be more harsh, or fluctuating in nature. The cyclic nature of the parameters cannot be directly related to the test performance. For this purpose studies on the performance under spectrum loading, variable speed and fluctuating temperature must be performed. This study includes tests to understand the effect of thermal variation on some of the most commonly used grease additives that perform well under ASTM D2266 testing conditions. The studied additives include most widely used industrial extreme pressure additive MoS2. Performance of ZDDP which is trying to replace MoS2 in its industrial applications has also been studied. The tests cover study of extreme pressure, anti-wear and friction modifier additives to get a general idea on the effects of thermal variation in three areas. Sulphur is the most common extreme pressure additive. Sulphur based MoS 2 is extensively used grease additive. Study to understand the tribological performance of this additive through wear testing and SEM/EDX studies has been done. This performance is also studied for other metallic sulfides like WS2 and sulphur based organic compound. The aim is to study the importance of the type of bond that sulphur shares in its additive's structure on its performance. The MoS2 film formation is found to be on the basis of the FeS formation on the substrate and protection through sacrificial monolayer deposition of the MoS2 sheared structure. The free Mo then tends to oxidise. An attempt to understand the effects of the addition of sulphur from a sulfurized olefin to MoS2 through mechanical processing has been conducted. This mechanically processed additive mixed is tested through regular ASTM D2266 test. The hypothesis was to make more shear able MoS 2 layers available by using the sulphur from the olefin to form the basic FeS layer that reduces the continuous wear rate. The results have been studied using SEM and EDX imaging.

Mechanisms for the export of archaeal lipids down the water column in the upwelling area off Cape Blanc, North-West Africa

NASA Astrophysics Data System (ADS)

Ebersbach, Friederike; Goldenstein, Nadine; Iversen, Morten; Mollenhauer, Gesine; Hinrichs, Kai-Uwe

2016-04-01

Transport mechanisms of microbial membrane lipids from surface waters to the seafloor are poorly understood. In particular, pelagic archaeal glycerol dibiphytanyl glycerol tetraethers (GDGTs) from planktonic archaea are frequently used for reconstruction of ancient sea surface temperatures (Schouten et al. 2013). Because planktonic archaea are too small and neutrally buoyant to sink independently, transport vehicles for efficient export of fossil archaeal biomarkers to the sediment are required. The surface ocean is coupled with the deep ocean through biogenic sinking particles, a process known as the biological pump (Volk and Hoffert 1985). Two different pathways for particle formation, mainly taking place in the mesopelagic zone, are distinguished: Direct aggregation of phytoplankton blooms or grazing, resulting in phyto-detrital aggregates or reprocessed faecal material, respectively. Grazing and packaging into sinking particles is a possible export mechanism for GDGTs (Huguet et al. 2006). Moreover, it is assumed that phyto-detrital aggregates also play an important role in transporting GDGTs to the deep (Mollenhauer et al. 2015), but processes behind this pathway remain unclear. However, there are only few studies that link GDGT signals in sinking particles to the composition of the exported particulate matter (e.g. Yamamoto et al., 2012; Mollenhauer et al. 2015). Here we investigate sinking particles and suspended particulate matter (SPM) from spring blooms in 2012 and 2013 in the upwelling region in the Atlantic Ocean off Cape Blanc, Mauritania. We compare for the first time material from free-floating sediment traps (100, 200 and 400 m; purely sinking particles) with sinking particles and SPM from size fractionated in-situ pump (ISP) filters (several depths between 40 and 2350 m). This setup allows to relate the signal from archaeal lipids to (i) the flux of particulate organic carbon and the particle assemblages as revealed by the characterisation of thousands of individual particles collected in gels in addition to (ii) the sinking particles and SPM present in different particle size fractions on the filters. First results show that the large size fraction carries relatively more intact lipids indicating fresh material being attached to sinking particles rather than suspended in the water column. Furthermore, the distribution of 1G-GDGTs over depths differs from that of 2G- and HPH-GDGTs which might relate to different archaeal communities at different depths. Our findings contribute to the mechanistic understanding of the export of organic molecules through the water column and support the validation of lipid-based paleoceanographic proxies. References Huguet, C., Cartes, J.E., Sinninghe Damsté, J.S., Schouten, S., 2006. Marine crenarchaeotal membrane lipids in decapods: Implications for the TEX86 paleothermometer. Geochemistry, Geophysics, Geosystems 7 (11), Q11010. Mollenhauer, G., Basse, A., Kim, J.-H., Sinninghe Damsté, J.S., Fischer, G., 2015. A four-year record of UK'37- and TEX86-derived sea surface temperature estimates from sinking particles in the filamentous upwelling region off Cape Blanc, Mauritania. Deep Sea Research Part I: Oceanographic Research Papers 97, 67-79. doi:10.1016/j.dsr.2014.11.015 Schouten, S., Hopmans, E.C., Sinninghe Damsté, J.S., 2013. The organic geochemistry of glycerol dialkyl glycerol tetraether lipids: A review. Organic Geochemistry 54, 19-61. Volk, T., Hoffert, M.I., 1985. Ocean carbon pumps: analysis of relative strengths and efficiencies in ocean-driven atmospheric CO2 changes. Geophysical Monographs 32, 99-110. Yamamoto, M., Shimamoto, A., Fukuhara, T., Tanaka, Y., Ishizaka, J., 2012. Glycerol dialkyl glycerol tetraethers and TEX86 index in sinking particles in the western North Pacific. Organic Geochemistry 53 (0), 52-62.

Synthesis of Spiro Indole-2-Ones Using Three Component Reaction of N-Alkylisatins and Triphenylphosphonium Intermediates.

PubMed

Moradi, Ali Varasteh

2017-01-01

A simple and efficient procedure is achieved for the synthesis of indole-2-one derivatives via three-component reaction of N-alkylisatin, activated acetylenic compounds and alkyl bromide in the presence of triphenylphosphine in water under two conditions; room temperature and microwave irradiation. All chemicals used in this work were prepared from Fluka (Buchs, Switzerland) and were used without further purification. N-alkylisatin were synthesized in the laboratory in the procedure that is reported in the literature. Electrothermal 9100 apparatus is employed for measuring of melting points of products. Elemental analyses for C, H, and N were performed with Heraeus CHN-O-Rapid analyzer. Mass spectra were recorded on a FINNIGAN-MAT 8430 spectrometer operating at an ionization potential of 70 eV. Measurement of IR spectra was performed by Shimadzu IR-460 spectrometer. 1H, and 13C NMR spectra were evaluated with a BRUKER DRX- 500 AVANCE spectrometer at 500.1 and 125.8 MHz, respectively. The results were demonstrated that simple mixing of N-alkylisatin, dialkyl acetylenedicarboxylate and alkyl bromides in the presence of triphenylphosphine by using of microwave condition is the efficient method for preparation of indole derivatives in good yields. In the optimized reaction conditions, water is solvent and temperature of the mixture of reaction is 80 oC. In this study, the reaction of activated acetylenic compounds with N-alkylisatin and alkyl bromide in the presence of triphenylphosphine is investigated which is led to a facile synthesis of some functionalized indoles. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Occupational exposure of air crews to tricresyl phosphate isomers and organophosphate flame retardants after fume events.

PubMed

Schindler, Birgit Karin; Weiss, Tobias; Schütze, Andre; Koslitz, Stephan; Broding, Horst Christoph; Bünger, Jürgen; Brüning, Thomas

2013-04-01

Aircraft cabin air can possibly be contaminated by tricresyl phosphates (TCP) from jet engine oils during fume events. o-TCP, a known neurotoxin, has been addressed to be an agent that might cause the symptoms reported by cabin crews after fume events. A total of 332 urine samples of pilots and cabin crew members in common passenger airplanes, who reported fume/odour during their last flight, were analysed for three isomers of tricresyl phosphate metabolites as well as dialkyl and diaryl phosphate metabolites of four flame retardants. None of the samples contained o-TCP metabolites above the limit of detection (LOD 0.5 μg/l). Only one sample contained metabolites of m- and p-tricresyl phosphates with levels near the LOD. Median metabolite levels of tributyl phosphate (TBP), tris-(2-chloroethyl) phosphate (TCEP) and triphenyl phosphate (TPP) (DBP 0.28 μg/l; BCEP 0.33 μg/l; DPP 1.1 μg/l) were found to be significantly higher than in unexposed persons from the general population. Median tris-(2-chloropropyl) phosphate (TCPP) metabolite levels were significantly not higher in air crews than in controls. Health complaints reported by air crews can hardly be addressed to o-TCP exposure in cabin air. Elevated metabolite levels for TBP, TCEP and TPP in air crews might occur due to traces of hydraulic fluid in cabin air (TBP, TPP) or due to release of commonly used flame retardants from the highly flame protected environment in the airplane. A slight occupational exposure of air crews to organophosphates was shown.

Factors Controlling the Distribution of Archaeal Tetraethers in Terrestrial Hot Springs▿

PubMed Central

Pearson, Ann; Pi, Yundan; Zhao, Weidong; Li, WenJun; Li, Yiliang; Inskeep, William; Perevalova, Anna; Romanek, Christopher; Li, Shuguang; Zhang, Chuanlun L.

2008-01-01

Glycerol dialkyl glycerol tetraethers (GDGTs) found in hot springs reflect the abundance and community structure of Archaea in these extreme environments. The relationships between GDGTs, archaeal communities, and physical or geochemical variables are underexamined to date and when reported often result in conflicting interpretations. Here, we examined profiles of GDGTs from pure cultures of Crenarchaeota and from terrestrial geothermal springs representing a wide distribution of locations, including Yellowstone National Park (United States), the Great Basin of Nevada and California (United States), Kamchatka (Russia), Tengchong thermal field (China), and Thailand. These samples had temperatures of 36.5 to 87°C and pH values of 3.0 to 9.2. GDGT abundances also were determined for three soil samples adjacent to some of the hot springs. Principal component analysis identified four factors that accounted for most of the variance among nine individual GDGTs, temperature, and pH. Significant correlations were observed between pH and the GDGTs crenarchaeol and GDGT-4 (four cyclopentane rings, m/z 1,294); pH correlated positively with crenarchaeol and inversely with GDGT-4. Weaker correlations were observed between temperature and the four factors. Three of the four GDGTs used in the marine TEX86 paleotemperature index (GDGT-1 to -3, but not crenarchaeol isomer) were associated with a single factor. No correlation was observed for GDGT-0 (acyclic caldarchaeol): it is effectively its own variable. The biosynthetic mechanisms and exact archaeal community structures leading to these relationships remain unknown. However, the data in general show promise for the continued development of GDGT lipid-based physiochemical proxies for archaeal evolution and for paleo-ecology or paleoclimate studies. PMID:18390673

Geochemical Approach to Archaeal Ecology: δ13C of GDGTs

NASA Astrophysics Data System (ADS)

Lichtin, S.; Warren, C.; Pearson, A.; Pagani, M.

2015-12-01

Over the last decade and a half, glycerol dialkyl glycerol tetraethers (GDGTs) have increasingly been used to reconstruct environmental temperatures; proxies like TEX86 that correlate the relative abundance of these archaeal cell membrane lipids to sea surface temperature are omnipresent in paleoclimatology literature. While it has become common to make claims about past temperatures using GDGTs, our present understanding of the organisms that synthesize the compounds is still quite limited. The generally accepted theory states that microorganisms like the Thaumarchaeota modify the structure of membrane lipids to increase intermolecular interactions, strengthening the membrane at higher temperatures. Yet to date, culture experiments have been largely restricted to a single species, Nitrosopumilus maritimes, and recent studies on oceanic archaeal rRNA have revealed that these biomarkers are produced in diverse, heterogeneous, and site-specific communities. This brings up questions as to whether different subclasses of GDGTs, and all subsequent proxies, represent adaptation within a single organismal group or a shift in community composition. To investigate whether GDGTs with different chain structures, from the simple isoprenoidal GDGT-0 to Crenarchaeol with its many cyclopentane groups, are sourced from archaea with similar or disparate metabolic pathways—and if that information is inherited in GDGTs trapped in marine sediments—this study examines the stable carbon isotope values (δ13C) of GDGTs extracted from the uppermost meters of sediment in the Orca Basin, Gulf of Mexico, using spooling-wire microcombustion isotope-ratio mass spectrometer (SWiM-IRMS), tackling a fundamental assumption of the TEX86 proxy that influences the way we perceive the veracity of existing temperature records.

STM investigations of Au(1 1 1) electrodes coated with vitamin B 12 derivatives

NASA Astrophysics Data System (ADS)

Szőcs, E.; Durrer, L.; Luginbühl, R.; Simic, N.; Viana, A. S.; Abrantes, L. M.; Keese, R.; Siegenthaler, H.

2006-01-01

Vitamin B 12 derivatives immobilized at flame-annealed Au(1 1 1) electrode surfaces have been investigated in close correlation with their structural properties and spatial arrangement at the electrode substrate by scanning tunneling microscopy (STM) in air and in aqueous 0.1 M NaClO 4 solution. The investigated compounds were symmetrical (B 12C 10S-SC 10B 12) and nonsymmetrical (B 12C 10S-SC 10) dialkyl disulfide derivatives of vitamin B 12, attached to the electrode surfaces by the S-Au bond. The ex situ and in situ STM experiments show the formation of a surface layer, whose packing density and structure is presumably controlled by the spatial arrangement of the large cobyrinate head groups. In presence of the symmetrical B 12 compound, a disordered surface layer is observed. Voltammetric investigations show that, in 0.1 M NaClO 4, this layer becomes unstable at potentials approximately ⩽ -1000 mV vs. MSE and is almost completely removed at more negative potentials. The STM imaging properties of the nonsymmetrical B 12 surface layer show a significant dependence on the tunneling distance. In particular, at small tunneling distances, a highly regular hexagonal surface pattern is observed that suggests strongly the presence of an ordered surface assembly. Modeling of the B 12 head group has been performed to provide information for a structure-related interpretation of the high-resolution STM images. The investigations are first STM results obtained at such B 12 modified electrodes.

Early Paleogene evolution of terrestrial climate in the SW Pacific, Southern New Zealand

NASA Astrophysics Data System (ADS)

Pancost, Richard D.; Taylor, Kyle W. R.; Inglis, Gordon N.; Kennedy, Elizabeth M.; Handley, Luke; Hollis, Christopher J.; Crouch, Erica M.; Pross, Jörg; Huber, Matthew; Schouten, Stefan; Pearson, Paul N.; Morgans, Hugh E. G.; Raine, J. Ian

2013-12-01

We present a long-term record of terrestrial climate change for the Early Paleogene of the Southern Hemisphere that complements previously reported marine temperature records. Using the MBT'-CBT proxy, based on the distribution of soil bacterial glycerol dialkyl glycerol tetraether lipids, we reconstructed mean annual air temperature (MAT) from the Middle Paleocene to Middle Eocene (62-42 Ma) for southern New Zealand. This record is consistent with temperature estimates derived from leaf fossils and palynology, as well as previously published MBT'-CBT records, which provides confidence in absolute temperature estimates. Our record indicates that through this interval, temperatures were typically 5°C warmer than those of today at such latitudes, with more pronounced warming during the Early Eocene Climate Optimum (EECO; ˜50 Ma) when MAT was ˜20°C. Moreover, the EECO MATs are similar to those determined for Antarctica, with a weak high-latitude terrestrial temperature gradient (˜5°C) developing by the Middle Eocene. We also document a short-lived cooling episode in the early Late Paleocene when MAT was comparable to present. This record corroborates the trends documented by sea surface temperature (SST) proxies, although absolute SSTs are up to 6°C warmer than MATs. Although the high-calibration error of the MBT'-CBT proxy dictates caution, the good match between our MAT results and modeled temperatures supports the suggestion that SST records suffer from a warm (summer?) bias, particularly during times of peak warming.

Electron transfer of quinone self-assembled monolayers on a gold electrode.

PubMed

Nagata, Morio; Kondo, Masaharu; Suemori, Yoshiharu; Ochiai, Tsuyoshi; Dewa, Takehisa; Ohtsuka, Toshiaki; Nango, Mamoru

2008-06-15

Dialkyl disulfide-linked naphthoquinone, (NQ-Cn-S)2, and anthraquinone, (AQ-Cn-S)2, derivatives with different spacer alkyl chains (Cn: n=2, 6, 12) were synthesized and these quinone derivatives were self-assembled on a gold electrode. The formation of self-assembled monolayers (SAMs) of these derivatives on a gold electrode was confirmed by infrared reflection-absorption spectroscopy (IR-RAS). Electron transfer between the derivatives and the gold electrode was studied by cyclic voltammetry. On the cyclic voltammogram a reversible redox reaction between quinone (Q) and hydroquinone (QH2) was clearly observed under an aqueous condition. The formal potentials for NQ and AQ derivatives were -0.48 and -0.58 V, respectively, that did not depend on the spacer length. The oxidation and reduction peak currents were strongly dependent on the spacer alkyl chain length. The redox behavior of quinone derivatives depended on the pH condition of the buffer solution. The pH dependence was in agreement with a theoretical value of E 1/2 (mV)=E'-59pH for 2H+/2e(-) process in the pH range 3-11. In the range higher than pH 11, the value was estimated with E 1/2 (mV)=E'-30pH , which may correspond to H+/2e(-) process. The tunneling barrier coefficients (beta) for NQ and AQ SAMs were determined to be 0.12 and 0.73 per methylene group (CH2), respectively. Comparison of the structures and the alkyl chain length of quinones derivatives on these electron transfers on the electrode is made.

Assessment of the sources of sedimentary organic matter in the Bohai Sea and the northern Yellow Sea using biomarker proxies

NASA Astrophysics Data System (ADS)

Xing, Lei; Hou, Di; Wang, Xinchen; Li, Li; Zhao, Meixun

2016-07-01

To evaluate the applicability of source proxies and to assess the sources of sedimentary organic matter in the Bohai Sea (BS) and the northern Yellow Sea (NYS), we analyzed total organic carbon (TOC), total nitrogen (TN), δ13C of TOC, n-alkanes, phytoplankton biomarkers, and glycerol dialkyl glycerol tetraethers (GDGTs) including branched GDGTs (brGDGTs) in 60 surface sediment samples covering the BS and the NYS. Spatial distribution comparison and principal component analysis indicate that with the exception of brGDGTs, terrestrial biomarkers have different spatial distribution pattern from marine biomarkers, suggesting that the sources control the distributions of these biomarkers in spite of hydrodynamic forcing. Significantly positive correlation (R2 = 0.5) between TOC normalized brGDGTs content and TOC normalized crenarchaeol content suggested in situ production of brGDGTs in the BS and the NYS. The δ13C values, TMBR [terrestrial and marine biomarker ratio: (C27 + C29 + C31n-alkanes)/[(C27 + C29 + C31n-alkanes) + (brassicasterol + dinosterol + alkenones)] ] and BIT (branched isoprenoid tetratether index) proxy indicated high terrestrial organic matter (TOM) input near the Huanghe River Estuary, while TOC/TON did not reveal similar distribution pattern. Quantitative estimates of TOM using a binary model revealed much higher TOM percentage from δ13C (avg. 58%) and TMBR (avg. 31%) than from BIT (avg. 7.4%). Our results suggest that, owing to significant in situ production of brGDGTs, the BIT is not a good proxy for indicating soil OM contribution in marine sediments from the BS and the NYS.

Effects of analogles of ethanolamine and choline on phospholipid metabolism in rat hepatocytes.

PubMed

Akesson, B

1977-12-15

1. Analogues of ethanolamine and choline were incubated with different labelled precursors of phospholipids and isolated hepatocytes and the effects on phospholipid synthesis were studied. 2. 2-Aminopropan-1-ol and 2-aminobutan-1-ol were the most efficient inhibitors of [(14)C]ethanolamine incorporation into phospholipids, whereas the incorporation of [(3)H]choline was inhibited most extensively by NN-diethylethanolamine and NN-dimethylethanolamine. 3. When the analogues were incubated with [(3)H]glycerol and hepatocytes, the appearance of (3)H in unnatural phospholipids indicated that they were incorporated, at least in part, via CDP-derivatives. The distribution of [(3)H]glycerol among molecular species of phospholipids containing 2-aminopropan-1-ol and 1-aminopropan-2-ol was the same as in phosphatidylethanolamine. In other phospholipid analogues the distribution of (3)H was more similar to that in phosphatidylcholine. 4. NN-Diethylethanolamine stimulated both the conversion of phosphatidylethanolamine into phosphatidylcholine and the incorporation of [Me-(14)C]methionine into phospholipids. Other N-alkyl- or NN-dialkyl-ethanolamines also stimulated [(14)C]methionine incorporation, but inhibited the conversion of phosphatidylethanolamine into phosphatidylcholine. This indicates that phosphatidyl-NN-diethylethanolamine is a poor methyl acceptor, in contrast with other N-alkylated phosphatidylethanolamines. 5. These results on the regulation of phospholipid metabolism in intact cells are discussed with respect to the possible control points. They also provide guidelines for future experiments on the manipulation of phospholipid polar-headgroup composition in primary cultures of hepatocytes.

Transfection Studies with Colloidal Systems Containing Highly Purified Bipolar Tetraether Lipids from Sulfolobus acidocaldarius

PubMed Central

Pinnapireddy, Shashank Reddy; Baghdan, Elias; Jedelská, Jarmila

2017-01-01

Lipid vectors are commonly used to facilitate the transfer of nucleic acids into mammalian cells. In this study, two fractions of tetraether lipids from the archaea Sulfolobus acidocaldarius were extracted and purified using different methods. The purified lipid fractions polar lipid fraction E (PLFE) and hydrolysed glycerol-dialkyl-nonitol tetraether (hGDNT) differ in their structures, charge, size, and miscibility from conventional lipids. Liposomes were prepared by mixing tetraether lipids with cholesterol (CH) and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) resulting in stable vectors for gene delivery. Lipoplexes were prepared by complexation of liposomes with a luciferase expressing plasmid (pCMV-luc) at certain nitrogen-to-phosphorus (N/P) ratios and optimised for the transient transfection of ovarian adenocarcinoma cells (SK-OV-3). Complexation efficacy was investigated by gel-red fluorescence assay. Biophysical properties, like size, surface charge, and morphology, were investigated by differential light scattering (DLS), atomic force microscopy (AFM), and scanning electron microscopy (Cryo-SEM), respectively, revealing structural differences between liposomes and lipoplexes. A range of stable transfecting agents containing tetraether lipids were obtained by incorporating 5 mol% of tetraether lipids. Lipoplexes showed a decrease in free gel-red with increasing N/P ratios indicating efficient incorporation of plasmid DNA (pDNA) and remarkable stability. Transfection experiments of the lipoplexes revealed successful and superior transfection of SK-OV-3 cell line compared to the commercially available DOTAP and branched polyethyleneimine (25 kDa bPEI). PMID:28239294

Linking isoprenoidal GDGT membrane lipid distributions with gene abundances of ammonia-oxidizing Thaumarchaeota and uncultured crenarchaeotal groups in the water column of a tropical lake (Lake Challa, East Africa).

PubMed

Buckles, Laura K; Villanueva, Laura; Weijers, Johan W H; Verschuren, Dirk; Damsté, Jaap S Sinninghe

2013-09-01

Stratified lakes are important reservoirs of microbial diversity and provide habitats for niche differentiation of Archaea. In this study, we used a lipid biomarker/DNA-based approach to reveal the diversity and abundance of Archaea in the water column of Lake Challa (East Africa). Concentrations of intact polar lipid (IPL) crenarchaeol, a specific biomarker of Thaumarchaeota, were enhanced (1 ng l(-1) ) at the oxycline/nitrocline. The predominance of the more labile IPL hexose-phosphohexose crenarchaeol indicated the presence of an actively living community of Thaumarchaeota. Archaeal 16S rRNA clone libraries revealed the presence of thaumarchaeotal groups 1.1a and 1.1b at and above the oxycline. In the anoxic deep water, amoA gene abundance was an order of magnitude lower than at the oxycline and high abundance (∼90 ng l(-1) ) of an IPL with the acyclic glycerol dialkyl glycerol tetraether (GDGT-0) was evident. The predominance of archaeal 16S rRNA sequences affiliated to the uncultured crenarchaeota groups 1.2 and miscellaneous crenarchaeotic group (MCG) points to an origin of GDGT-0 from uncultured crenarchaeota. This study demonstrates the importance of thermal stratification and nutrient availability in the distribution of archaeal groups in lakes, which is relevant to constrain and validate temperature proxies based on archaeal GDGTs (i.e. TEX86 ). © 2013 John Wiley & Sons Ltd and Society for Applied Microbiology.

Correlating Charge Transport with Structure in Deconstructed Diketopyrrolopyrrole Oligomers: A Case Study of a Monomer in Field-Effect Transistors.

PubMed

Pickett, Alec; Torkkeli, Mika; Mukhopadhyay, Tushita; Puttaraju, Boregowda; Laudari, Amrit; Lauritzen, Andreas E; Bikondoa, Oier; Kjelstrup-Hansen, Jakob; Knaapila, Matti; Patil, Satish; Guha, Suchismita

2018-06-13

Copolymers based on diketopyrrolopyrrole (DPP) cores have attracted a lot of attention because of their high p-type as well as n-type carrier mobilities in organic field-effect transistors (FETs) and high power conversion efficiencies in solar cell structures. We report the structural and charge transport properties of n-dialkyl side-chain-substituted thiophene DPP end-capped with a phenyl group (Ph-TDPP-Ph) monomer in FETs which were fabricated by vacuum deposition and solvent coating. Grazing-incidence X-ray diffraction (GIXRD) from bottom-gate, bottom-contact FET architectures was measured with and without biasing. Ph-TDPP-Ph reveals a polymorphic structure with π-conjugated stacking direction oriented in-plane. The unit cell comprises either one monomer with a = 20.89 Å, b = 13.02 Å, c = 5.85 Å, α = 101.4°, β = 90.6°, and γ = 94.7° for one phase (TR1) or two monomers with a = 24.92 Å, b = 25.59 Å, c = 5.42 Å, α = 80.3°, β = 83.5°, and γ = 111.8° for the second phase (TR2). The TR2 phase thus signals a shift from a coplanar to herringbone orientation of the molecules. The device performance is sensitive to the ratio of the two triclinic phases found in the film. Some of the best FET performances with p-type carrier mobilities of 0.1 cm 2 /V s and an on/off ratio of 10 6 are for films that comprise mainly the TR1 phase. GIXRD from in operando FETs demonstrates the crystalline stability of Ph-TDPP-Ph.

Exposure of Preschool-Age Greek Children (RHEA Cohort) to Bisphenol A, Parabens, Phthalates, and Organophosphates.

PubMed

Myridakis, Antonis; Chalkiadaki, Georgia; Fotou, Marianna; Kogevinas, Manolis; Chatzi, Leda; Stephanou, Euripides G

2016-01-19

Phthalate esters (PEs), bisphenol A (BPA), and parabens (PBs), which are used in numerous consumer products, are known for their endocrine disrupting properties. Organophosphate chemicals (OPs), which form the basis of the majority of pesticides, are known for their neurotoxic activity in humans. All of these chemicals are associated with health problems to which children are more susceptible. Once they enter the human body, PEs, BPA, PBs, and OPs are metabolized and/or conjugated and finally excreted via urine. Hence, human exposure to these substances is examined through a determination of the urinary concentrations of their metabolites. This study assessed the exposure of Greek preschool-age children to PEs, BPA, PBs, and OPs by investigating the urinary levels of seven PEs metabolites, six PBs, BPA, and six dialkyl phosphate metabolites in five-hundred samples collected from 4-year-old children, subjects of the "RHEA" mother-child cohort in Crete, Greece. Daily intake of endocrine disruptors, calculated for 4 year old children, was lower than the corresponding daily intake for 2.5 year old children, which were determined in an earlier study of the same cohort. In some cases the daily intake levels exceeded the U.S. Environmental Protection Agency Tolerable Daily Intake (TDI) values and the EFSA Reference Doses (RfD) (e.g., for di-2-ethyl-hexyl phthalate, 3.6% and 1% of the children exceeded RfD and TDi, respectively). Exposure was linked to three main sources: PEs-BPA to plastic, PBs-diethyl phthalate to personal hygiene products, and OPs to food.

A climate and environmental context for hominid evolution: Preliminary biomarker and compound specific isotope data from Lake Magadi, Kenya

NASA Astrophysics Data System (ADS)

Werne, J. P.; Ferland, T.; Cohen, A. S.; Lowenstein, T. K.; Deocampo, D.; Renaut, R.; Bernhart, O. R.

2016-12-01

The Hominid Sites and Paleolakes Drilling Project (HSPDP) seeks to understand the paleoclimatic and paleoenvironmental context of human evolution and development by analysis of paleolacustrine cores taken near key hominin fossil and artifact localities in Kenya and Ethiopia. Here, we present biomarker and compound specific isotope data from a 200 m drill core from Lake Magadi, Kenya. Located 20 km from the Koora Plain in the southern Kenya Rift, and adjacent to the Olorgesailie basin, Lake Magadi is in one of the richest Early-Late Pleistocene archaeological localities in Africa, a region that has been key in debates about the relationship between climate and evolution. Preliminary biomarker work has shown promising abundances of leaf waxes, whose isotopic compositions of hydrogen and carbon are commonly used as proxies for paleoprecipitation and watershed vegetation composition, respectively. A complementary record of glycerol dialkyl glycerol tetraethers (GDGTs), which can serve as a proxy for temperature, soil input, and/or pH, will be presented alongside the leaf wax data to enhance the paleoenvironmental reconstruction of Lake Magadi. Present-day Lake Magadi is a saline pan, a descendant of a series of paleolakes that have occupied its drainage basin for approximately one million years. Hominid evolution milestones such as the mastering of fire as a tool, rapid encephalization, and the emergence of Homo sapiens all are thought to have occurred in the time frame encompassed by our record.

Variability of Organophosphorous Pesticide Metabolite Levels in Spot and 24-hr Urine Samples Collected from Young Children during 1 Week

PubMed Central

Kogut, Katherine; Eisen, Ellen A.; Jewell, Nicholas P.; Quirós-Alcalá, Lesliam; Castorina, Rosemary; Chevrier, Jonathan; Holland, Nina T.; Barr, Dana Boyd; Kavanagh-Baird, Geri; Eskenazi, Brenda

2012-01-01

Background: Dialkyl phosphate (DAP) metabolites in spot urine samples are frequently used to characterize children’s exposures to organophosphorous (OP) pesticides. However, variable exposure and short biological half-lives of OP pesticides could result in highly variable measurements, leading to exposure misclassification. Objective: We examined within- and between-child variability in DAP metabolites in urine samples collected during 1 week. Methods: We collected spot urine samples over 7 consecutive days from 25 children (3–6 years of age). On two of the days, we collected 24-hr voids. We assessed the reproducibility of urinary DAP metabolite concentrations and evaluated the sensitivity and specificity of spot urine samples as predictors of high (top 20%) or elevated (top 40%) weekly average DAP metabolite concentrations. Results: Within-child variance exceeded between-child variance by a factor of two to eight, depending on metabolite grouping. Although total DAP concentrations in single spot urine samples were moderately to strongly associated with concentrations in same-day 24-hr samples (r ≈ 0.6–0.8, p < 0.01), concentrations in spot samples collected > 1 day apart and in 24-hr samples collected 3 days apart were weakly correlated (r ≈ –0.21 to 0.38). Single spot samples predicted high (top 20%) and elevated (top 40%) full-week average total DAP excretion with only moderate sensitivity (≈ 0.52 and ≈ 0.67, respectively) but relatively high specificity (≈ 0.88 and ≈ 0.78, respectively). Conclusions: The high variability we observed in children’s DAP metabolite concentrations suggests that single-day urine samples provide only a brief snapshot of exposure. Sensitivity analyses suggest that classification of cumulative OP exposure based on spot samples is prone to type 2 classification errors. PMID:23052012

Historical changes in organic matter input to the muddy sediments along the Zhejiang-Fujian Coast, China over the past 160 years

USGS Publications Warehouse

Chen, Li-lei; Liu, Jian; Xing, Lei; Krauss, Ken W.; Wang, Jia-sheng; Xu, Gang; Li, Li

2017-01-01

The burial of sedimentary organic matter (SOM) in the large river-influenced estuarine-coastal regions is affected by hydrodynamic sorting, diagenesis and human activities. Typically, the inner shelf region of the East China Sea is a major carbon sink of the Yangtze River-derived fine-grained sediments. Most of the previous work concentrated on the studies of surface sediments or used a single-proxy in this region. In this study, two cores from the Zhejiang-Fujian Coast were analyzed using bulk (TOC, TN and δ13CTOC) and molecular biomarker (n-alkane, brassicasterol, dinosterol and glycerol dialkyl glycerol tetraether lipids) techniques to clarify the sources, spatiotemporal distribution and fate of SOM in the Yangtze River Estuary and adjacent shelf. Results from this study indicated that the effects of diagenesis and diffusion on different sedimentary biomarkers resulted in overestimation of the relative contribution of terrestrial organic matter (%OMterr), compared with those based on δ13CTOC. The amounts of terrestrial plant organic matter (OMplant) and%OMterr in sediments decreased offshore. In contrast, the amounts of marine organic matter (OMmarine) increased offshore, but closer to the Yangtze River mouth, the amounts of soil organic matter (OMsoil) increased. Moreover, the amounts of TOC, OMplant and OMmarine biomarkers increased, but OMsoil and%OMterrdecreased over time in recent decades. Our study suggests that spatial organic matter distribution patterns in marine shelf sediments were controlled primarily by hydrodynamic sorting and nutrient concentrations, and temporally diverse patterns were controlled predominantly by anthropogenic influence (e.g., dam construction and soil conservation, reclamation and agricultural plantations, anthropogenic nutrient input, dust storms, eutrophication, etc) and climate events (e.g., interdecadal climatic jump and heavy rain events) in the geological period.

The C- and N-Terminal Residues of Synthetic Heptapeptide Ion Channels Influence Transport Efficacy Through Phospholipid Bilayers

PubMed Central

Djedovič, Natasha; Ferdani, Riccardo; Harder, Egan; Pajewska, Jolanta; Pajewski, Robert; Weber, Michelle E.; Schlesinger, Paul H.; Gokel, George W.

2008-01-01

The synthetic peptide, R2N-COCH2OCH2CO-Gly-Gly-Gly-Pro-Gly-Gly-Gly-OR’, was shown to be selective for Cl- over K+ when R is n-octadecyl and R’ is benzyl. Nineteen heptapeptides have now been prepared in which the N-terminal and C-terminal residues have been varied. All of the N-terminal residues are dialkyl but the C-terminal chains are esters, 2° amides, or 3° amides. The compounds having varied N-terminal anchors and C-terminal benzyl groups are as follows: 1, R = n-propyl; 2, R = n-hexyl; 3, R = n-octyl; 4, R = n-decyl; 5, R = n-dodecyl; 6, R = n-tetradecyl; 7, R = n-hexadecyl; 8, R = n-octadecyl. Compounds 9-19 have R = n-octadecyl and C-terminal residues as follows: 9, OR’ = OCH2CH3; 10, OR’ = OCH(CH3)2; 11, OR’ = O(CH2)6CH3; 12, OR’ = OCH2-c-C6H11; 13, OR’ = O(CH2)9CH3; 14, OR’ = O (CH2)17CH3; 15, NR’2 = N[(CH2)6CH3]2; 16, NHR’ = NH(CH2)9CH3; 17, NR’2 = N[(CH2)9CH3]2; 18, NHR’ = NH(CH2)17CH3; 19, NR’2 = N[(CH2)17CH3]2. The highest anion transport activities were observed as follows. For the benzyl esters whose N-terminal residues were varied, i.e. 1-8, compound 3 was most active. For the C18 anchored esters 10-14, n-heptyl ester 11 was most active. For the C18 anchored, C-terminal amides 15-19, di-n-decylamide 17 was most active. It was concluded that both the C- and N-terminal anchors were important for channel function in the bilayer but that activity was lost unless only one of the two anchoring groups was dominant. PMID:19633728

Autocatalytic, bistable, oscillatory networks of biologically relevant organic reactions.

PubMed

Semenov, Sergey N; Kraft, Lewis J; Ainla, Alar; Zhao, Mengxia; Baghbanzadeh, Mostafa; Campbell, Victoria E; Kang, Kyungtae; Fox, Jerome M; Whitesides, George M

2016-09-29

Networks of organic chemical reactions are important in life and probably played a central part in its origin. Network dynamics regulate cell division, circadian rhythms, nerve impulses and chemotaxis, and guide the development of organisms. Although out-of-equilibrium networks of chemical reactions have the potential to display emergent network dynamics such as spontaneous pattern formation, bistability and periodic oscillations, the principles that enable networks of organic reactions to develop complex behaviours are incompletely understood. Here we describe a network of biologically relevant organic reactions (amide formation, thiolate-thioester exchange, thiolate-disulfide interchange and conjugate addition) that displays bistability and oscillations in the concentrations of organic thiols and amides. Oscillations arise from the interaction between three subcomponents of the network: an autocatalytic cycle that generates thiols and amides from thioesters and dialkyl disulfides; a trigger that controls autocatalytic growth; and inhibitory processes that remove activating thiol species that are produced during the autocatalytic cycle. In contrast to previous studies that have demonstrated oscillations and bistability using highly evolved biomolecules (enzymes and DNA) or inorganic molecules of questionable biochemical relevance (for example, those used in Belousov-Zhabotinskii-type reactions), the organic molecules we use are relevant to metabolism and similar to those that might have existed on the early Earth. By using small organic molecules to build a network of organic reactions with autocatalytic, bistable and oscillatory behaviour, we identify principles that explain the ways in which dynamic networks relevant to life could have developed. Modifications of this network will clarify the influence of molecular structure on the dynamics of reaction networks, and may enable the design of biomimetic networks and of synthetic self-regulating and evolving chemical systems.

Distribution of ether lipids and composition of the archaeal community in terrestrial geothermal springs: impact of environmental variables.

PubMed

Xie, Wei; Zhang, Chuanlun L; Wang, Jinxiang; Chen, Yufei; Zhu, Yuanqing; de la Torre, José R; Dong, Hailiang; Hartnett, Hilairy E; Hedlund, Brian P; Klotz, Martin G

2015-05-01

Archaea can respond to changes in the environment by altering the composition of their membrane lipids, for example, by modification of the abundance and composition of glycerol dialkyl glycerol tetraethers (GDGTs). Here, we investigated the abundance and proportions of polar GDGTs (P-GDGTs) and core GDGTs (C-GDGTs) sampled in different seasons from Tengchong hot springs (Yunnan, China), which encompassed a pH range of 2.5-10.1 and a temperature range of 43.7-93.6°C. The phylogenetic composition of the archaeal community (reanalysed from published work) divided the Archaea in spring sediment samples into three major groups that corresponded with spring pH: acidic, circumneutral and alkaline. Cluster analysis showed correlation between spring pH and the composition of P- and C-GDGTs and archaeal 16S rRNA genes, indicating an intimate link between resident Archaea and the distribution of P- and C-GDGTs in Tengchong hot springs. The distribution of GDGTs in Tengchong springs was also significantly affected by temperature; however, the relationship was weaker than with pH. Analysis of published datasets including samples from Tibet, Yellowstone and the US Great Basin hot springs revealed a similar relationship between pH and GDGT content. Specifically, low pH springs had higher concentrations of GDGTs with high numbers of cyclopentyl rings than neutral and alkaline springs, which is consistent with the predominance of high cyclopentyl ring-characterized Sulfolobales and Thermoplasmatales present in some of the low pH springs. Our study suggests that the resident Archaea in these hot springs are acclimated if not adapted to low pH by their genetic capacity to effect the packing density of their membranes by increasing cyclopentyl rings in GDGTs at the rank of community. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

Mono- and Dialkyl Glycerol Ether Lipids in Anaerobic Bacteria: Biosynthetic Insights from the Mesophilic Sulfate Reducer Desulfatibacillum alkenivorans PF2803T

PubMed Central

Mollex, Damien; Vinçon-Laugier, Arnauld; Hakil, Florence; Pacton, Muriel; Cravo-Laureau, Cristiana

2015-01-01

Bacterial glycerol ether lipids (alkylglycerols) have received increasing attention during the last decades, notably due to their potential role in cell resistance or adaptation to adverse environmental conditions. Major uncertainties remain, however, regarding the origin, biosynthesis, and modes of formation of these uncommon bacterial lipids. We report here the preponderance of monoalkyl- and dialkylglycerols (1-O-alkyl-, 2-O-alkyl-, and 1,2-O-dialkylglycerols) among the hydrolyzed lipids of the marine mesophilic sulfate-reducing proteobacterium Desulfatibacillum alkenivorans PF2803T grown on n-alkenes (pentadec-1-ene or hexadec-1-ene) as the sole carbon and energy source. Alkylglycerols account for one-third to two-thirds of the total cellular lipids (alkylglycerols plus acylglycerols), depending on the growth substrate, with dialkylglycerols contributing to one-fifth to two-fifths of the total ether lipids. The carbon chain distribution of the lipids of D. alkenivorans also depends on that of the substrate, but the chain length and methyl-branching patterns of fatty acids and monoalkyl- and dialkylglycerols are systematically congruent, supporting the idea of a biosynthetic link between the three classes of compounds. Vinyl ethers (1-alken-1′-yl-glycerols, known as plasmalogens) are not detected among the lipids of strain PF2803T. Cultures grown on different (per)deuterated n-alkene, n-alkanol, and n-fatty acid substrates further demonstrate that saturated alkylglycerols are not formed via the reduction of hypothetic alken-1′-yl intermediates. Our results support an unprecedented biosynthetic pathway to monoalkyl/monoacyl- and dialkylglycerols in anaerobic bacteria and suggest that n-alkyl compounds present in the environment can serve as the substrates for supplying the building blocks of ether phospholipids of heterotrophic bacteria. PMID:25724965

Relationship between Urinary Pesticide Residue Levels and Neurotoxic Symptoms among Women on Farms in the Western Cape, South Africa

PubMed Central

Motsoeneng, Portia M.; Dalvie, Mohamed A.

2015-01-01

Background: This cross-sectional study aimed to investigate the relationship between urinary pesticide residue levels and neurotoxic symptoms amongst women working on Western Cape farms in South Africa. Method: A total of 211 women were recruited from farms (n = 121) and neighbouring towns (n = 90). Participant assessment was via a Q16 questionnaire, reporting on pesticide exposures and measurement of urinary OP metabolite concentrations of dialkyl phosphates (DAP) and chlorpyriphos, 3,5,6-trichloropyridinol (TCPY) and of pyrethroid (PYR) metabolite concentrations (3- phenoxybenzoic acid (3PBA), 4-fluoro-3-phenoxybenzoic acid (4F3PBA), cis-2,2-dibromovinyl-2,2-dimethylcyclopropane-1-carboxylic acid (DBCA), and the cis- and trans isomers of 2,2-dichlorovinyl-2,2-dimethylcyclopropane-1-carboxylic acid. Results: Median urinary pesticide metabolites were slightly (6%–49%) elevated in the farm group compared to the town group, with 2 metabolites significantly higher and some lower in the farm group. The prevalence of all Q16 symptoms was higher amongst farm women compared to town women. Three Q16 symptoms (problems with buttoning, reading and notes) were significantly positively associated with three pyrethroid metabolites (cis- and trans-DCCA and DBCA), although associations may due to chance as multiple comparisons were made. The strongest association for a pyrethroid metabolite was between problems with buttoning and DBCA (odds ratio (OR) = 8.93, 95% confidence interval (CI):1.71–46.5. There was no association between Q16 symptoms and OP metabolites. Conclusions: Women farm residents and rural women from neighbouring towns in the Western Cape are exposed to OP and PYR pesticides. The study did not provide strong evidence that pesticides are associated with neurotoxic symptoms but associations found could be explored further. PMID:26042367

Evaluation of the irritancy and hypersensitivity potential following topical application of didecyldimethylammonium chloride

PubMed Central

Anderson, Stacey E.; Shane, Hillary; Long, Carrie; Lukomska, Ewa; Meade, B. Jean; Marshall, Nikki B.

2016-01-01

Didecyldimethylammonium chloride (DDAC) is a dialkyl-quaternary ammonium compound that is used in numerous products for its bactericidal, virucidal and fungicidal properties. There have been clinical reports of immediate and delayed hypersensitivity reactions in exposed individuals; however, the sensitization potential of DDAC has not been thoroughly investigated. The purpose of these studies was to evaluate the irritancy and sensitization potential of DDAC following dermal exposure in a murine model. DDAC induced significant irritancy (0.5 and 1%), evaluated by ear swelling in female Balb/c mice. Initial evaluation of the sensitization potential was conducted using the local lymph node assay (LLNA) at concentrations ranging from 0.0625–1%. A concentration-dependent increase in lymphocyte proliferation was observed with a calculated EC3 value of 0.17%. Dermal exposure to DDAC did not induce increased production of IgE as evaluated by phenotypic analysis of draining lymph node B-cells (IgE+B220+) and measurement of total serum IgE levels. Additional phenotypic analyses revealed significant and dose-responsive increases in the absolute number of B-cells, CD4+ T-cells, CD8+ T-cells and dendritic cells in the draining lymph nodes, along with significant increases in the percentage of B-cells (0.25% and 1% DDAC) at Day 10 following 4 days of dermal exposure. There was also a significant and dose-responsive increase in the number of activated CD44 + CD4 + and CD8+ T-cells and CD86+ B-cells and dendritic cells following exposure to all concentrations of DDAC. These results demonstrate the potential for development of irritation and hypersensitivity responses to DDAC following dermal exposure and raise concerns about the use of this chemical and other quaternary ammonium compounds that may elicit similar effects. PMID:27216637

Effect of double-tailed surfactant architecture on the conformation, self-assembly, and processing in polypeptide-surfactant complexes.

PubMed

Junnila, Susanna; Hanski, Sirkku; Oakley, Richard J; Nummelin, Sami; Ruokolainen, Janne; Faul, Charl F J; Ikkala, Olli

2009-10-12

This work describes the solid-state conformational and structural properties of self-assembled polypeptide-surfactant complexes with double-tailed surfactants. Poly(L-lysine) was complexed with three dialkyl esters of phosphoric acid (i.e., phosphodiester surfactants), where the surfactant tail branching and length was varied to tune the supramolecular architecture in a facile way. After complexation with the branched surfactant bis(2-ethylhexyl) phosphate in an aqueous solution, the polypeptide chains adopted an alpha-helical conformation. These rod-like helices self-assembled into cylindrical phases with the amorphous alkyl tails pointing outward. In complexes with dioctyl phosphate and didodecyl phosphate, which have two linear n-octyl or n-dodecyl tails, respectively, the polypeptide formed antiparallel beta-sheets separated by alkyl layers, resulting in well-ordered lamellar self-assemblies. By heating, it was possible to trigger a partial opening of the beta-sheets and disruption of the lamellar phase. After repeated heating/cooling, all of these complexes also showed a glass transition between 37 and 50 degrees C. Organic solvent treatment and plasticization by overstoichiometric amount of surfactant led to structure modification in poly(L-lysine)-dioctyl phosphate complexes, PLL(diC8)(x) (x = 1.0-3.0). Here, the alpha-helical PLL is surrounded by the surfactants and these bottle-brush-like chains self-assemble in a hexagonal cylindrical morphology. As x is increased, the materials are clearly plasticized and the degree of ordering is improved: The stiff alpha-helical backbones in a softened surfactant matrix give rise to thermotropic liquid-crystalline phases. The complexes were examined by Fourier transform infrared spectroscopy, small- and wide-angle X-ray scattering, transmission electron microscopy, differential scanning calorimetry, polarized optical microscopy, and circular dichroism.

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Travis S. Grimes; Richard D. Tillotson; Leigh R. Martin

TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln3+) from minor actinides (MAs) Am3+ and Cm3+. Traditional TALSPEAK organic phase is comprised of a monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0-2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. TALSPEAK balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. Although TALSPEAK is considered a successfulmore » separations scheme, recent fundamental studies have highlighted complex chemical interactions occurring in the aqueous and organic phases during the extraction process. Previous attempts to model the system have shown thermodynamic models do not accurately predict the observed extraction trends in the p[H+] range 2.5-4.8. In this study, the aqueous phase is modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2) and separations were performed without any effect on phase transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H+] 1.6-3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.« less

Myopia and Exposure to Organophosphate and Pyrethroid Pesticides in the General United States Population.

PubMed

Migneron-Foisy, Vincent; Bouchard, Maryse F; Freeman, Ellen E; Saint-Amour, Dave

2017-09-01

Previous research suggests that exposure to pesticides might be associated with human myopia, although data were obtained only from highly exposed individuals. The present study aimed to assess whether exposure to organophosphates and pyrethroids in the United States general population was associated with the prevalence of myopia. Data were obtained from the National Health and Nutrition Examination Survey (NHANES, years 1999-2008). One-spot urine samples were used to estimate the concentration of several pesticide metabolites. Exposure data and equivalent spherical refraction errors were available for 5147 and 2911 individuals for organophosphates and pyrethroids, respectively. Multiple logistic regression models were used to assess the relation between log10-transformed urinary levels of pesticide metabolites and the risk of moderate (≤-1 and >-5 diopters [D]) and high myopia (≤-5 D) in adolescents (12- to 19-years old) and young adults (20- to 40-years old). Models were adjusted for sex, age, ethnicity, diabetes, creatinine, cadmium and lead concentrations, and income in both age groups, but also for education level and cigarette and alcohol consumption in the adult group. No association between organophosphates or pyrethroid metabolites and myopia was observed. However, after adjusting for education level and cigarette and alcohol consumption, a statistically significant decreased risk of high myopia in those with a 10-fold increase of dialkyl phosphate metabolites was found in adults but only in men (P < 0.05). Our results suggest that exposure to organophosphates or pyrethroids do not increase the risk of myopia in the United States general population.

Factors controlling the distribution of archaeal tetraethers in terrestrial hot springs.

PubMed

Pearson, Ann; Pi, Yundan; Zhao, Weidong; Li, WenJun; Li, Yiliang; Inskeep, William; Perevalova, Anna; Romanek, Christopher; Li, Shuguang; Zhang, Chuanlun L

2008-06-01

Glycerol dialkyl glycerol tetraethers (GDGTs) found in hot springs reflect the abundance and community structure of Archaea in these extreme environments. The relationships between GDGTs, archaeal communities, and physical or geochemical variables are underexamined to date and when reported often result in conflicting interpretations. Here, we examined profiles of GDGTs from pure cultures of Crenarchaeota and from terrestrial geothermal springs representing a wide distribution of locations, including Yellowstone National Park (United States), the Great Basin of Nevada and California (United States), Kamchatka (Russia), Tengchong thermal field (China), and Thailand. These samples had temperatures of 36.5 to 87 degrees C and pH values of 3.0 to 9.2. GDGT abundances also were determined for three soil samples adjacent to some of the hot springs. Principal component analysis identified four factors that accounted for most of the variance among nine individual GDGTs, temperature, and pH. Significant correlations were observed between pH and the GDGTs crenarchaeol and GDGT-4 (four cyclopentane rings, m/z 1,294); pH correlated positively with crenarchaeol and inversely with GDGT-4. Weaker correlations were observed between temperature and the four factors. Three of the four GDGTs used in the marine TEX(86) paleotemperature index (GDGT-1 to -3, but not crenarchaeol isomer) were associated with a single factor. No correlation was observed for GDGT-0 (acyclic caldarchaeol): it is effectively its own variable. The biosynthetic mechanisms and exact archaeal community structures leading to these relationships remain unknown. However, the data in general show promise for the continued development of GDGT lipid-based physiochemical proxies for archaeal evolution and for paleo-ecology or paleoclimate studies.

Evidence that two alkyl ester quaternary ammonium compounds lack substantial human skin-sensitizing potential.

PubMed

Jowsey, Ian R; Kligman, Albert M; White, Ian R; Goossens, An; Basketter, David A

2007-03-01

Alkyl ester quaternary ammonium compounds (ester quats) are used extensively in fabric rinse conditioners. It is important to document in the literature the outcome of historical studies that were performed to assess the risk of adverse skin effects associated with their use. (1) To document the outcomes of historical studies performed to evaluate the skin sensitizing potential of two ester quats (the di-[hardened tallow fatty acid] ester of 2,3-dihydroxypropyl-trimethyl ammonium chloride [HEQ] and the dialkyl ester of triethanol ammonium methyl sulfate [TEA-Quat]) and (2) to demonstrate that these ester quats lack marked skin-sensitizing potential in humans, such that they do not present a risk of contact allergy for consumers who use fabric rinse conditioners. Each material was assessed in the human maximization test in a panel of 25 volunteers. Diagnostic patch testing was also performed with each material in a population of 239 patients undergoing routine patch testing for suspected allergic contact dermatitis. These data are also considered in the context of an exposure-based quantitative risk assessment. Neither HEQ nor TEA-Quat was found to cause skin sensitization under the conditions of the human maximization test. No evidence of contact allergy to the materials was found among the relatively small population assessed by diagnostic patch testing. This study provides evidence that HEQ and TEA-Quat lack substantial skin-sensitizing potential in humans. Taken together with similar data for other ester quats, it suggests that compounds in this class are unlikely to be significant human contact allergens.

Enrichment of the Amino Acid L-Isovaline by Aqueous Alteration on CI and CM Meteorite Parent Bodies

NASA Technical Reports Server (NTRS)

Glavin, Daniel P.; Dworkin, Jason P.

2009-01-01

The distribution and enantiomeric composition of the 5-carbon (C(sub 5)) amino acids found in Cl-, CM-, and CR-type carbonaceous meteorites were investigated by using liquid chromatography fluorescence detection/TOF-MS coupled with o-phthaldialdehyde/Nacetyl- l-cysteine derivatization. A large L-enantiomeric excess (ee) of the a-methyl amino acid isovaline was found in the CM meteorite Murchison (L(sub ee) = 18.5 +/- 2.6%) and the Cl meteorite Orguell (L(sub ee) = 15.2 +/- 4.0%). The measured value for Murchison is the largest enantiomeric excess in any meteorite reported to date, and the Orgueil measurement of an isovaline excess has not been reported previously for this or any Cl meteorite. The L-isovaline enrichments in these two carbonaceous meteorites cannot be the result of interference from other C(sub 5) amino acid isomers present in the samples, analytical biases, or terrestrial amino acid contamination. We observed no L-isovaline enrichment for the most primitive unaltered Antarctic CR meteorites EET 92042 and QUE 99177. These results are inconsistent with UV circularly polarized light as the primary mechanism for L-isovaline enrichment and indicate that amplification of a small initial isovaline asymmetry in Murchison and Orgueil occurred during an extended aqueous alteration phase on the meteorite parent bodies. The large asymmetry in isovaline and other alpha-dialkyl amino acids found in altered Ct and CM meteorites suggests that amino acids delivered by asteroids, comets, and their fragments would have biased the Earth's prebiotic organic inventory with left-handed molecules before the origin of life.

Discovery of novel Tetrahydrobenzo[b]thiophene and pyrrole based scaffolds as potent and selective CB2 receptor ligands: The structural elements controlling binding affinity, selectivity and functionality.

PubMed

Osman, Noha A; Ligresti, Alessia; Klein, Christian D; Allarà, Marco; Rabbito, Alessandro; Di Marzo, Vincenzo; Abouzid, Khaled A; Abadi, Ashraf H

2016-10-21

CB2-based therapeutics show strong potential in the treatment of diverse diseases such as inflammation, multiple sclerosis, pain, immune-related disorders, osteoporosis and cancer, without eliciting the typical neurobehavioral side effects of CB1 ligands. For this reason, research activities are currently directed towards the development of CB2 selective ligands. Herein, the synthesis of novel heterocyclic-based CB2 selective compounds is reported. A set of 2,5-dialkyl-1-phenyl-1H-pyrrole-3-carboxamides, 5-subtituted-2-(acylamino)/(2-sulphonylamino)-thiophene-3-carboxylates and 2-(acylamino)/(2-sulphonylamino)-tetrahydrobenzo[b]thiophene-3-carboxylates were synthesized. Biological results revealed compounds with remarkably high CB2 binding affinity and CB2/CB1 subtype selectivity. Compound 19a and 19b from the pyrrole series exhibited the highest CB2 receptor affinity (Ki = 7.59 and 6.15 nM, respectively), as well as the highest CB2/CB1 subtype selectivity (∼70 and ∼200-fold, respectively). In addition, compound 6b from the tetrahydrobenzo[b]thiophene series presented the most potent and selective CB2 ligand in this series (Ki = 2.15 nM and CB2 subtype selectivity of almost 500-fold over CB1). Compound 6b showed a full agonism, while compounds 19a and 19b acted as inverse agonists when tested in an adenylate cyclase assay. The present findings thus pave the way to the design and optimization of heterocyclic-based scaffolds with lipophilic carboxamide and/or retroamide substituent that can be exploited as potential CB2 receptor activity modulators. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Isolation, Characterization, and Ecology of Sulfur-Respiring Crenarchaea Inhabiting Acid-Sulfate-Chloride-Containing Geothermal Springs in Yellowstone National Park▿ †

PubMed Central

Boyd, Eric S.; Jackson, Robert A.; Encarnacion, Gem; Zahn, James A.; Beard, Trevor; Leavitt, William D.; Pi, Yundan; Zhang, Chuanlun L.; Pearson, Ann; Geesey, Gill G.

2007-01-01

Elemental sulfur (S0) is associated with many geochemically diverse hot springs, yet little is known about the phylogeny, physiology, and ecology of the organisms involved in its cycling. Here we report the isolation, characterization, and ecology of two novel, S0-reducing Crenarchaea from an acid geothermal spring referred to as Dragon Spring. Isolate 18U65 grows optimally at 70 to 72°C and at pH 2.5 to 3.0, while isolate 18D70 grows optimally at 81°C and pH 3.0. Both isolates are chemoorganotrophs, dependent on complex peptide-containing carbon sources, S0, and anaerobic conditions for respiration-dependent growth. Glycerol dialkyl glycerol tetraethers (GDGTs) containing four to six cyclopentyl rings were present in the lipid fraction of isolates 18U65 and 18D70. Physiological characterization suggests that the isolates are adapted to the physicochemical conditions of Dragon Spring and can utilize the natural organic matter in the spring as a carbon and energy source. Quantitative PCR analysis of 16S rRNA genes associated with the S0 flocs recovered from several acid geothermal springs using isolate-specific primers indicates that these two populations together represent 17 to 37% of the floc-associated DNA. The physiological characteristics of isolates 18U65 and 18D70 are consistent with their potential widespread distribution and putative role in the cycling of sulfur in acid geothermal springs throughout the Yellowstone National Park geothermal complex. Based on phenotypic and genetic characterization, the designations Caldisphaera draconis sp. nov. and Acidilobus sulfurireducens sp. nov. are proposed for isolates 18U65 and 18D70, respectively. PMID:17720836

Terrestrial soil pH and MAAT records based on the MBT/CBT in the southern South China Sea: implications for the atmospheric CO2 evolution in Southeast Asia

NASA Astrophysics Data System (ADS)

Dong, L.; Li, L.; Li, Q.; Zhang, C.

2013-12-01

Liang Dong1, Li Li1, Qianyu Li1,2, Chuanlun L. Zhang1,3 1State Key Laboratory of Marine Geology, Tongji University, Shanghai 200092, China 2School of Earth and Environment Sciences, University of Adelaide, SA 5005, Australia 3Department of Marine Sciences, University of Georgia, Athens, GA 30602, USA The methylation index of branched tetraethers (MBT) and/or the cyclization ratio of branched tetraethers (CBT) are derived from the branched glycerol dialkyl Glycerol tetraethers (GDGTs) of bacterial origin and are widely used to reconstruct the terrestrial soil pH and mean annual air temperature (MAAT); however, these proxies are less frequently used in the oceanic settings. Here we provide the first high resolution records of soil pH and MAAT since the last glacial maximum based on the sedimentary core of MD05-2896 in the southern South China Sea. The MAAT record exhibited typical glacial and interglacial cycles and was consistent with the winter insolation variation. The pH values were lower (6.4-7) in the glacial time and higher (7-8.4) in the interglacial time. Changes in soil pH allowed the evaluation of changes in soil CO2 based on the atmosphere-soil CO2 balance. The results imply that the lower winter MAAT variation with a lower winter atmospheric CO2 concentration might have resulted in a higher pH in the interglacial period. Our records provide a new insight into the evolution of atmospheric CO2 between glacial and interglacial cycles in East Asia. Key words: South China Sea, MBT/CBT, b-GDGTs, MAAT, pH

Descent toward the Icehouse: Eocene sea surface cooling inferred from GDGT distributions

NASA Astrophysics Data System (ADS)

Inglis, Gordon N.; Farnsworth, Alexander; Lunt, Daniel; Foster, Gavin L.; Hollis, Christopher J.; Pagani, Mark; Jardine, Phillip E.; Pearson, Paul N.; Markwick, Paul; Galsworthy, Amanda M. J.; Raynham, Lauren; Taylor, Kyle. W. R.; Pancost, Richard D.

2015-07-01

The TEX86 proxy, based on the distribution of marine isoprenoidal glycerol dialkyl glycerol tetraether lipids (GDGTs), is increasingly used to reconstruct sea surface temperature (SST) during the Eocene epoch (56.0-33.9 Ma). Here we compile published TEX86 records, critically reevaluate them in light of new understandings in TEX86 palaeothermometry, and supplement them with new data in order to evaluate long-term temperature trends in the Eocene. We investigate the effect of archaea other than marine Thaumarchaeota upon TEX86 values using the branched-to-isoprenoid tetraether index (BIT), the abundance of GDGT-0 relative to crenarchaeol (%GDGT-0), and the Methane Index (MI). We also introduce a new ratio, %GDGTRS, which may help identify Red Sea-type GDGT distributions in the geological record. Using the offset between TEX86H and TEX86L (ΔH-L) and the ratio between GDGT-2 and GDGT-3 ([2]/[3]), we evaluate different TEX86 calibrations and present the first integrated SST compilation for the Eocene (55 to 34 Ma). Although the available data are still sparse some geographic trends can now be resolved. In the high latitudes (>55°), there was substantial cooling during the Eocene (~6°C). Our compiled record also indicates tropical cooling of ~2.5°C during the same interval. Using an ensemble of climate model simulations that span the Eocene, our results indicate that only a small percentage (~10%) of the reconstructed temperature change can be ascribed to ocean gateway reorganization or paleogeographic change. Collectively, this indicates that atmospheric carbon dioxide (pCO2) was the likely driver of surface water cooling during the descent toward the icehouse.

Identification of terpenoids from Rubus corchorifolius L. f. leaves and their anti-proliferative effects on human cancer cells.

PubMed

Chen, Xuexiang; Gao, Zili; Song, Mingyue; Ouyang, Wen; Wu, Xian; Chen, Yunjiao; Zhou, Liping; William, Dixon; Cai, Xiaokun; Cao, Yong; Zhou, Shuangde; Tang, Zhonghai; Xiao, Hang

2017-03-22

The leaves of Rubus corchorifolius L. f. have been consumed as a herbal tea for a long time. In this study, two novel (1 and 5) and four known (2, 3, 4 and 6) terpenoids were isolated from the leaves of Rubus corchorifolius L. f. Structural analysis was performed using various spectroscopic methods ( 1 H NMR, 13 C NMR and MS) to identify the following six compounds: (16α)-16,17,18-trihydroxy-ent-kauran-18-O-β-d-glucoside (1), ent-16β,17-dialkyl-3-oxygen-kaurane (2), ent-kaurane-3α,16β,17-triol (3), ent-kaurane(5R,8S,9R,10R,13R,16R)-2-one-16α,17-diol (4), (16R)-16β,17,19-trihydroxy-ent-kaur-3-one (5) and ent-16α,17-dihydroxy-kauran-19-oic-acid (6). These compounds showed different inhibitory effects on various human cancer cells. Compounds 3 and 6 exhibited stronger inhibitory effects on human colon cancer HCT116 cells than the other 4 compounds. Flow cytometry analysis demonstrated that both compounds 3 and 6 caused cell cycle arrest at the G0/G1 phase and induced cellular apoptosis in HCT116 cells. Compounds 3 and 6 modulated the expression levels of key signaling proteins closely related to cell proliferation and apoptosis, i.e., increasing the levels of poly(ADP-ribose) polymerase, p53, and p27, and decreasing the levels of EGFR, cyclin D1, CDK2 and CDK4. Overall, our findings provided insight into the anticancer components of Rubus corchorifolius L. f. leaves, which could facilitate their utilization as functional food ingredients.

Enrichment of the amino acid l-isovaline by aqueous alteration on CI and CM meteorite parent bodies

PubMed Central

Glavin, Daniel P.; Dworkin, Jason P.

2009-01-01

The distribution and enantiomeric composition of the 5-carbon (C5) amino acids found in CI-, CM-, and CR-type carbonaceous meteorites were investigated by using liquid chromatography fluorescence detection/TOF-MS coupled with o-phthaldialdehyde/N-acetyl-l-cysteine derivatization. A large l-enantiomeric excess (ee) of the α-methyl amino acid isovaline was found in the CM meteorite Murchison (lee = 18.5 ± 2.6%) and the CI meteorite Orgueil (lee = 15.2 ± 4.0%). The measured value for Murchison is the largest enantiomeric excess in any meteorite reported to date, and the Orgueil measurement of an isovaline excess has not been reported previously for this or any CI meteorite. The l-isovaline enrichments in these two carbonaceous meteorites cannot be the result of interference from other C5 amino acid isomers present in the samples, analytical biases, or terrestrial amino acid contamination. We observed no l-isovaline enrichment for the most primitive unaltered Antarctic CR meteorites EET 92042 and QUE 99177. These results are inconsistent with UV circularly polarized light as the primary mechanism for l-isovaline enrichment and indicate that amplification of a small initial isovaline asymmetry in Murchison and Orgueil occurred during an extended aqueous alteration phase on the meteorite parent bodies. The large asymmetry in isovaline and other α-dialkyl amino acids found in altered CI and CM meteorites suggests that amino acids delivered by asteroids, comets, and their fragments would have biased the Earth's prebiotic organic inventory with left-handed molecules before the origin of life. PMID:19289826

Silibinin derivatives as anti-prostate cancer agents: Synthesis and cell-based evaluations.

PubMed

Vue, Bao; Zhang, Sheng; Zhang, Xiaojie; Parisis, Konstantinos; Zhang, Qiang; Zheng, Shilong; Wang, Guangdi; Chen, Qiao-Hong

2016-02-15

This study aims to systematically explore the alkylation effect of 7-OH in silibinin and 2,3-dehydrosilibinin on the antiproliferative potency toward three prostate cancer cell lines. Eight 7-O-alkylsilibinins, eight 7-O-alkyl-2,3-dehydrosilibinins, and eight 3,7-O-dialkyl-2,3-dehydrosilibinins have been synthesized from commercially available silibinin for the in vitro cell-based evaluation. The WST-1 cell proliferation assay indicates that nineteen out of twenty-four silibinin derivatives have significantly improved antiproliferative potency when compared with silibinin. 7-O-Methylsilibinin (2) and 7-O-ethylsilibinin (3) have been identified as the most potent compounds with 98- and 123-fold enhanced potency against LNCaP human androgen-dependent prostate cancer cell line. Among 2,3-dehydrosilibinin derivatives, 7-O-methyl-2,3-dehydrosilibinin (10) and 7-O-ethyl-2,3-dehydrosilibinin (11) have been identified as the optimal compounds with the highest potency towards both androgen-dependent LNCaP and androgen-independent PC-3 prostate cancer cell lines. 7-O-Ethyl-2,3-dehydrosilibinin (11) was demonstrated to arrest PC-3 cell cycle at the G0/G1 phase and to induce PC-3 cell apoptosis. The findings in this study suggest that antiproliferative potency of silibinin and 2,3-dehydrosilibinin can be appreciably enhanced through suitable chemical modifications on the phenolic hydroxyl group at C-7 and that introduction of a chemical moiety with the potential to improve bioavailability through a linker to 7-OH in silibinin and 2,3-dehydrosilibinin would be a feasible strategy for the development of silibinin derivatives as anti-prostate cancer agents. Published by Elsevier Masson SAS.

Photochemical properties of squarylium cyanine dyes.

PubMed

Ferreira, D P; Conceição, D S; Ferreira, V R A; Graça, V C; Santos, P F; Vieira Ferreira, L F

2013-11-01

This study presents several new squarylium dyes derived from benzothiazole and benzoselenazole with several structural variations, namely the nature of the heteroaromatic ring and the length of the N,N'-dialkyl groups. Before being investigated in connection with their effect on living cells and/or tissues, these novel compounds were characterized, namely with respect to the determination of their main photophysical parameters. Therefore, a study of the ground state absorption, fluorescence emission (quantum yields and lifetimes) and singlet oxygen generation quantum yields was performed for all the compounds synthesized in order to evaluate their efficiency as photosensitizers. An increase of the alkyl chain length from ethyl to hexyl did not produce a clear change in the fluorescence quantum yields, showing no influence on the photoisomerization process. Heavy atom inclusion (Se instead of S) enhanced the singlet oxygen generation efficiency and decreased the intensity of the fluorescence emission. The external heavy atom effect (I(-) as a counterion instead of CF3SO3(-)) produced a significant increase in the singlet oxygen formation quantum yield (about 20%). Transient absorption studies in aerated and oxygen free samples revealed that the photoisomerization process, which could compete with the triplet state formation for all dyes in solution, is a negligible pathway for the excited state deactivation, in accordance with the rigidity introduced by the squaric ring into the polymethine chain of the dye, both in chloroform and ethanol. However, in the case of the chloroform solution a new transient was detected in air equilibrated solutions, resulting from a reaction of the excited squarylium dye in the singlet state with CHCl3˙, and assigned to the radical cation (SQ(+)˙) of the dye.

Multi-proxy Organic Geochemical Reconstruction of Holocene Hydroclimate Near the Western Greenland Ice Sheet Margin

NASA Astrophysics Data System (ADS)

Cluett, A.; Thomas, E. K.

2017-12-01

Anthropogenic warming is projected to drive profound change to the Arctic hydrological cycle within the century, most notably in the intensification of rainfall, with potential feedbacks to the climate system and cryosphere. However, the relationship between hydroclimate and cryosphere variability is poorly constrained in the long-term due to a scarcity of high-resolution hydroclimate records from the Arctic. We analyze the stable hydrogen isotopes (dD) of leaf wax biomarkers from lacustrine sediments spanning the Holocene to 9000 cal. year B.P. from Lake Gus (67.032ºN, 52.427ºW, 300 m a.s.l.; informal name), a small lake approximately 90 km from the modern western margin of the Greenland Ice Sheet. We interpret the signal of aquatic leaf wax isotopes in the context of a survey of 100 modern lake water samples from western Greenland across an aridity gradient to better understand the combined climatological and hydrological controls on lake water dD in the study area. We compare variability of aquatic and terrestrial leaf wax isotopes to infer changes in relative moisture throughout the Holocene, and complement our leaf wax record with analysis of glycerol dialkyl glycerol tetraethers (GDGTs) and alkenones, to produce records of summer temperature. Pairing temperature and leaf wax isotope records provides a means to constrain the changing dD-temperature relationship throughout the Holocene and infer moisture source variability. In combination, these proxies produce a comprehensive hydroclimate record at approximately centennial scale to evaluate shifts in relative moisture, temperature, and moisture source, and to investigate the interaction between hydroclimate and Greenland Ice Sheet margin fluctuations through the Holocene.

Electrical transport characteristics of single-layer organic devices from theory and experiment

NASA Astrophysics Data System (ADS)

Martin, S. J.; Walker, Alison B.; Campbell, A. J.; Bradley, D. D. C.

2005-09-01

An electrical model based on drift diffusion is described. We have explored systematically how the shape of the current density-voltage (J-V) curves is determined by the input parameters, information that isessential when deducing values of these parameters by fitting to experimental data for an ITO/PPV/Al organic light-emitting device (OLED), where ITO is shorthand for indium tin oxide and PPV is poly(phenylene vinylene). Our conclusion is that it is often possible to obtain a unique fit even with several parameters to fit. Our results allowing for a tunneling current show remarkable resemblance to experimental data before and after the contacts are conditioned. We have demonstrated our model on single-layer devices with ITO/PFO/Au and ITO/PEDOT/PFO/Au at room temperature and ITO/TPD/Al over temperatures from 130 to 290 K. PFO is shorthand for poly(9,9'-dialkyl-fluorene-2,7-dyl) and TPD is shorthand for N,N'-diphenyl-N,N'-bis(3-methylphenyl)1-1'-biphenyl-4,4'-diamine. Good fits to experimental data have been obtained, but in the case of the TPD device, only if a larger value for the relative permittivity ɛs than would be expected is used. We infer that a layer of dipoles at the ITO/TPD interface could be responsible for the observed J-V characteristics by locally causing changes in ɛs. The strong temperature dependence of the hole barrier height from fitting J-V characteristics to the experimental data may indicate that the temperature dependence of the thermionic emission model is incorrect.

Construction of protocellular structures under simulated primitive earth conditions

NASA Astrophysics Data System (ADS)

Yanagawa, Hiroshi; Ogawa, Yoko; Kojima, Kiyotsugu; Ito, Masahiko

1988-09-01

We have developed experimental approaches for the construction of protocellular structures under simulated primitive earth conditions and studied their formation and characteristics. Three types of envelopes; protein envelopes, lipid envelopes, and lipid-protein envelopes are considered as candidates for protocellular structures. Simple protein envelopes and lipid envelopes are presumed to have originated at an early stage of chemical evolution, interaction mutually and then evolved into more complex envelopes composed of both lipids and proteins. Three kinds of protein envelopes were constructedin situ from amino acids under simulated primitive earth conditions such as a fresh water tide pool, a warm sea, and a submarine hydrothermal vent. One protein envelope was formed from a mixture of amino acid amides at 80 °C using multiple hydration-dehydration cycles. Marigranules, protein envelope structures, were produced from mixtures of glycine and acidic, basic and aromatic amino acids at 105 °C in a modified sea medium enriched with essential transition elements. Thermostable microspheres were also formed from a mixture of glycine, alanine, valine, and aspartic acid at 250 °C and above. The microspheres did not form at lower temperatures and consist of silicates and peptide-like polymers containing imide bonds and amino acid residues enriched in valine. Amphiphilic proteins with molecular weights of 2000 were necessary for the formation of the protein envelopes. Stable lipid envelopes were formed from different dialkyl phospholipids and fatty acids. Large, stable, lipid-protein envelopes were formed from egg lecithin and the solubilized marigranules. Polycations such as polylysine and polyhistidine, or basic proteins such as lysozyme and cytochromec also stabilized lipid-protein envelopes.

Cross-reactions between xanthates and rubber additives.

PubMed

Sasseville, Denis; Al-Sowaidi, Mowza; Moreau, Linda

2007-09-01

We previously described allergic contact dermatitis from xanthates used in the recovery of metals from mining ores. We observed cross-reactions with carbamates, believed to be due to the common "dithio" nucleus shared by both groups. The present study was undertaken to establish the rate of cross-reactions between xanthates and rubber additives. Between November 2002 and December 2005, 1,220 consecutive patients were patch-tested with sodium isopropyl xanthate 10% in petrolatum (pet) and with potassium amyl xanthate 10% pet and later 5% pet, in addition to the North American Contact Dermatitis Group standard series and other series as required by their conditions. Fifty-one patients reacted to xanthates, carbamates, or thiurams; 26 reacted to xanthates only, and these reactions were felt to be irritant. Twenty-five patients reacted to xanthates and/or to one or more of the rubber additives, 12 had positive reactions to xanthates and to either carba mix or thiuram mix, 10 reacted to xanthates and carba mix, 9 reacted to xanthates and thiuram mix, and 8 showed positive reactions to xanthates and both mixes. However, 13 patients had positive reactions to carba mix and thiuram mix but did not react to xanthates. Six patients reacted to other rubber additives such as mercaptobenzothiazole, black rubber mix, and mixed dialkyl thioureas. Five of these patients also reacted to xanthates, 4 reacted to xanthates and carba mix, and 3 reacted to xanthates, carba mix, and thiuram mix. Of patients sensitized to carbamates, thiurams, or mercaptobenzothiazole, 50% exhibit cross-reactions with xanthates. Xanthates are irritants, and their patch-test concentrations should be lowered to 5% or less.

Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

NASA Technical Reports Server (NTRS)

Jahnke, Linda L.; Edger, Wolfgang; Huber, Robert; Hinrichs, Kai-Uwe; Hayes, John M.; DesMarais, David J.; Cady, Sherry; Hope, Janet M.; Summons, Roger E.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

Extremely thermophilic microbial communities associated with the siliceous vent walls and outflow channel of Octopus Spring, Yellowstone National Park, have been examined for lipid biomarkers and carbon isotopic signatures. These data were compared with that obtained from representatives of three Aquificales genera. Thermocrinis ruber. "Thermocrinis sp. HI", Hydrogenobacter thermophilus TK-6, Aquifex pyrophilus and Aquifex aeolicus all contained phospholipids composed not only of the usual ester-linked fatty acids, but also ether-linked alkyls. The fatty acids of all cultured organisms were dominated by a very distinct pattern of n-C-20:1 and cy-C-21 compounds. The alkyl glycerol ethers were present primarily as CIS() monoethers with the expection of the Aquifex spp. in which dialkyl glycerol ethers with a boarder carbon-number distribution were also present. These Aquificales biomarker lipids were the major constituents in the lipid extracts of the Octopus Spring microbial samples. Two natural samples, a microbial biofilm growing in association with deposition of amorphous silica on the vent walls at 92 C, and the well-known 'pink-streamers community' (PSC), siliceous filaments of a microbial consortia growing in the upper outflow channel at 87 C were analyzed. Both the biofilm and PSC samples contained mono and dialkyl glycerol ethers with a prevalence of C-18 and C-20 alkyls. Phospholipid fatty acids were comprised of both the characteristic Aquificales n-C-20:1 and cy-C-21, and in addition, a series of iso-branched fatty acids from i-C-15:0 to i-C-21:0, With i-C-17:0 dominant in the PSC and i-C-19:0 in the biofilm, suggesting the presence of two major bacterial groups. Bacteriohopanepolyols were absent and the minute quantities of archaeol detected showed that Archaea were only minor constituents. Carbon isotopic compositions of the PSC yielded information about community structure and likely physiology. Biomass was C-13-depleted (10.9%) relative to available CO2 from the source water inorganic carbon pool with lipids further depleted by 6.3% relative to biomass The C-20-21 Aquificales fatty acids of the PSC were somewhat heavier than the iso-branched fatty acids. The carbon isotopic signatures of lipid biomarkers were also explored using a pure culture, T ruber, previously isolated from the PSC. Cells grown on C02 with O2 and both H2 and thiosulfate as electron donors were only slightly depleted (3.3%) relative to the C-source while cells grown on formate with O2 showed a major discrimination (19.7%), possibly the result of a metabolic branch point involving the assimilation of C-formate to biomass and the dissimilation to CO2 associated with energy production. T. ruber lipids were slightly heavier than biomass (+1.3%) whether cells were grown using CO2 or formate. Fatty acids from CO2 grown T. ruber cells were a so slightly heavier (average +2.1%) than biomass. The relatively depleted PSC C-20-21 fatty acids suggest that any associated Thermocrinis biomass would also be similarly depleted and much too light to be explained by growth on CO2. The C-fractionations determined with the pure culture suggest that growth of Thermocrinis in the PSC is more likely to occur on formate, presumably generated by geothermal activity. This study points to the value of the analysis of the structural and isotopic composition of lipid blomarkers both in pure culture studies, and in establishing community structure and physiology, as a complement to genomic profiles of microbial diversity. This is especially so when the members of the microbial community are novel and difficult to cultivate in the laboratory.

In vitro antitumor activity, metal uptake and reactivity with ascorbic acid and BSA of some gold(III) complexes with N,N'-ethylenediamine bidentate ester ligands.

PubMed

Pantelić, Nebojša; Zmejkovski, Bojana B; Kolundžija, Branka; Crnogorac, Marija Đorđić; Vujić, Jelena M; Dojčinović, Biljana; Trifunović, Srećko R; Stanojković, Tatjana P; Sabo, Tibor J; Kaluđerović, Goran N

2017-07-01

Four novel gold(III) complexes of general formulae [AuCl 2 {(S,S)-R 2 eddl}]PF 6 (R 2 eddl=O,O'-dialkyl-(S,S)-ethylenediamine-N,N'-di-2-(4-methyl)pentanoate, R=n-Pr, n-Bu, n-Pe, i-Bu; 1-4, respectively), were synthesized and characterized by elemental analysis, UV/Vis, IR, and NMR spectroscopy, as well as high resolution mass spectrometry. Density functional theory calculations pointed out that (R,R)-N,N'-configuration diastereoisomers were energetically the most favorable. Duo to high cytotoxic activity complex 3 was chosen for stability study in DMSO, no decomposition occurs within 24h, and for the reaction with ascorbic acid in which was reduced immediately. Additionally, 3 interacts with bovine serum albumin (BSA) as proven by UV/Vis spectroscopy. In vitro antitumor activity was determined against human cervix adenocarcinoma (HeLa), human myelogenous leukemia (K562), and human melanoma (Fem-x) cancer cell lines, as well as against non-cancerous human embryonic lung fibroblast cells MRC-5. The highest activity was observed against K562 cells (IC 50 : 5.04-6.51μM). Selectivity indices showed that these complexes are less toxic than cisplatin. 3 had a similar viability kinetics on HeLa cells as cisplatin. Drug accumulation studies in HeLa cells showed that the total gold uptake increased much faster than that of cisplatin pointing out that 3 more efficiently enters the cells than cisplatin. Furthermore, morphological and cell cycle analysis reveal that gold(III) complexes induced apoptosis in time- and dose-dependent manner. Copyright © 2017 Elsevier Inc. All rights reserved.

Prenatal Exposure to Organophosphate Pesticides and IQ in 7-Year-Old Children

PubMed Central

Bouchard, Maryse F.; Chevrier, Jonathan; Harley, Kim G.; Kogut, Katherine; Vedar, Michelle; Calderon, Norma; Trujillo, Celina; Johnson, Caroline; Bradman, Asa; Barr, Dana Boyd

2011-01-01

Context: Organophosphate (OP) pesticides are neurotoxic at high doses. Few studies have examined whether chronic exposure at lower levels could adversely affect children’s cognitive development. Objective: We examined associations between prenatal and postnatal exposure to OP pesticides and cognitive abilities in school-age children. Methods: We conducted a birth cohort study (Center for the Health Assessment of Mothers and Children of Salinas study) among predominantly Latino farmworker families from an agricultural community in California. We assessed exposure to OP pesticides by measuring dialkyl phosphate (DAP) metabolites in urine collected during pregnancy and from children at 6 months and 1, 2, 3.5, and 5 years of age. We administered the Wechsler Intelligence Scale for Children, 4th edition, to 329 children 7 years of age. Analyses were adjusted for maternal education and intelligence, Home Observation for Measurement of the Environment score, and language of cognitive assessment. Results: Urinary DAP concentrations measured during the first and second half of pregnancy had similar relations to cognitive scores, so we used the average of concentrations measured during pregnancy in further analyses. Averaged maternal DAP concentrations were associated with poorer scores for Working Memory, Processing Speed, Verbal Comprehension, Perceptual Reasoning, and Full-Scale intelligence quotient (IQ). Children in the highest quintile of maternal DAP concentrations had an average deficit of 7.0 IQ points compared with those in the lowest quintile. However, children’s urinary DAP concentrations were not consistently associated with cognitive scores. Conclusions: Prenatal but not postnatal urinary DAP concentrations were associated with poorer intellectual development in 7-year-old children. Maternal urinary DAP concentrations in the present study were higher but nonetheless within the range of levels measured in the general U.S. population. PMID:21507776

Ether- and Ester-Bound iso-Diabolic Acid and Other Lipids in Members of Acidobacteria Subdivision 4

PubMed Central

Rijpstra, W. Irene C.; Hopmans, Ellen C.; Foesel, Bärbel U.; Wüst, Pia K.; Overmann, Jörg; Tank, Marcus; Bryant, Donald A.; Dunfield, Peter F.; Houghton, Karen; Stott, Matthew B.

2014-01-01

Recently, iso-diabolic acid (13,16-dimethyl octacosanedioic acid) has been identified as a major membrane-spanning lipid of subdivisions 1 and 3 of the Acidobacteria, a highly diverse phylum within the Bacteria. This finding pointed to the Acidobacteria as a potential source for the bacterial glycerol dialkyl glycerol tetraethers that occur ubiquitously in peat, soil, lakes, and hot springs. Here, we examined the lipid composition of seven phylogenetically divergent strains of subdivision 4 of the Acidobacteria, a bacterial group that is commonly encountered in soil. Acid hydrolysis of total cell material released iso-diabolic acid derivatives in substantial quantities (11 to 48% of all fatty acids). In contrast to subdivisions 1 and 3 of the Acidobacteria, 6 out of the 7 species of subdivision 4 (excepting “Candidatus Chloracidobacterium thermophilum”) contained iso-diabolic acid ether bound to a glycerol in larger fractional abundance than iso-diabolic acid itself. This is in agreement with the analysis of intact polar lipids (IPLs) by high-performance liquid chromatography-mass spectrometry (HPLC-MS), which showed the dominance of mixed ether-ester glycerides. iso-Diabolic acid-containing IPLs were not identified, because these IPLs are not released with a Bligh-Dyer extraction, as observed before when studying lipid compositions of subdivisions 1 and 3 of the Acidobacteria. The presence of ether bonds in the membrane lipids does not seem to be an adaptation to temperature, because the five mesophilic isolates contained a larger amount of ether lipids than the thermophile “Ca. Chloracidobacterium thermophilum.” Furthermore, experiments with Pyrinomonas methylaliphatogenes did not reveal a major influence of growth temperature over the 50 to 69°C range. PMID:24928878

Autocatalytic, bistable, oscillatory networks of biologically relevant organic reactions

NASA Astrophysics Data System (ADS)

Semenov, Sergey N.; Kraft, Lewis J.; Ainla, Alar; Zhao, Mengxia; Baghbanzadeh, Mostafa; Campbell, Victoria E.; Kang, Kyungtae; Fox, Jerome M.; Whitesides, George M.

2016-09-01

Networks of organic chemical reactions are important in life and probably played a central part in its origin. Network dynamics regulate cell division, circadian rhythms, nerve impulses and chemotaxis, and guide the development of organisms. Although out-of-equilibrium networks of chemical reactions have the potential to display emergent network dynamics such as spontaneous pattern formation, bistability and periodic oscillations, the principles that enable networks of organic reactions to develop complex behaviours are incompletely understood. Here we describe a network of biologically relevant organic reactions (amide formation, thiolate-thioester exchange, thiolate-disulfide interchange and conjugate addition) that displays bistability and oscillations in the concentrations of organic thiols and amides. Oscillations arise from the interaction between three subcomponents of the network: an autocatalytic cycle that generates thiols and amides from thioesters and dialkyl disulfides; a trigger that controls autocatalytic growth; and inhibitory processes that remove activating thiol species that are produced during the autocatalytic cycle. In contrast to previous studies that have demonstrated oscillations and bistability using highly evolved biomolecules (enzymes and DNA) or inorganic molecules of questionable biochemical relevance (for example, those used in Belousov-Zhabotinskii-type reactions), the organic molecules we use are relevant to metabolism and similar to those that might have existed on the early Earth. By using small organic molecules to build a network of organic reactions with autocatalytic, bistable and oscillatory behaviour, we identify principles that explain the ways in which dynamic networks relevant to life could have developed. Modifications of this network will clarify the influence of molecular structure on the dynamics of reaction networks, and may enable the design of biomimetic networks and of synthetic self-regulating and evolving chemical systems.

Determination of glycation sites by tandem mass spectrometry in a synthetic lactose-bovine serum albumin conjugate, a vaccine model prepared by dialkyl squarate chemistry

PubMed Central

Jahouh, Farid; Hou, Shu-jie; Kováč, Pavol; Banoub, Joseph H.

2012-01-01

RATIONALE Neoglycoconjugate vaccines synthesized by the squaric acid spacer method allow single point attachment of the carbohydrate antigen to the protein carrier. However, the localization of the carbohydrate antigen sites of conjugation on the protein carrier has been an elusive task difficult to achieve. METHOD Covalent attachment of the lactose antigen to the bovine serum albumin (BSA) was prepared by the squaric acid method using a hapten:BSA ratio of 20:1. Different reaction times were used during the conjugation reaction and two different lactose-BSA glycoconjugate vaccines were obtained. The carbohydrate antigen hapten:BSA ratios of these lactose-BSA glycoconjugate vaccines were determined by MALDI-TOF/RTOF-MS and the glycation sites in the neoglycoconjugates were determined using nano-LC/ESI-QqTOF-MS/MS analysis of the trypsin and GluC V8 digests of the conjugates. RESULTS We have identified a total of 15 glycation sites located on the BSA lysine residues for the neoglycoconjugate vaccine formed with a hapten:BSA ratio of 5.1:1, However, the tryptic and GluC V8 digests of the hapten-BSA glycoconjugate with a hapten:BSA ratio of 19.0:1 allowed identification of 30 glycation sites located on the BSA. These last results seem to indicate that this conjugation results in formation of various glycoforms. CONCLUSIONS It was observed that the number of identified glycation sites increased when the hapten:BSA ratio of glycoconjugate formation increased, and that the location of the glycation sites appears to be mainly on the outer surface of the BSA carrier molecule which is in line with the assumption that the sterically more accessible lysine residues, namely those located on the outer surface of the BSA, would be conjugated preferentially. PMID:22368054

A rapid method to assess a broad inventory of organic species in marine sediments using ultra-high resolution mass spectrometry.

PubMed

Radović, Jagoš R; Silva, Renzo C; Snowdon, Ryan W; Brown, Melisa; Larter, Steve; Oldenburg, Thomas B P

2016-06-15

A broad range of organic species in marine sediments is routinely used as biogeochemical proxies of Earth history. These species are typically analyzed using different analytical methods, targeting very specific components and often including time-intensive sample preparation. There is, therefore, a need for a more comprehensive, rapid and high-throughput approach to simultaneously analyze a broad range of known sedimentary polar species and also have a surveillance capability able to identify candidate new species classes. Whole solvent extracts from recently deposited Gulf of Mexico marine sediments were obtained after a simple, one-step extraction. They were analyzed by Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), using atmospheric pressure photoionization in positive ion mode (APPI-P), over a broad mass range (m/z 150-1500). From 3000 to over 5000 peaks per sample were assigned molecular formulae, and the majority of assignments (90%) showed an absolute error lower than 200 ppb. The detected species belong to the NO1-7 , N4 O2-8 , O1-9 , HC, N and OS compound classes, including known biomarker species such as pigments (e.g. tetrapyrrole macrocycles and carotenoids) and lipids (e.g. glycerol dialkyl glycerol tetraethers, GDGTs), but also compounds of still unknown detailed molecular structure, but with clear potential geochemical relevance. The reported method enables rapid (12 min FTICR-MS analysis time) and simultaneous detection of a broad range of multi-heteroatom, polar organic species in whole sediment extracts. This allows for higher sample throughput, a more comprehensive investigation of sedimentary geochemistry, and potentially the discovery of new components and derivation of novel, multi-species proxies. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Transport of branched tetraether lipids from the Tagus River basin to the coastal ocean of the Portuguese margin: consequences for the interpretation of the MBT'/CBT paleothermometer

NASA Astrophysics Data System (ADS)

Zell, C.; Kim, J.-H.; Balsinha, M.; Dorhout, D.; Fernandes, C.; Baas, M.; Sinninghe Damsté, J. S.

2014-10-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs), which are thought to be transported from soil to marine sediment by rivers, have been used to reconstruct the mean annual air temperature (MAAT) and soil pH of the drainage basin using the methylation index of branched tetraethers (MBT, recently refined as MBT') and cyclization index of branched tetraethers (CBT) from coastal marine sediment records. In this study, we trace the brGDGTs from source to sink in the Tagus River basin, the longest river system on the Iberian Peninsula, by determining their concentration and distribution in soils, river suspended particulate matter (SPM), riverbank sediments, marine SPM, and marine surface sediments. The concentrations of brGDGTs in river SPM were substantially higher and their distributions were different compared to those of the drainage basin soils. This indicates that brGDGTs are mainly produced in the river itself. In the marine environment, the brGDGT concentrations rapidly decreased with increasing distance from the Tagus estuary. At the same time, the brGDGT distributions in marine sediments also changed, indicating that marine in situ production also takes place. These results show that there are various problems that complicate the use of the MBT'/CBT for paleoreconstructions using coastal marine sediments in the vicinity of a river. However, if the majority of brGDGTs are produced in the river, it might be possible to reconstruct the environmental (temperature and pH) conditions of the river water using appropriate aquatic calibrations, provided that marine core locations are chosen in such a way that the brGDGTs in their sediments are predominantly derived from riverine in situ production.

Dependence of the cyclization of branched tetraethers on soil moisture in alkaline soils from arid-subhumid China: implications for palaeorainfall reconstructions on the Chinese Loess Plateau

NASA Astrophysics Data System (ADS)

Wang, H.; Liu, W.; Zhang, C. L.

2014-12-01

The use of branched glycerol dialkyl glycerol tetraethers (bGDGTs) in loess-palaeosol sequences (LPSs) has shown promises in continental palaeotemperature reconstructions. Thus far, however, little is known about the effect of soil moisture on their distributions in the water-limited Chinese Loess Plateau (CLP). In this study, the relationships between environmental variables and the cyclization of branched tetraethers (CBT) were investigated in arid-subhumid China using 97 surface soils in the CLP and its vicinity, as well as 78 soils with pH > 7 which have been previously published. We find that CBT correlates best with soil water content (SWC) or mean annual precipitation (MAP) for the overall data set. This indicates that CBT is mainly controlled by soil moisture instead of soil pH in alkaline soils from arid-subhumid regions, where water availability is a limiting factor for the producers of bGDGTs. Therefore, we suggest that CBT can potentially be used as a palaeorainfall proxy on the alkaline CLP. According to the preliminary CBT-MAP relationship for modern CLP soils (CBT = -0.0021 × MAP + 1.7, n = 37, r = -0.93), palaeorainfall history was reconstructed from three LPSs (Yuanbao, Lantian, and Mangshan) with published bGDGT data spanning the past 70 ka. The CBT-derived MAP records of the three sites consistently show precession-driven variation resembling the monsoon record based on speleothem δ18O, supporting CBT as a reasonable proxy for palaeorainfall reconstruction in LPS. The direct application of CBT as a palaeorainfall proxy in corroboration with the bGDGT-based temperature proxy may enable us to further assess the temperature/hydrological association for palaeoclimate studies on the CLP.

Altitudinal effect of soil glycerol dialkyl glycerol tetraether on the southeastern Tibetan Plateau: availability as a paleoaltitude proxy

NASA Astrophysics Data System (ADS)

Bai, Y.

2016-12-01

Tibetan Plateau uplift was an important dynamic factor in global climate change during the Late Cenozoic, which in turn strongly influenced the development of the Asian monsoon system. Recently, the distribution of branched GDGTs (brGDGTs) has been proposed as a new paleoaltitude proxy. However, the suitability and reliability of the MBT'/CBT ratio (i.e., the ratio between the methylation and cyclization indices of branched tetraethers) as a paleoaltitude proxy has not been fully verified. In this study, we present the distribution of bacterial brGDGTs in 88 soils along two vapor transport pathways (comprising four transects) running across the southeastern Tibetan Plateau (SE TP), i.e., the South Himalayan Transect (SH; altitude range 1.66-5.05 km* above sea level (asl), representing the Southern Himalayan airmass), and the Bayi-Lhasa (BL; altitude 3.05-4.97 km asl), Bomi-Bayi (BB; altitude 2.030-4.555 km asl) and Zayu-Bomi (ZB; altitude 1.468-4.8 km asl) transects, together representing the Brahmaputra-Yarlung Zangbo River Valley airmass, to verify the suitability, and examine the reliability, of the MBT'/CBT ratio as a paleoaltitude proxy. MBT'/CBT-derived temperatures and MBT' exhibit a strong relation with altitude (R2=0.84 and R2=0.70, respectively) for all of the sampled localities with neutral and acidic soils, compared to the relation between n-alkane δDwax and altitude (R2=0.78; n=76). These findings have significant implications for using neutral and acidic sediments in paleoaltitude reconstructions. We found that alkaline soils with pH values >7.0 had lower MBT' and MBT'/CBT-derived temperatures, and that the brGDGTs' proxies were greatly optimized, based on separating 6-methyl brGDGTs.

Lipid biomarker patterns of methane-derived carbonates from Dongsha area, the northern of South China Sea

NASA Astrophysics Data System (ADS)

Yu, X.; Lei, J.; Yang, K.; Fang, Y.

2012-12-01

Carbonate and sediment samples collected from the Dongsha area the South China by TV-grab. The δ13C values of the carbonate indicate that the carbonate carbon is mainly derived from the oxidation of methane. According to the δ13C value of two groups carbonates could be divided: Group1 (G1) is 13C-depleted as reported previously, the δ13C value lighter than -50‰ PDB; group2 (G2) is enriched in 13C relatively, the δ13C value is around -30‰PDB. The δ13C value of sediments associated with carbonate varying from -19.2 to -30.4‰PDB. G1 and G2 have similar n-alkanes distribution and with 13C-depleted PMI, but glycerol dialkyl glycerol tetraethers (GDGTs) patterns obviously different. The G1 with the higher GDGTs concentration, up to 0.37 ug/g (dry weight), and the isoprenoid GDGTs is dominantly, with a acyclic > monocyclic > bicyclic > tricyclic > tetracyclic biphytane distribution, the branch GDGTs is less than 2%. The G2 with the quite lower GDGTs concentration, varying from 0.025~0.063ug/g (dry weight), the isoprenoid GDGTs content is less than 70%, with a acyclic > tetracyclic > bicyclic > monocyclic > tricyclic biphytane distribution, the branch GDGT is more than 30%. The sediment associated with carbonate has the similar GDGTs pattern with the G2, but the GDGTs concentration is between G1 and G2. The molecular structure and their carbon isotopic composition suggest that the organism mainly derived from methane oxidizing archaea and more carbonate precipitation by AOM within the G1 carbonates. Meanwhile, partly organism derived from crenachaeol and terrestrial, some carbonate precipitation originated from water column within the G2 carbonates. The G2 carbonates contain the similar biomarkers as found in nearby sediments, suggesting that the organisms associated with carbonate precipitation are the similar

The Reaction of Hydrogen Sulfide with Disulfides: Formation of a Stable Trisulfide and Implications to Biological Systems.

PubMed

Bianco, Christopher L; Akaike, Takaaki; Ida, Tomoaki; Nagy, Peter; Bogdandi, Virag; Toscano, John P; Kumagai, Yoshito; Henderson, Catherine F; Goddu, Robert N; Lin, Joseph; Fukuto, Jon M

2018-05-29

The signaling associated with hydrogen sulfide (H 2 S) remains to be established and recent studies have alluded to the possibility that H 2 S-derived species play important roles. Of particular interest are hydropersulfides (RSSH) and related polysulfides (RSS n R, n>1). This work elucidates the fundamental chemical relationship between these sulfur species as well as examine their biological effects. Using standard analytical techniques ( 1 H-NMR and mass spectrometry), the equilibrium reactions between H 2 S, disulfides (RSSR), RSSH, dialkyltrisulfides (RSSSR) and thiols (RSH) were examined. Their ability to protect cells from electrophilic and/or oxidative stress was also examined using cell culture. H 2 S, RSSR, RSSH, RSSSR and RSH are all in a dynamic equilibrium. In a biological system, these species can exist simultaneously and thus it is difficult to discern which species is (are) the biological effector (s). Treatment of cells with the dialkyl trisulfide cysteine trisulfide (Cys-SSS-Cys) results in high intracellular levels of hydropersulfides and protection from electrophilic stress. In aqueous systems, the reaction between H 2 S and RSSR results in the formation of equilbria whereby H 2 S, RSH, RSSR, RSSH and RSSSR are present. In a biological system, any of these species can be responsible for the observed biological activity. These equilibrium species can also be generated via the reaction of RSH with RSSSR. Due to these equilibria, Cys-SSS-Cys can be a method for generating any of the other species. Importantly, HEK293T cells treated with Cys-SSS-Cys results in increased levels of hydropersulfides, allowing examination of the biological effects of RSSH. This article is protected by copyright. All rights reserved.

Spatial and temporal variations in core- and polar- isoprenoid tetraether lipids along a salinity gradient from the lower Pearl River to its estuary

NASA Astrophysics Data System (ADS)

Jia, C.; Gao, S.; Wang, J. X.; Zhang, C. L.

2014-12-01

Isoprenoid glycerol dialkyl glycerol tetraethers (iGDGTs) are major archaeal lipids that widely occur in nature and have been used to study paleo-climate and paleo-environments. Estuaries are a dynamic ecosystem that links or divides terrestrial and marine processes. However, factors controlling changes in iGDGTs in estuaries are poorly known. In this study we performed monthly sampling of sediments between July 2012 and May 2013 at four sites from the lower Pearl River to the estuary. Total lipids were extracted to obtain core- and polar-GDGTs, which were identified and quantified using liquid chromatography-mass spectrometry (LC-MS). The average concentrations of archaeal lipids were highest at the seawater station (C-iGDGTs: 1804.0 ng/g; P-iGDGTs: 986.9 ng/g) and lowest at the brackish water station (C-iGDGTs: 364.1 ng/g; P-iGDGTs: 324.4 ng/g) with C-iGDGTs being more abundant than P-iGDGTs in most samples. The composition of iGDGTs varied widely from station to station, but was generally dominated by GDGT-0 or crenarchaeol in both C- and P-iGDGTs. At the freshwater station in the lower Pearl River, the relative abundance of C- and P-iGDGTs varied from month to month, whereas such temporal changes were much less at stations in the brackish and marine environments. These results suggest that Archaea living in freshwater might be more sensitive to environmental variation. A significant positive correlation (R2>0.80, p<0.01) was found between the ratio of Cren./(Cren.+GDGT-0) or ring index and salinity in both C- and P-iGDGT fractions, indicating that salinity is the most important factor affecting the composition of iGDGTs in the estuary environment.

The French human biomonitoring program: First lessons from the perinatal component and future needs.

PubMed

Dereumeaux, Clémentine; Fillol, Clémence; Charles, Marie-Aline; Denys, Sébastien

2017-03-01

This paper presents a progress report of the French human biomonitoring (HBM) program established in 2010. This program has been designed to provide a national representative estimation of the French population's exposure to various environmental chemicals and to study the determinants of exposure. This program currently consists in two surveys: a perinatal component related to a selection of 4145 pregnant women who have been enrolled in the Elfe cohort (the French Longitudinal Study since Childhood) in 2011, and a general population survey related to adults aged 18-74 years and children as from 6 years (Esteban). The aim of this manuscript is to present highlights of the French human biomonitoring program with particular focus on the prioritization of biomarkers to be analyzed in the program and the selection of biomarkers applied to both program components. The Delphi method was used to establish a consensual list of prioritized biomarkers in 2011. First results of the perinatal component of the French HBM program have shown that the biomarkers prioritized were relevant, as almost all pregnant women were exposed to them. However, for some biomarkers, levels' decreases have been observed which may partly be explained by measures taken to prohibit some of these chemicals (e.g. atrazine) and by industrial processes evolutions leading to the substitution of others (e.g. bisphenol A, di-2-ethylhexyl phthalate/DEHP, dialkyl phosphates). Therefore, the list of biomarkers to be monitored in the French HBM program has been implemented to include some substitutes of biomarkers prioritized in the first instance (e.g. bisphenol S, F). Finally, this method combines rigor and flexibility and helped us to build a prioritized list that will be shared and supported by many if not all actors. Copyright © 2016 Elsevier GmbH. All rights reserved.

Evolution of biomolecular loadings along a major river system

NASA Astrophysics Data System (ADS)

Freymond, Chantal V.; Kündig, Nicole; Stark, Courcelle; Peterse, Francien; Buggle, Björn; Lupker, Maarten; Plötze, Michael; Blattmann, Thomas M.; Filip, Florin; Giosan, Liviu; Eglinton, Timothy I.

2018-02-01

Understanding the transport history and fate of organic carbon (OC) within river systems is crucial in order to constrain the dynamics and significance of land-ocean interactions as a component of the global carbon cycle. Fluvial export and burial of terrestrial OC in marine sediments influences atmospheric CO2 over a range of timescales, while river-dominated sedimentary sequences can provide valuable archives of paleoenvironmental information. While there is abundant evidence that the association of organic matter (OM) with minerals exerts an important influence on its stability as well as hydrodynamic behavior in aquatic systems, there is a paucity of information on where such associations form and how they evolve during fluvial transport. Here, we track total organic carbon (TOC) and terrestrial biomarker concentrations (plant wax-derived long-chain fatty acids (FA), branched glycerol dialkyl glycerol tetraethers (brGDGTs) and lignin-derived phenols) in sediments collected along the entire course of the Danube River system in the context of sedimentological parameters. Mineral-specific surface area-normalized biomarker and TOC concentrations show a systematic decrease from the upper to the lower Danube basin. Changes in OM loading of the available mineral phase correspond to a net decrease of 70-80% of different biomolecular components. Ranges for biomarker loadings on Danube River sediments, corresponding to 0.4-1.5 μgFA/m2 for long-chain (n-C24-32) fatty acids and 17-71 ngbrGDGT/m2 for brGDGTs, are proposed as a benchmark for comparison with other systems. We propose that normalizing TOC as well as biomarker concentrations to mineral surface area provides valuable quantitative constraints on OM dynamics and organo-mineral interactions during fluvial transport from terrigenous source to oceanic sink.

Exposure to organophosphate pesticides and male hormone profile in floriculturist of the state of Morelos, Mexico.

PubMed

Blanco-Muñoz, Julia; Morales, Magally Mayanin; Lacasaña, Marina; Aguilar-Garduño, Clemente; Bassol, Susana; Cebrián, Mariano E

2010-07-01

Studies on experimental animals have found that organophosphate (OP) pesticides may act as endocrine disruptors; however, their effects on the human hormonal profile have not yet been adequately characterized. We evaluate the association between exposure to OP pesticides, measured through dialkyl phosphate (DAP) metabolites urinary levels, and the male hormone profile. A cross-sectional study was performed in 104 floriculturists of Morelos, Mexico. A structured questionnaire was applied to get information on sociodemographic characteristics, anthropometry, clinical history, alcohol and tobacco consumption, and work history. DAP metabolites [dimethylphosphate (DMP), dimethylthiophosphate, dimethyldithiophosphate, diethylphosphate (DEP), diethylthiophosphate (DETP) and diethyldithiophosphate] were determined using gas-liquid chromatography. Serum levels of FSH, LH, prolactin, testosterone, inhibin B and estradiol were determined using enzyme-linked immunosorbent assay. Multiple linear regression was used to study the association between DAP metabolite levels and male hormonal profile. Data were adjusted by p,p'-dichlorodiphenyldichloroethene serum levels and other potential confounders. There was a negative association between inhibin B and urinary levels of DMP, DEP, DETP and total DAP metabolites. DEP levels were negatively associated with serum FSH concentrations, but marginally and positively associated with those of testosterone. DETP was marginally associated with lower LH serum levels. There were no other significant associations among OP metabolites and serum hormone levels. Inhibin B and FSH vary according to levels of DAP metabolites in men occupationally exposed to OP pesticides. These results suggest that OP pesticides could act as endocrine disruptors in humans; however, most hormonal values fell within the wide normal range and associations were small. There is, therefore, a need for further investigation to elucidate their biological and clinical relevance.

Synthesis and antimalarial and antituberculosis activities of a series of natural and unnatural 4-methoxy-6-styryl-pyran-2-ones, dihydro analogues and photodimers

PubMed Central

McCracken, Stephen T.; Kaiser, Marcel; Boshoff, Helena I.; Boyd, Peter D. W.; Copp, Brent R.

2012-01-01

Previous studies have identified the 3,6-dialkyl-4-hydroxy-pyran-2-one marine microbial metabolites pseudopyronines A and B to be modest growth inhibitors of Mycobacterium tuberculosis and a range of tropical diseases including Plasmodium falciparum and Leishmania donovani. In an effort to expand the structure-activity relationship of this compound class towards. infectious diseases, a library of natural product and natural product-like 4-methoxy-6-styryl-pyran-2-ones and a subset of catalytically reduced examples were synthesised. In addition, the photochemical reactivity of several of the 4-methoxy-6-styryl-pyran-2-ones were investigated yielding head-to-head and head-to-tail cyclobutane dimers as well as examples of asymmetric aniba-dimer A-type dimers. All compounds were evaluated for cytotoxicity and activity against M. tuberculosis, P. falciparum, L. donovani, Trypanosoma brucei rhodesiense and T. cruzi. Of the styryl-pyranones, natural product 3 and non-natural styrene and naphthalene substituted examples 13, 18, 21, 22 and 23 exhibited antimalarial activity (IC50 < 10 μM) with selectivity indices (SI) > 10. Δ7 Dihydro analogues were typically less active or lacked selectivity. Head-to-head and head-to-tail photodimers 5 and 34 exhibited moderate IC50s of 2.3 to 17 μM towards several of the parasitic organisms, while the aniba-dimer-type asymmetric dimers 31 and 33 were identified as being moderately active towards P. falciparum (IC50 1.5 and 1.7 μM) with good selectivity (SI ∼ 80). The 4-tert-butyl aniba-dimer A analogue 33 also exhibited activity towards L. donovani (IC50 4.5 μM), suggesting further elaboration of this latter scaffold could lead to the identification of new leads for the dual treatment of malaria and leishmaniasis. PMID:22285027

Natronobiforma cellulositropha gen. nov., sp. nov., a novel haloalkaliphilic member of the family Natrialbaceae (class Halobacteria) from hypersaline alkaline lakes.

PubMed

Sorokin, Dimitry Y; Khijniak, Tatiana V; Kostrikina, Nadezhda A; Elcheninov, Alexander G; Toshchakov, Stepan V; Bale, Nicole J; Damsté, Jaap S Sinninghe; Kublanov, Ilya V

2018-04-27

Six strains of extremely halophilic and alkaliphilic euryarchaea were enriched and isolated in pure culture from surface brines and sediments of hypersaline alkaline lakes in various geographical locations with various forms of insoluble cellulose as growth substrate. The cells are mostly flat motile rods with a thin monolayer cell wall while growing on cellobiose. In contrast, the cells growing with cellulose are mostly nonmotile cocci covered with a thick external EPS layer. The isolates, designated AArcel, are obligate aerobic heterotrophs with a narrow substrate spectrum. All strains can use insoluble celluloses, cellobiose, a few soluble glucans and xylan as their carbon and energy source. They are extreme halophiles, growing within the range from 2.5 to 4.8M total Na + (optimum at 4M) and obligate alkaliphiles, with the pH range for growth from 7.5 to 9.9 (optimum at 8.5-9). The core archaeal lipids of strain AArcel5 T were dominated by C 20 -C 20 dialkyl glycerol ether (DGE) (i.e. archaeol) and C 20 -C 25 DGE in nearly equal proportion. The 16S rRNA gene analysis indicated that all six isolates belong to a single genomic species mostly related to the genera Saliphagus-Natribaculum-Halovarius. Taking together a substantial phenotypic difference of the new isolates from the closest relatives and the phylogenetic distance, it is concluded that the AArcel group represents a novel genus-level branch within the family Natrialbaceae for which the name Natronobiforma cellulositropha gen. nov., sp. nov. is proposed with AArcel5 T as the type strain (JCM 31939 T =UNIQEM U972 T ). Copyright © 2018 The Authors. Published by Elsevier GmbH.. All rights reserved.

PON1 and Neurodevelopment in Children from the CHAMACOS Study Exposed to Organophosphate Pesticides in Utero

PubMed Central

Eskenazi, Brenda; Huen, Karen; Marks, Amy; Harley, Kim G.; Bradman, Asa; Barr, Dana Boyd; Holland, Nina

2010-01-01

Background Paraoxonase 1 (PON1) detoxifies oxon derivatives of some organophosphate (OP) pesticides, and its genetic polymorphisms influence enzyme activity and quantity. We previously reported that maternal urinary concentrations of dialkyl phosphate (DAP) metabolites, a marker of OP pesticide exposure, were related to poorer mental development and maternally reported symptoms consistent with pervasive developmental disorder (PDD) in 2-year-olds participating in the Center for the Health Assessment of Mothers and Children of Salinas (CHAMACOS) study. Objective We determined whether PON1 genotypes and enzyme measurements were associated with child neurobehavioral development and whether PON1 modified the association of in utero exposure to OPs (as assessed by maternal DAPs) and neurobehavior. Methods We measured DAP concentrations in maternal urine during pregnancy, PON1192 and PON1−108 genotypes in mothers and children, and arylesterase (ARYase) and paraoxonase (POase) in maternal, cord, and 2-year-olds’ blood. We assessed 353 2-year-olds on the Mental Development Index (MDI) and Psychomotor Development Index (PDI) of the Bayley Scales of Infant Development and queried their mothers on the Child Behavior Checklist to obtain a score for PDD. Results Children with the PON1−108T allele had poorer MDI scores and somewhat poorer PDI scores. Children were less likely to display PDD when they or their mothers had higher ARYase activity and when their mothers had higher POase activity. The association between DAPs and MDI scores was strongest in children with PON1−108T allele, but this and other interactions between DAPs and PON1 polymorphisms or enzymes were not significant. Conclusion PON1 was associated with child neurobehavioral development, but additional research is needed to confirm whether it modifies the relation with in utero OP exposure. PMID:21126941

Association of Organophosphate Pesticide Exposure and Paraoxonase with Birth Outcome in Mexican-American Women

PubMed Central

Harley, Kim G.; Huen, Karen; Aguilar Schall, Raul; Holland, Nina T.; Bradman, Asa; Barr, Dana Boyd; Eskenazi, Brenda

2011-01-01

Background Epidemiologic studies suggest that maternal organophosphorus (OP) pesticide exposure is associated with poorer fetal growth, but findings are inconsistent. We explored whether paraoxonase (PON1), a key enzyme involved in detoxification of OPs, could be an effect modifier in this association. Methods The study population included 470 pregnant women enrolled in the CHAMACOS Study, a longitudinal cohort study of mothers and children living in an agricultural region of California. We analyzed urine samples collected from mothers twice during pregnancy for dialkyl phosphate (DAP) metabolites of OP pesticides. We analyzed maternal and fetal (cord) blood samples for PON1 genotype (PON1192 and PON1−108) and enzyme activity (paraoxonase and arylesterase). Infant birth weight, head circumference, and gestational age were obtained from medical records. Results Infants' PON1 genotype and activity were associated with birth outcome, but mothers' were not. Infants with the susceptible PON1−108TT genotype had shorter gestational age (β = −0.5 weeks, 95% Confidence Interval (CI): −0.9, 0.0) and smaller head circumference (β = −0.4 cm, 95% CI: −0.7, 0.0) than those with the PON1−108CC genotype. Infants' arylesterase and paraoxonase activity were positively associated with gestational age. There was some evidence of effect modification with DAPs: maternal DAP concentrations were associated with shorter gestational age only among infants of the susceptible PON1−108TT genotype (p-valueinteraction = 0.09). However, maternal DAP concentrations were associated with larger birth weight (p-valueinteraction = 0.06) and head circumference (p-valueinteraction<0.01) in infants with non-susceptible genotypes. Conclusions Infants whose PON1 genotype and enzyme activity levels suggested that they might be more susceptible to the effects of OP pesticide exposure had decreased fetal growth and length of gestation. PON1 may be another factor contributing to preterm or low birth weight birth. PMID:21904599

Atmospheric pressure photoionization mass spectrometry as a tool for the investigation of the hydrolysis reaction mechanisms of phosphite antioxidants

NASA Astrophysics Data System (ADS)

Papanastasiou, M.; McMahon, A. W.; Allen, N. S.; Johnson, B. W.; Keck-Antoine, K.; Santos, L.; Neumann, M. G.

2008-08-01

The hydrolysis reaction mechanism of phosphite antioxidants is investigated by liquid chromatography-mass spectrometry (LC/MS). The phosphites were chosen because they differed in chemical structure and phosphorus content. Dopant assisted-atmospheric pressure photoionization (DA-APPI) is chosen as the ion source for the ionization of the compounds. In our previous work, DA-APPI was shown to offer an attractive alternative to atmospheric pressure chemical ionization (APCI) since it provided background-ion free mass spectra and higher sensitivity [M. Papanastasiou, et al., Polymer Degradation and Stability 91 (11) (2006) 2675-2682]. In positive ion mode, the molecules are generally detected in their protonated form. In negative ion mode, the phosphites are unstable and only fragment ions are observed; these however, are characteristic of each phosphite and may be used for the identification of the analytes in complex mixtures. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites, with phenol substituents producing very hydrolytically stable structures. Alkanox P24 and PEP-36 follow a similar hydrolytic pathway via the scission of the first and then the second POphenol bonds, eventually leading to the formation of phenol, phosphorous acid and pentaerythritol as end products. HP-10 exhibits a rather different structure and the products detected suggest scission of either the POhydrocarbon or one of the POphenol bonds. A phenomenon similar to that of autocatalysis is observed for all phosphites and is attributed to the formation of dialkyl phosphites as intermediate products.

Mid-latitude continental temperatures through the early Eocene in western Europe

NASA Astrophysics Data System (ADS)

Inglis, Gordon N.; Collinson, Margaret E.; Riegel, Walter; Wilde, Volker; Farnsworth, Alexander; Lunt, Daniel J.; Valdes, Paul; Robson, Brittany E.; Scott, Andrew C.; Lenz, Olaf K.; Naafs, B. David A.; Pancost, Richard D.

2017-02-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are increasingly used to reconstruct mean annual air temperature (MAAT) during the early Paleogene. However, the application of this proxy in coal deposits is limited and brGDGTs have only been detected in immature coals (i.e. lignites). Using samples recovered from Schöningen, Germany (∼48°N palaeolatitude), we provide the first detailed study into the occurrence and distribution of brGDGTs through a sequence of early Eocene lignites and associated interbeds. BrGDGTs are abundant and present in every sample. In comparison to modern studies, changes in vegetation type do not appear to significantly impact brGDGT distributions; however, there are subtle differences between lignites - representing peat-forming environments - and siliciclastic nearshore marine interbed depositional environments. Using the most recent brGDGT temperature calibration (MATmr) developed for soils, we generate the first continental temperature record from central-western continental Europe through the early Eocene. Lignite-derived MAAT estimates range from 23 to 26 °C while those derived from the nearshore marine interbeds exceed 20 °C. These estimates are consistent with other mid-latitude environments and model simulations, indicating enhanced mid-latitude, early Eocene warmth. In the basal part of the section studied, warming is recorded in both the lignites (∼2 °C) and nearshore marine interbeds (∼2-3 °C). This culminates in a long-term temperature maximum, likely including the Early Eocene Climatic Optimum (EECO). Although this long-term warming trend is relatively well established in the marine realm, it has rarely been shown in terrestrial settings. Using a suite of model simulations we show that the magnitude of warming at Schöningen is broadly consistent with a doubling of CO2, in agreement with late Paleocene and early Eocene pCO2 estimates.

Introducing TEX86 as a Water pH Proxy for Alkaline Lakes on the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Wang, M.; Tian, Q.; Li, X.; Liang, J.; Yue, H.; Hou, J.

2017-12-01

Lake water pH represents one of the most important indicators for lake evolution and factors influencing the evolution of aquatic ecosystem, however, which is less studied on the Tibetan Plateau (TP). Applicability of diatom assemblages, an effective proxy of lake water pH variation in freshwater lakes, is highly limited on the TP because the widespread distribution of alkaline lakes is unfavorable for preservation of diatom shells. Glycerol dialkyl glycerol tetraethers (GDGTs) are a series of specific membrane lipids biosynthesized by archaea and bacteria, which appear to be a promising method to reflect lake water pH variation. Here we present the distribution of iGDGTs compounds in surface sediments across the TP to discuss the effect of various environmental factors on iGDGTs distribution. The results show that TEX86 is a promising proxy for lake water pH in high-elevation alkaline lakes, as water pH appears to be the most important factor to affect the cyclization of iGDGTs. We proposed the water pH calibration for lakes (salinity<20g/L) on TP, pH=1.8176×TEX86+8.2376 (n=31, r=0.86, RMSE=0.24). To evaluate its performance, we applied the calibration at Bangong Co in western TP and reconstructed past changes in lake water pH. The TEX86-derived pH at Bangong Co varied from 8.69 to 9.49 since the last 16 kyr BP, which is generally consistent with precipitation isotope variation that was reconstructed from leaf wax D/H ratios in the same sediment core, suggesting the lake water pH was mainly controlled by local hydrology. We believe that TEX86 will be able to infer past water pH of alkaline lakes over TP and could be a potentially useful tool for reconstructing pH in alkaline lakes worldwide after regional calibrated.

New Amphiphilic Neamine Derivatives Active against Resistant Pseudomonas aeruginosa and Their Interactions with Lipopolysaccharides

PubMed Central

Sautrey, Guillaume; Zimmermann, Louis; Deleu, Magali; Delbar, Alicia; Souza Machado, Luiza; Jeannot, Katy; Van Bambeke, Françoise; Buyck, Julien M.; Decout, Jean-Luc

2014-01-01

The development of novel antimicrobial agents is urgently required to curb the widespread emergence of multidrug-resistant bacteria like colistin-resistant Pseudomonas aeruginosa. We previously synthesized a series of amphiphilic neamine derivatives active against bacterial membranes, among which 3′,6-di-O-[(2″-naphthyl)propyl]neamine (3′,6-di2NP), 3′,6-di-O-[(2″-naphthyl)butyl]neamine (3′,6-di2NB), and 3′,6-di-O-nonylneamine (3′,6-diNn) showed high levels of activity and low levels of cytotoxicity (L. Zimmermann et al., J. Med. Chem. 56:7691–7705, 2013). We have now further characterized the activity of these derivatives against colistin-resistant P. aeruginosa and studied their mode of action; specifically, we characterized their ability to interact with lipopolysaccharide (LPS) and to alter the bacterial outer membrane (OM). The three amphiphilic neamine derivatives were active against clinical colistin-resistant strains (MICs, about 2 to 8 μg/ml), The most active one (3′,6-diNn) was bactericidal at its MIC and inhibited biofilm formation at 2-fold its MIC. They cooperatively bound to LPSs, increasing the outer membrane permeability. Grafting long and linear alkyl chains (nonyl) optimized binding to LPS and outer membrane permeabilization. The effects of amphiphilic neamine derivatives on LPS micelles suggest changes in the cross-bridging of lipopolysaccharides and disordering in the hydrophobic core of the micelles. The molecular shape of the 3′,6-dialkyl neamine derivatives induced by the nature of the grafted hydrophobic moieties (naphthylalkyl instead of alkyl) and the flexibility of the hydrophobic moiety are critical for their fluidifying effect and their ability to displace cations bridging LPS. Results from this work could be exploited for the development of new amphiphilic neamine derivatives active against colistin-resistant P. aeruginosa. PMID:24867965

Transport of branched tetraether lipids from the Tagus River basin to the coastal ocean of the Portuguese margin: consequences for the interpretation of the MBT'/CBT paleothermometer

NASA Astrophysics Data System (ADS)

Zell, C.; Kim, J.-H.; Balsinha, M.; Dorhout, D.; Fernandes, C.; Baas, M.; Sinninghe Damsté, J. S.

2014-03-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs), which are transported from soil to marine sediment by rivers, have been used to reconstruct the mean annual air temperature (MAAT) and soil pH of the drainage basin using the methylation index of branched tetraethers (MBT, recently refined as MBT') and cyclization index of branched tetraethers (CBT) from coastal marine sediment records. In this study we are tracing the brGDGTs from source to sink in the Tagus River basin, the longest river system on the Iberian Peninsula, by determining their concentration and distribution in soils, river suspended particulate matter (SPM), riverbank sediments, marine SPM, and marine surface sediments. The concentrations of brGDGTs in river SPM were substantially higher and their distributions were different compared to those of the drainage basin soils. This indicates that brGDGTs are mainly produced in the river itself. In the marine environment, the brGDGT concentrations rapidly decreased with increasing distance from the Tagus estuary. At the same time, the brGDGT distributions in marine sediments also changed, indicating that marine in-situ production also takes place. These results show that there are various problems that complicate the use of the MBT'/CBT for paleoreconstructions using coastal marine sediments in the vicinity of a river. However, if the majority of brGDGTs are produced in the river, it might be possible to reconstruct the environmental (temperature and pH) conditions of the river water using appropriate aquatic calibrations, provided that marine core locations are chosen in such a way that the brGDGTs in their sediments are predominantly derived from riverine in-situ production.

Transport of branched tetraether lipids from the Tagus River basin to the coastal ocean of the Portuguese margin: Consequences for the interpretation of the MBT'/CBT paleothermometer

NASA Astrophysics Data System (ADS)

Zell, Claudia; Kim, Jung-Hyun; Balinsha, Maria; Dorhout, Denise; Santos Fernandez, Cten; Baas, Marianne; Sinninghe Damsté, Jaap S.

2014-05-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs), which are transported from soil to marine sediment by rivers, have been used to reconstruct the mean annual air temperature(MAAT) and soil pH of the drainage basin using the methylation index of branched tetraethers(MBT, recently refined as MBT') and cyclization index of branched tetraethers (CBT) from coastal marine sediment records. In this study we are tracing the brGDGTs from source to sink in the Tagus River basin, the longest river system on the Iberian Peninsula, by determining their concentration and distribution in soils, river suspended particulate matter (SPM), riverbank sediments, marine SPM, and marine surface sediments. The concentrations of brGDGTs in river SPM were substantially higher and their distributions were different compared to those of the drainage basin soils. This indicates that brGDGTs are mainly produced in the river itself. In the marine environment, the brGDGT concentrations rapidly decreased with increasing distance from the Tagus estuary. At the same time, the brGDGT distributions in marine sediments also changed,indicating that marine in-situ production also takes place. These results show that there are various problems that complicate the use of the MBT'/CBT for paleoreconstructions using coastal marine sediments in the vicinity of a river. However, if the majority of brGDGTs are produced in the river, it might be possible to reconstruct the environmental (temperature and pH) conditions of the river water using appropriate aquatic calibrations, provided that marine core locations are chosen in such a way that the brGDGTs in their sediments are predominantly derived from riverine in-situ production.

The isolation of the temperature effect on branched GDGT distribution in an elevation transect of the Eastern Cordillera, Colombia

NASA Astrophysics Data System (ADS)

Anderson, V. J.; Shanahan, T. M.; Saylor, J.; Horton, B. K.

2012-12-01

Recently, the distribution of branched GDGT's (glycerol dialkyl glycerol tetraethers) has been proposed as a proxy for temperature and pH in soils via the MBT/CBT index, and has been used to reconstruct past temperature variations in a number of settings ranging from marine sediments to loess deposits and paleosols. However, empirical calibrations of the MBT/CBT index against temperature show significant scatter, leading to uncertainties as large as ±2 degrees C . In this study we seek to add to and improve upon the existing soil calibration using a new set of samples spanning a large elevation (and temperature) gradient in the Eastern Cordillera of Colombia. At each site we buried temperature loggers to constrain the diurnal and seasonal temperature experienced by each soil sample. Located only 5 degrees north of the equator, our sites experience a very small seasonal temperature variation - most sites display an annual range of less than 4 degrees C. In addition, the pH of all of the soils is almost invariant across the transect, with the vast majority of samples having pH's between 4 and 5. This dataset represents a "best-case" scenario - small variations in seasonal temperature, pH, and well-constrained instrumental data - which allow us to examine the brGDGT-temperature relationship in the absence of major confounding factors such as seasonality and soil chemistry. Interestingly, the relationship between temperature and the MBT/CBT index is not improved using this dataset, suggesting that these factors are not the cause of the anomalous scatter in the calibration dataset. However, we find that using other parameterizations for the regression equation instead of the MBT and CBT indices, the errors in our temperature estimates are significantly reduced.

Early childhood adversity potentiates the adverse association between prenatal organophosphate pesticide exposure and child IQ: The CHAMACOS cohort.

PubMed

Stein, Lauren J; Gunier, Robert B; Harley, Kim; Kogut, Katherine; Bradman, Asa; Eskenazi, Brenda

2016-09-01

Previous studies have observed an adverse association between prenatal exposure to organophosphate pesticide (OPs) and child cognition, but few studies consider the potential role of social stressors in modifying this relationship. We seek to explore the potential role of early social adversities in modifying the relationship between OPs and child IQ in an agricultural Mexican American population. Participants from the Center for the Health Assessment of Mothers and Children of Salinas (CHAMACOS) study, a prospective longitudinal pre-birth cohort study, include 329 singleton infants and their mothers followed from pregnancy through age 7. Dialkyl phosphate metabolite concentrations (DAPs), a biomarker of organophosphate pesticide exposure, were measured in maternal urine collected twice during pregnancy and averaged. Child cognitive ability was assessed at 7 years using the Wechsler Intelligence Scale for Children - Fourth Edition. Demographic characteristics and adversity information were collected during interviews and home visits at numerous time points from pregnancy until age 7. Among low-income Latina mothers and their children in the Salinas Valley, total adversity and specific domains of adversity including poor learning environment and adverse parent-child relationships were negatively associated with child cognition. Adverse associations between DAP concentrations and IQ were stronger in children experiencing greater adversity; these associations varied by child sex. For example, the association between prenatal OP exposure and Full-Scale IQ is potentiated among boys who experienced high adversity in the learning environment (β=-13.3; p-value <0.01). Greater total and domain-specific adversity modifies negative relationships between prenatal OP exposure and child IQ differently among male and female children. These findings emphasize the need to consider plausible interactive pathways between social adversities and environmental exposures. Copyright © 2016 Elsevier B.V. All rights reserved.

Design and synthesis of novel sulfonamide-containing bradykinin hB2 receptor antagonists. 1. Synthesis and SAR of alpha,alpha-dimethylglycine sulfonamides.

PubMed

Fattori, Daniela; Rossi, Cristina; Fincham, Christopher I; Berettoni, Marco; Calvani, Federico; Catrambone, Fernando; Felicetti, Patrizia; Gensini, Martina; Terracciano, Rosa; Altamura, Maria; Bressan, Alessandro; Giuliani, Sandro; Maggi, Carlo A; Meini, Stefania; Valenti, Claudio; Quartara, Laura

2006-06-15

We recently published the extensive in vivo pharmacological characterization of MEN 16132 (J. Pharmacol. Exp. Ther. 2005, 616-623; Eur. J. Pharmacol. 2005, 528, 7), a member of the sulfonamide-containing human B(2) receptor (hB(2)R) antagonists. Here we report, in detail, how this family of compounds was designed, synthesized, and optimized to provide a group of products with subnanomolar affinity for the hB(2)R and high in vivo potency after topical administration to the respiratory tract. The series was designed on the basis of indications from the X-ray structures of the key structural motifs A and B present in known antagonists and is characterized by the presence of an alpha,alpha-dialkyl amino acid. The first lead (17) of the series was submitted to extensive chemical work to elucidate the structural requirements to increase hB(2) receptor affinity and antagonist potency in bioassays expressing the human B(2) receptor (hB(2)R). The following structural features were selected: a 2,4-dimethylquinoline moiety and a piperazine linker acylated with a basic amino acid. The representative lead compound 68 inhibited the specific binding of [(3)H]BK to hB(2)R with a pKi of 9.4 and antagonized the BK-induced inositolphosphate (IP) accumulation in recombinant cell systems expressing the hB(2)R with a pA(2) of 9.1. Moreover, compound 68 when administered (300 nmol/kg) intratracheally in the anesthetized guinea pig, was able to significantly inhibit BK-induced bronchoconstriction for up to 120 min after its administration, while having a lower and shorter lasting effect on hypotension.

Archaeal and bacterial H-GDGTs are abundant in peat and their relative abundance is positively correlated with temperature

NASA Astrophysics Data System (ADS)

Naafs, B. D. A.; McCormick, D.; Inglis, G. N.; Pancost, R. D.; T-GRES Peat Database Collaborators

2018-04-01

Glycerol monoalkyl glycerol tetraether lipids (GMGTs; also called 'H-GDGTs') differ from the more commonly studied glycerol dialkyl glycerol tetraether (GDGTs) in that they have an additional covalent bond that links the two alkyl chains. Six different archaeal isoprenoidal H-GDGTs (H-isoGDGTs) and one branched H-GDGT (H-brGDGT), presumably produced by bacteria, have previously been found. However, the function of H-GDGTs in both domains of life is unknown. It is thought that the formation of this additional covalent bond results in enhanced membrane stability, accounting for the high abundance of H-GDGTs in extreme environments such as geothermal settings, but so far there has been little evidence to support this hypothesis. Here we report the distribution of H-GDGTs in a global peat database (n = 471) with a broad range in mean annual air temperature (MAAT) and pH. This is the first finding of H-GDGTs in soils (specifically, peat), highlighting that H-GDGTs are widespread in mesophilic settings. In addition, we report the presence of two new H-brGDGTs with one (H-1034) and two (H-1048) additional methyl groups, respectively. Our results suggest that the relative abundance of both bacterial and archaeal H-GDGTs compared to regular GDGTs is related to temperature with the highest relative abundance of H-GDGTs in tropical peats. Although other factors besides temperature likely also play a role, these results do support the hypothesis that H-GDGTs are an adaptation to temperature to maintain membrane stability. The observation that both bacterial and archaeal membrane lipids respond to temperature indicates the same adaption across the lipid divide between these two domains of life, suggesting parallel or convergent evolution (potentially facilitated by lateral gene transfer).

Sources of core and intact branched tetraether membrane lipids in the lacustrine environment: Anatomy of Lake Challa and its catchment, equatorial East Africa

NASA Astrophysics Data System (ADS)

Buckles, Laura K.; Weijers, Johan W. H.; Verschuren, Dirk; Sinninghe Damsté, Jaap S.

2014-09-01

The MBT/CBT palaeotemperature proxy uses the distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs), membrane lipids that are supposed to derive from soil bacteria, to reconstruct mean annual air temperature (MAAT). Applied successfully in coastal marine sediments, its extension to lake-sediment records with potentially high time resolution would greatly expand its utility. Over the last years, however, studies have indicated the presence of additional sources of brGDGTs within lake systems. To constrain the factors influencing the MBT/CBT palaeotemperature proxy in lakes, detailed investigation of brGDGT fluxes in a modern lake system is necessary to identify their potential sources. This study concentrates on Lake Challa, a permanently stratified crater lake in equatorial East Africa with limited catchment area. An almost 3-year time series of approximately monthly samples of settling particles, supplemented with a depth profile of suspended particulate matter (SPM) and sets of profundal surface-sediment and catchment soil samples, were analysed for both the 'living' intact polar lipids (IPLs) and 'fossil' core lipids (CLs) of GDGTs. We found that brGDGTs are produced in oxic, suboxic and anoxic zones of the water column, and in substantial amounts compared to influxes from catchment soils. Additional in situ production within the lake sediments is most probable, but cannot be definitely confirmed at this time. These lacustrine brGDGTs display a different response to temperature variation than soil-derived brGDGTs, signifying either a different physiological adaptation to changing conditions within the water column and/or a different composition of the respective bacterial communities. Using this specific relationship with temperature, a local calibration based on brGDGT distributions in SPM generates relatively accurate water temperature estimates from settling particles but fails for surface sediments.

Exploring ancient microbial community assemblages by creating complex lipid biomarker profiles for stromatolites and microbial mats in Hamelin Pool, Shark Bay, Australia

NASA Astrophysics Data System (ADS)

Myers, E.; Summons, R. E.; Schubotz, F.; Matys, E. D.

2015-12-01

Stromatolites that are biogenic in origin, a characteristic that can be determined by the coexistence of microbial mats (active microbial communities) and stromatolites (lithified structures) like in Hamelin Pool, comprise one of the best modern analogs to ancient microbial community assemblages. Comprehensive lipid biomarker profiles that include lipids of varying persistence in the rock record can help determine how previously living microbial communities are represented in lithified stromatolites. To create these profiles, the samples analyzed included non-lithified smooth, pustular, and colloform microbial mats, as well as smooth and colloform stromatolites. Select samples were separated into upper and lower layers of 5cm depth each. Intact polar lipids, glycerol dialkyl glycerol tetraethers, and bacteriohopanepolyols were analyzed via liquid chromatography-mass spectrometry (LC-MS) coupled to a Quadropole Time-of-Flight (QTOF) mass spectrometer; additionally, fatty acids from each sample were analyzed using gas chromatography-mass spectrometry (GC-MS) to prove consistent signatures with those determined by Allen et al. in 2010 for similar microbial mat samples. In accordance with those findings, 2-methylhopanoids were detected, as well as limited signals from higher (vascular) plants, the latter of which suggests terrestrial inputs, potentially from runoff. The rarely detected presence of 3-methylhopanoids appears in a significant portion of the samples, though further isolations of the molecule are needed to confirm. While all lipid profiles were relatively similar, certain differences in relative composition are likely attributable to morphological differences of the mats, some of which allow deeper oxygen and/or sunlight penetration, which influence the microbial community. However, overall similarities of transient and persistent lipids suggest that the microbial communities of both the non-lithified microbial mats and stromatolites are similar.

New Temperature Calibrations and Validation Tests of 5- and 6-Methyl brGDGTs in Lake Sediment

NASA Astrophysics Data System (ADS)

Russell, J. M.; Williams, J. W.; Jackson, S. T.; S Sinninghe Damsté, J.; Watson, B. I.

2017-12-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are increasingly used to reconstruct changes in temperature and other environmental variables. There are now multiple methods to measure brGDGTs, many different brGDGT calibrations for different environments, and many applications of the brGDGT proxy, yet brGDGT-based temperature reconstructions have rarely been tested against independent paleoclimate data to evaluate and validate the proxy. We present new temperature calibrations of brGDGTs preserved in 65 lake sediment samples determined using new, improved chromatographic methods that separate 5- and 6-methyl brGDGT isomers. We test these new calibrations, as well as calibrations using older methods that do not separate brGDGT isomers, in a sediment core spanning the last deglaciation from a classic North American site (Silver Lake, USA) against independent pollen-derived temperature estimates. The distributions of and environmental controls on 5- and 6-methyl brGDGTs differs significantly in lake sediments versus soils, suggesting different controls on bacterial membrane lipid compositions in the two environments. This results in different calibrations in soils and lake sediments; however, like soils, separation of 5- and 6-methyl isomers significantly improves the errors statistics of some brGDGT-temperature calibrations, with calibration errors of 2-2.5 ºC. Applying these calibrations to sediments from Silver Lake, we observe warming from the last glacial maximum to the Holocene of 10.5 ºC as well as clear Bolling-Allerod and Younger Dryas responses. The amplitude and structure of temperature changes inferred from brGDGTs match well with estimates from pollen, with correlations (r2) as high as 0.88, indicating GDGTs can provide accurate temperature reconstructions. We further observe relationships between brGDGT- and pollen-inferred temperature estimates that suggest GDGT proxies can provide information on vegetation responses to climate changes in the past.

Application of Lacustrine Biomarkers to Reconstruct Late Holocene Temperature Change in the Saskatchewan Prairies.

NASA Astrophysics Data System (ADS)

Cavazzin, B.; Toney, J. L.; Pearson, E. J.; Schouten, S.; Leavitt, P.; Haig, H.

2016-12-01

Extreme hydrological events such as prolonged droughts are among Canada's costliest natural calamities resulting in disastrous impacts on agriculture, forestry, industry, and ecosystems. Investigations into climate variations prior to significant anthropogenic modification are essential to build effective projection models and adaptation strategies needed to reduce economic, social and environmental vulnerability within the prairies eco-region. In this study we use organic geochemical analysis of lipids produced by bacteria, archaea and algae in lake and catchment sediments. These organic compounds are highly resistant to degradation and accumulate in the sediments as geochemical fossils or biomarkers. In particular we focus on Glycerol Dialkyl Glycerol Tetraethers (GDGT) biomarkers which are ubiquitous in soils and lacustrine environments and can be applied as quantitative temperature proxies in regions of the world where other proxies cannot be used. The aim of this study is to examine the relationship between GDGT distribution and temperature and assess the potential for establishing a GDGT-based paleothermometer for the Canadian prairies lakes. Our training set includes GDGT data from core-top sediments from 105 lakes across spanning a 5° latitudinal gradient and spring surface water temperature gradient of about 9°C. We identified 30 known bacterial and archaeal GDGTs, including the novel archaeal tetraether lipids with a cyclohexyl ring. These compounds are present in varying proportions in all the lakes investigated, suggesting a broad range of GDGT inputs and also potential in-situ production. We analysed the relationships between individual GDGT compounds against temperature, pH, conductivity, water depth and other environmental variables. We also examined previously published GDGT-environment indices in order to test the applicability of previously developed GDGT-based paleotemperature calibrations to the prairies lakes and assess whether a new calibration is needed specifically for this region.

Distribution of branched GDGTs in surface sediments from the Colville River, Alaska: Implications for the MBT'/CBT paleothermometer in Arctic marine sediments

NASA Astrophysics Data System (ADS)

Hanna, Andrea J. M.; Shanahan, Timothy M.; Allison, Mead A.

2016-07-01

Significant climate fluctuations in the Arctic over the recent past, and additional predicted future temperature changes, highlight the need for high-resolution Arctic paleoclimate records. Arctic coastal environments supplied with terrigenous sediment from Arctic rivers have the potential to provide annual to subdecadal resolution records of climate variability over the last few millennia. A potential tool for paleotemperature reconstructions in these marine sediments is the revised methylation index of branched tetraethers (MBT')/cyclization ratio of branched tetraethers (CBT) proxy based on branched glycerol dialkyl glycerol tetraethers (brGDGTs). In this study, we examine the source of brGDGTs in the Colville River, Alaska, and the adjacent Simpson Lagoon and reconstruct temperatures from Simpson Lagoon sediments to evaluate the applicability of this proxy in Arctic estuarine environments. The Colville catchment soils, fluvial sediments, and estuarine sediments contain statistically similar brGDGT distributions, indicating that the brGDGTs throughout the system are soil derived with little alteration from in situ brGDGT production in the river or coastal waters. Temperatures reconstructed from the MBT'/CBT indices for surface samples show good agreement with regional summer (June through September) temperatures, suggesting a seasonal bias in Arctic temperature reconstructions from the Colville system. In addition, we reconstruct paleotemperatures from an estuarine sediment core that spans the last 75 years, revealing an overall warming trend in the twentieth century that is consistent with trends observed in regional instrumental records. These results support the application of this brGDGT-based paleotemperature proxy for subdecadal-scale summer temperature reconstructions in Arctic estuaries containing organic material derived from sediment-laden, episodic rivers.

Continental temperatures through the early Eocene in western central Europe

NASA Astrophysics Data System (ADS)

Inglis, G. N.; Collinson, M. E.; Riegel, W.; Wilde, V.; Farnsworth, A.; Lunt, D. J.; Robson, B.; Scott, A. C.; Lenz, O.; Pancost, R.

2016-12-01

In contrast to the marine realm, our understanding of terrestrial temperature change during greenhouse climates is poorly constrained. Recently, branched glycerol dialkyl glycerol tetraethers (brGDGTs) have been used to successfully reconstruct mean annual air temperature (MAAT) during the early Paleogene. However, despite the potential to provide new insights into terrestrial climate, the application of this proxy in lignite and coal deposits is still limited. Using samples recovered from Schöningen, Germany ( 48°N), we provide the first detailed study into the occurrence and distribution of brGDGTs through a sequence of Early Eocene lignites and associated marine interbeds. Branched GDGTs are abundant and present in every sample. In comparison to modern studies, changes in vegetation type do not appear to significantly impact brGDGT distributions; however, there are subtle differences in these distributions between lignites and siliciclastic nearshore marine interbed sediments. Using the most recent brGDGT temperature calibration, we generate the first continental temperature record from central-western continental Europe through the Early Eocene. Lignite-derived MAAT estimates range from 23 to 26°C and those derived from the nearshore marine interbeds always exceed 20°C. These estimates are consistent with other mid-latitude palaeoclimate proxy records which indicate enhanced early Eocene warmth. In the basal part of the section, warming is recorded in both the lignites ( 2°C) and nearshore marine interbeds ( 2-3°C). This culminates in a long-term temperature maximum, likely including the Early Eocene Climatic Optimum (EECO). Although this trend is relatively well established in marginal marine sediments within the SW Pacific, it has rarely been shown in other regions or terrestrial settings. Using a suite of new climate model simulations, our warming trend is consistent with a doubling of CO2 (from 560ppmv to 1120ppmv) which broadly agrees with proxy-derived CO2 estimates from the early Paleogene

Dependence of the cyclization of branched tetraethers (CBT) on soil moisture in the Chinese Loess Plateau and the adjacent areas: implications for palaeorainfall reconstructions

NASA Astrophysics Data System (ADS)

Wang, H.; Liu, W.; Zhang, C. L.

2014-06-01

Branched glycerol dialkyl glycerol tetraethers (bGDGTs) have been show promising for continental paleotemperature studies in loess-paleosol sequences (LPSs). Thus far, however, little is known about the effect of soil moisture on their distributions on the Chinese Loess Plateau (CLP). In this study, the relationships between environmental variables and the cyclization of bGDGTs (the so called CBT index) were investigated in a comprehensive set of surface soils in the CLP and its adjacent arid/semi-arid areas. We find that CBT correlates best with soil water content (SWC) or mean annual precipitation (MAP) for the total sample set. Particularly for the CLP soils, there is a significant positive relationship between CBT and MAP (CBT = -0.0021 · MAP + 1.7, n = 37, R2 = 0.87; MAP range: 210-680 mm). This indicates that CBT is mainly controlled by soil moisture in the alkalescent soils (pH > 7) in arid/semi-arid regions, where it is not sensitive to soil pH. Therefore, we suggest that CBT can potentially be used as a palaeorainfall proxy on the CLP. According to the preliminary CBT-MAP relationship for modern CLP soils, palaeorainfall history was reconstructed from three LPSs (Yuanbao, Lantian, and Mangshan) with published bGDGT data spanning the past 70 ka. The CBT-derived MAP records of the three sites consistently show precession-driven variations resembling the speleothem δ18O monsoon record, and are also in general accord with the fluctuations of the respective magnetic susceptibility (MS) record, supporting CBT as a reasonable proxy for palaeorainfall reconstruction in LPS studies. Moreover, the comparison of CBT-derived MAP and bGDGT-derived temperature may enable us to further assess the relative timing and magnitude of hydrological and thermal changes on the CLP, independent of chronology.

Paleoaltimetry proxies based on bacterial branched tetraether membrane lipids in soils

NASA Astrophysics Data System (ADS)

Yang, Huan; Xiao, Wenjie; Jia, Chengling; Xie, Shucheng

2015-03-01

The MBT/CBT (Methylation Index of Branched Tetraethers/Cyclisation ratio of Branched Tetraether) proxy, a terrestrial paleothermometer based on bacterial branched glycerol dialkyl glycerol tetraethers (bGDGTs), was employed to indicate altimetry; however, the mechanistic control on this proxy is still ambiguous. Here, we investigated the bGDGTs' distribution and associated environmental factors along an altitude transect of Mt. Shennongjia in China in order to determine the applicability of bGDGT-based proxies to altimetry reconstruction. The MBT index exhibits only a weak correlation with estimated mean annual air temperature (MATe, estimated according to the meteorological record and lapse rate) or altitude. Likewise, MBT shows weak or no relationship with temperature or altitude at four other mountains (Mts. Meghalaya, Jianfengling, Gongga, and Rungwe). It is notable that mean annual air temperature (MAT) or altitude estimated by the MBT/CBT proxy largely relies on CBT, rather than on MBT, which was generally acknowledged. The poor relationship between MBTand MATe for Mt. Shennongjia can be ascribed to the insensitive response of bGDGT-I to temperature. Our data from this mountain imply that care should be taken if the MBT/CBT proxy is employed as an indication of paleoaltimetry. We propose that the fractional abundance of bGDGTs may be a better paleoaltimeter than the MBT/CBT proxy, because specific bGDGT subsets that might show the most sensitive response to temperature can be preferentially selected using a statistical method and used to establish local calibration. This local calibration was applied to Mt. Shennongjia and apparently improves the accuracy of temperature and altimetry reconstruction. The differential response of bGDGTs to temperature among mountains suggests that local calibrations are needed to better constrain the altimetry.

Biomonitoring of organophosphate exposure of pesticide sprayers and comparison of exposure levels with other population groups in Thessaly (Greece).

PubMed

Koureas, Michalis; Tsakalof, Andreas; Tzatzarakis, Manolis; Vakonaki, Elena; Tsatsakis, Aristidis; Hadjichristodoulou, Christos

2014-02-01

To evaluate the exposure of different population groups in Thessaly (Greece) to organophosphate pesticides (OPs) and investigate the dependence of exposure levels on pesticide application practices, personal protective and hygienic measures taken. For the exposure assessment, four dialkyl phosphate (DAP) metabolites of organophosphate pesticides were quantified in spot urine samples of 77 pesticide sprayers, 75 residents of the studied agricultural area non-involved in agricultural activities and 112 urban residents who served as a control group. Structured questionnaires were used to record demographic characteristics, pesticide application parameters and protective measures taken. Univariate and multivariate analysis of the obtained cross-sectional data was performed to identify potential risk factors associated with biomarker levels. It was found that total DAP median level in the sprayers' group was 24.9 μg/g creatinine (IQR: 13.0-42.1), while the rural and urban residents had significantly lower (p<0.001) levels of 11.3 μg/g creatinine (IQR: 5.3-18.7) and 11.9 μg/g creatinine (IQR: 6.3-20.3), respectively. In sprayers who had recently applied an OP pesticide (n=28), the median levels of DAP metabolites were 31.8 μg/g creatinine (IQR: 22.3-117.2). Logistic regression analysis showed that the use of full body coveralls while handling and spraying pesticides was significantly associated with lower DAP levels (OR 4.05, 95% CI 1.22 to 13.46). Also, changing clothes immediately after accidental contamination of clothing with pesticide amounts was found to be significantly associated with lower exposure levels (OR 4.04, CI 1.05 to 15.57). Our study findings confirm the increased exposure to OPs in pesticide sprayers and underline the importance of protective measures especially those that focus on dermal exposure mitigation.

A biomarker perspective on dust, productivity, and sea surface temperature in the Pacific sector of the Southern Ocean

NASA Astrophysics Data System (ADS)

Jaeschke, Andrea; Wengler, Marc; Hefter, Jens; Ronge, Thomas A.; Geibert, Walter; Mollenhauer, Gesine; Gersonde, Rainer; Lamy, Frank

2017-05-01

In this study, we present a new multiproxy data set of terrigenous input, marine productivity and sea surface temperature (SST) from 52 surface sediment samples collected along E-W transects in the Pacific sector of the Southern Ocean. Allochthonous terrigenous input was characterized by the distribution of plant wax n-alkanes and soil-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs). 230Th-normalized burial of both compound groups were highest close to the potential sources in Australia and New Zealand and are strongly related to lithogenic contents (232Th), indicating common sources and transport. Detection of both long-chain n-alkanes and brGDGTs at the most remote sites in the open ocean strongly suggests a primarily eolian transport mechanism to at least 110°W, i.e. by prevailing westerly winds. Two independent organic SST proxies were used, the U37K‧ based on alkenones, and the TEX86 based on isoprenoid GDGTs. Both, U37K‧ and TEX86 indices show robust relationships with temperature over a temperature range between 0.5 and 20 °C, likely implying different seasonal and regional imprints on the temperature signal. Alkenone-based temperature estimates best reflect modern summer SST in the study area when using the polar calibration of Sikes et al. (1997). In contrast, TEX86-derived temperatures may reflect a subsurface signal rather than surface. 230Th-normalized burial of alkenones is highest close to the Subtropical Front and is positively related to the deposition of lithogenic material throughout the study area. In contrast, highest isoGDGT burial south of the Antarctic Polar Front may be largely controlled by diatom blooms, and thus high opal fluxes during austral summer.

Novel Cu(I)-selective chelators based on a bis(phosphorothioyl)amide scaffold.

PubMed

Amir, Aviran; Ezra, Alon; Shimon, Linda J W; Fischer, Bilha

2014-08-04

Bis(dialkyl/aryl-phosphorothioyl)amide (BPA) derivatives are versatile ligands known by their high metal-ion affinity and selectivity. Here, we synthesized related chelators based on bis(1,3,2-dithia/dioxaphospholane-2-sulfide)amide (BTPA/BOPA) scaffolds targeting the chelation of soft metal ions. Crystal structures of BTPA compounds 6 (N(-)R3NH(+)) and 8 (NEt) revealed a gauche geometry, while BOPA compound 7 (N(-)R3NH(+)) exhibited an anti-geometry. Solid-state (31)P magic-angle spinning NMR spectra of BTPA 6-Hg(II) and 6-Zn(II) complexes imply a square planar or tetrahedral geometry of the former and a distorted tetrahedral geometry of the latter, while both BTPA 6-Ni(II) and BOPA 7-Ni(II) complexes possibly form a polymeric structure. In Cu(I)-H2O2 system (Fenton reaction conditions) BTPA compounds 6, 8, and 10 (NCH2Ph) were identified as most potent antioxidants (IC50 32, 56, and 29 μM, respectively), whereas BOPA analogues 7, 9 (NEt), and 11 (NCH2Ph) were found to be poor antioxidants. In Fe(II)-H2O2 system, IC50 values for both BTPA and BOPA compounds exceeded 500 μM indicating high selectivity to Cu(I) versus the borderline Fe(II)-ion. Neither BTPA nor BOPA derivatives showed radical scavenging properties in H2O2 photolysis, implying that inhibition of the Cu(I)-induced Fenton reaction by both BTPA and BOPA analogues occurred predominantly through Cu(I)-chelation. In addition, NMR-monitored Cu(I)- and Zn(II)-titration of BTPA compounds 8 and 10 showed their high selectivity to a soft metal ion, Cu(I), as compared to a borderline metal ion, Zn(II). In summary, lipophilic BTPA analogues are promising highly selective Cu(I) ion chelators.

The interactions among organophosphate pesticide exposure, oxidative stress, and genetic polymorphisms of dopamine receptor D4 increase the risk of attention deficit/hyperactivity disorder in children.

PubMed

Chang, Chia-Huang; Yu, Ching-Jung; Du, Jung-Chieh; Chiou, Hsien-Chih; Chen, Hsin-Chang; Yang, Winnie; Chung, Ming-Yi; Chen, Ying-Sheue; Hwang, Betau; Mao, I-Fang; Chen, Mei-Lien

2018-01-01

The aim of this study was to clarify the association between organophosphate pesticides (OPs) and attention-deficit/hyperactivity disorder (ADHD) related to oxidative stress and genetic polymorphisms. This case-control study enrolled 93 children with ADHD and 112 control children in north Taiwan. Six dialkyl phosphate (DAP) metabolites of OPs and oxidative stress biomarkers were analyzed. Polymorphisms of the dopamine receptor D4 gene (DRD4) were identified. Children with ADHD had significantly higher dimethylphosphate (DMP, 236.69nmol/g cre. vs. 186.84nmol/g cre., p value = 0.01) and 4-hydroxy-2-nonenal-mercapturic acid (HNE-MA, 28.95µg/g cre. vs. 16.55µg/g cre., p value<0.01) concentrations than control children. Children who carried DRD4 GA/AA genotypes (rs752306) were less likely than those who carried the DRD4 GG genotype to have ADHD (odds ratio [OR]: 0.45, 95% CI: 0.24-0.84). The estimated value of the AP (attributable proportion due to interaction) was 0.59 (95% CI: 0.13-1.05), indicating that 59% of ADHD cases in DMP-exposed children with the DRD4 GG genotype were due to the gene-environment interaction. After adjustment for other covariates, children who carried the DRD4 GG genotype, had been exposed to high DMP levels (more than the median), and had high HNE-MA levels had a significantly increased risk for developing ADHD (OR = 11.74, 95% CI: 2.12-65.04). This study indicated a gene-environment interaction in the risk of ADHD in children. The association between DMP and ADHD in children might relate to the mechanism of lipid peroxidation. Dose-response relationships and the combined effects of OPs, oxidative stress, and genetic polymorphism on ADHD should not be neglected. Copyright © 2017 Elsevier Inc. All rights reserved.

Levels of metabolites of organophosphate pesticides, phthalates, and bisphenol A in pooled urine specimens from pregnant women participating in the Norwegian Mother and Child Cohort Study (MoBa)

PubMed Central

Ye, Xibiao; Pierik, Frank H.; Angerer, Jürgen; Meltzer, Helle Margrete; Jaddoe, Vincent W.V.; Tiemeier, Henning; Hoppin, Jane A.; Longnecker, Matthew P.

2013-01-01

Concerns about reproductive and developmental health risks of exposure to organophosphate (OP) pesticides, phthalates, and bisphenol A (BPA) among the general population are increasing. Six dialkyl phosphate (DAP) metabolites, 3,5,6-trichloro-2-pyridinol (TCPy), BPA, and fourteen phthalate metabolites were measured in 10 pooled urine samples representing 110 pregnant women who participated in the Norwegian Mother and Child Birth Cohort (MoBa) study in 2004. Daily intakes were estimated from urinary data and compared with reference doses (RfDs) and daily tolerable intakes (TDIs). The MoBa women had a higher mean BPA concentration (4.50 μg/L) than the pregnant women in the Generation R Study (Generation R) in the Netherlands and the National Health and Nutrition Examination Survey (NHANES) in the United States. The mean concentration of total DAP metabolites (24.20 μg/L) in MoBa women was higher than that in NHANES women but lower than that in Generation R women. The diethyl phthalate metabolite mono-ethyl phthalate (MEP) was the dominant phthalate metabolite in all three studies, with the mean concentrations of greater than 300 μg/L. The MoBa and Generation R women had higher mean concentrations of mono-n-butyl phthalate (MnBP) and mono-isobutyl phthalate (MiBP) than the NHANES women. The estimated average daily intakes of BPA, chlorpyrifos/chlorpyrfios-methyl and phthalates in MoBa (and the other two studies) were below the RfDs and TDIs. The higher levels of metabolites in the MoBa participants may have been from intake via pesticide residues in food (organophosphates), consumption of canned food, especially fish/seafood (BPA), and use of personal care products (selected phthalates). PMID:19394271

Univariate predictors of maternal concentrations of environmental chemicals: The MIREC study.

PubMed

Lewin, Antoine; Arbuckle, Tye E; Fisher, Mandy; Liang, Chun Lei; Marro, Leonora; Davis, Karelyn; Abdelouahab, Nadia; Fraser, William D

2017-03-01

The developing fetus and pregnant woman can be exposed to a variety of environmental chemicals that may adversely affect their health. Moreover, environmental exposure and risk disparities are associated with different social determinants, including socioeconomic status (SES) and demographic indicators. Our aim was to investigate whether and how maternal concentrations of a large panel of persistent and non-persistent environmental chemicals vary according to sociodemographic and lifestyle characteristics in a large pregnancy and birth cohort. Data were analyzed from the Maternal-Infant Research on Environmental Chemicals (MIREC) Study, a cohort of pregnant women (N=2001) recruited over four years (2008-2011) in 10 cities across Canada. In all, 1890 urine and 1938 blood samples from the first trimester (1st and 3rd trimester for metals) were analysed and six sociodemographic and lifestyle indicators were assessed: maternal age, household income, parity, smoking status, country of birth and pre-pregnancy body mass index (BMI). We found these indicators to be significantly associated with many of the chemicals measured in maternal blood and urine. Women born outside Canada had significantly higher concentrations of di-2-ethylhexyl and diethyl phthalate metabolites, higher levels of all metals except cadmium (Cd), as well as higher levels of polychlorinated biphenyls (PCBs) and legacy organochlorine pesticides (OCPs). Nulliparity was associated with higher concentrations of dialkyl phosphates (DAPs), arsenic, dimethylarsinic acid (DMAA), perfluoroalkyl substances (PFASs) and many of the persistent organic pollutants. Smokers had higher levels of bisphenol A, Cd and perfluorohexane sulfonate, while those women who had never smoked had higher levels of triclosan, DMAA, manganese and some OCPs. Our results demonstrated that inequitable distribution of exposure to chemicals among populations within a country can occur. Sociodemographic and lifestyle factors are an important component of a thorough risk assessment as they can impact the degree of exposure and may modify the individual's susceptibility to potential health effects due to differences in lifestyle, cultural diets, and aging. Copyright © 2017 The Authors. Published by Elsevier GmbH.. All rights reserved.

O-H bond dissociation enthalpies in oximes: order restored.

PubMed

Pratt, Derek A; Blake, Jessie A; Mulder, Peter; Walton, John C; Korth, Hans-Gert; Ingold, Keith U

2004-09-01

The O-H bond dissociation enthalpies (BDEs) of 13 oximes, RR'C=NOH, having R and/or R' = H, alkyl, and aryl are reported. Experimental anchor points used to validate the results of theoretical calculations include (1) the O-H BDEs of (t-Bu)2C=NOH, t-Bu(i-Pr)C=NOH, and t-Bu(1-Ad)C=NOH determined earlier from the heat released in the reaction of (t-Bu)2C=NO* with (PhNH)2 in benzene and EPR spectroscopy (Mahoney, L. R.; Mendenhall, G. D.; Ingold, K. U. J. Am. Chem. Soc. 1973, 95, 8610), all of which were decreased by 1.7 kcal/mol to reflect a revision to the heat of formation of (E)-azobenzene (which has significant ramifications for other BDEs) and to correct for the heat of hydrogen bonding of (t-Bu)2C=NOH (alphaH2 = 0.43 measured in this work) to benzene, and (2) the measured rates of thermal decomposition of six RR'C=NOCH2Ph at 423 or 443 K, which were used to derive O-H BDEs for the corresponding RR'C=NOH. Claims (Bordwell, F. G.; Ji, G. Z. J. Org. Chem. 1992, 57, 3019; Bordwell, F. G.; Zhang, S. J. Am. Chem. Soc. 1995, 117, 4858; and Bordwell, F. G.; Liu, W.-Z. J. Am. Chem. Soc. 1996, 118, 10819) that the O-H BDEs in mono- and diaryloximes are significantly lower than those for alkyloximes due to delocalization of the unpaired electron into the aromatic ring have always been inconsistent with the known structures of iminoxyl radicals as are the purported perpendicular structures, i.e., phi(Calpha-C=N-O*) = 90 degrees, for sterically hindered dialkyl iminoxyl radicals. The present results confirm the 1973 conclusion that simple steric effects, not electron delocalization or dramatic geometric changes, are responsible for the rather small differences in oxime O-H BDEs. Copyright 2004 American Chemical Society

Soil Organic Carbon Transport in Headwater Tributaries of the Amazon River Traced by Branched GDGTs

NASA Astrophysics Data System (ADS)

Kirkels, F.; Peterse, F.; Ponton, C.; Feakins, S. J.; West, A. J.

2016-12-01

Transfer of soil organic carbon from land to sea by rivers plays a key role in the global carbon cycle by enabling long-term storage upon deposition in the marine environment, and generates archives of paleoinformation. Specific soil bacterial membrane lipids (branched glycerol dialkyl glycerol tetraethers, brGDGTs) can trace soil inputs to a river. BrGDGT distributions relate to soil pH and mean annual air temperature and can be inferred by a novel calibration [1]. In the Amazon Fan, down-core changes in brGDGTs have been used for paleoclimate reconstructions [2]. However, the effects of fluvial sourcing and transport on brGDGT signals in sedimentary deposits are largely unknown. In this study, we investigated the implications of upstream dynamics and hydrological variability (wet/dry season) on brGDGT distributions carried by the Madre de Dios River (Peru), a tributary of the upper Amazon River. The Madre de Dios basin covers a 4.5 km elevation gradient draining the eastern flank of the Andes to the Amazonian floodplains [3], along which we examined organic and mineral soils, and river suspended particulate matter (SPM). BrGDGT signals of SPM indicate sourcing of soils within the catchment, with concentrations increasing downstream indicating accumulation of this biomarker. River depth profiles demonstrated uniform brGDGT distributions and concentrations, suggesting no preferential transport and that brGDGTs are well-mixed in the river. These findings add to prior studies on brGDGTs in the downstream Amazon River [4, 5]. Our study highlights the importance of the upstream drainage basin to constrain the source of brGDGTs in rivers, to better interpret climate reconstructions with this proxy. [1] De Jonge et al. (2014) Geochim Cosmochim Act 141, 97-112 [2] Bendle et al. (2010) Geochem Geoph Geosy 11 [3] Ponton et al. (2014) Geophys. Res. Lett 41, 6420-6427. [4] Kim et al. (2012) Geochim Cosmochim Act 90, 163-180. [5] Zell et al. (2013) Front Microbio 4, 228.

Source, transport and fate of soil organic matter inferred from microbial biomarker lipids on the East Siberian Arctic Shelf

NASA Astrophysics Data System (ADS)

Bischoff, Juliane; Sparkes, Robert B.; Doğrul Selver, Ayça; Spencer, Robert G. M.; Gustafsson, Örjan; Semiletov, Igor P.; Dudarev, Oleg V.; Wagner, Dirk; Rivkina, Elizaveta; van Dongen, Bart E.; Talbot, Helen M.

2016-09-01

The Siberian Arctic contains a globally significant pool of organic carbon (OC) vulnerable to enhanced warming and subsequent release by both fluvial and coastal erosion processes. However, the rate of release, its behaviour in the Arctic Ocean and vulnerability to remineralisation is poorly understood. Here we combine new measurements of microbial biohopanoids including adenosylhopane, a lipid associated with soil microbial communities, with published glycerol dialkyl glycerol tetraethers (GDGTs) and bulk δ13C measurements to improve knowledge of the fate of OC transported to the East Siberian Arctic Shelf (ESAS). The microbial hopanoid-based soil OC proxy R'soil ranges from 0.0 to 0.8 across the ESAS, with highest values nearshore and decreases offshore. Across the shelf R'soil displays a negative linear correlation with bulk δ13C measurements (r2 = -0.73, p = < 0.001). When compared to the GDGT-based OC proxy, the branched and isoprenoid tetraether (BIT) index, a decoupled (non-linear) behaviour on the shelf was observed, particularly in the Buor-Khaya Bay, where the R'soil shows limited variation, whereas the BIT index shows a rapid decline moving away from the Lena River outflow channels. This reflects a balance between delivery and removal of OC from different sources. The good correlation between the hopanoid and bulk terrestrial signal suggests a broad range of hopanoid sources, both fluvial and via coastal erosion, whilst GDGTs appear to be primarily sourced via fluvial transport. Analysis of ice complex deposits (ICDs) revealed an average R'soil of 0.5 for the Lena Delta, equivalent to that of the Buor-Khaya Bay sediments, whilst ICDs from further east showed higher values (0.6-0.85). Although R'soil correlates more closely with bulk OC than the BIT, our understanding of the endmembers of this system is clearly still incomplete, with variations between the different East Siberian Arctic regions potentially reflecting differences in environmental conditions (e.g. temperature, pH), but other physiological controls on microbial bacteriohopanepolyol (BHP) production under psychrophilic conditions are as yet unknown.

Decreasing urinary organophosphate pesticide metabolites among pregnant women and their offspring in Jerusalem: Impact of regulatory restrictions on agricultural organophosphate pesticides use?

PubMed

Ein-Mor, Eliana; Ergaz-Shaltiel, Zivanit; Berman, Tamar; Göen, Thomas; Natsheh, Juma; Ben-Chetrit, Avraham; Haimov-Kochman, Ronit; Calderon-Margalit, Ronit

2018-06-01

Maternal urinary levels of dialkyl phosphate (DAP) metabolites of organophosphate pesticides (OP) during pregnancy are associated with adverse outcomes in the offspring. Between 2012 and 2014, eighteen active OP ingredients were restricted or banned in Israel for agricultural use. We aimed to study trends of urinary DAP metabolites among pregnant women and their offspring in the era of the new regulations. Pregnant women were recruited at 11-18 weeks of gestation and provided spot urine samples (n = 273). Soon after birth, neonatal urine samples were collected (n = 107). All urine specimens analyzed for DAP metabolites. Trends in DAP metabolites were tested using Mann-Kendall trend statistic (M-K S) and linear regression models were constructed to estimate the association between calendar period and DAP levels between September 2012 and March 2016. Over the study period, median maternal ∑DAP levels decreased from 248 nmol/L to 148 nmol/L. Time of recruitment was associated with a statistically significant decrease in DAP metabolites, which remained significant after multivariate adjustment. Overall, the results for the analysis of before and after June 2014 showed a significant decrease in ∑DAP of -0.198 log10 nmol/L (95%CI: -0.311,-0.084) which corresponds with a decrease of 36.6% in ∑DAP. A similar trend was found for DAP metabolites in neonatal urine. Compared to other studies, pregnant women in Jerusalem had higher ∑DAP levels, even at the end of the study period. We observed significant reductions in maternal and neonatal DAP urinary levels during the period of 2012-2016. Regulations restricting agricultural use of OP seem to be effective in reducing population exposure to OP, in an era when residential use of OP is banned. Copyright © 2018 Elsevier GmbH. All rights reserved.

Source to Sink Transport of Terrestrial Biomarkers in a Monsoon-driven Fluvial System

NASA Astrophysics Data System (ADS)

Kirkels, F.; Zwart, H. M.; Usman, M.; Basu, S.; Martes, C.; Eglinton, T. I.; Peterse, F.

2016-12-01

Rivers are an important link in global organic carbon (OC) cycling by connecting soils and marine sediments. Whereas deposition of terrestrial carbon in marine settings may form a large OC sink, the extent of OC loss during river transport by CO2 outgassing is highly uncertain. In this context, it is crucial to better constrain the composition and sources of OC in rivers. The Godavari River in Central India is very dynamic with intense rainfall and high soil erosion rates during the monsoon and low transport during the dry period, representative of low frequency, high-impact erosion events expected worldwide due to climate change. In this study, we did a high-resolution sampling of soils, river sediments (bulk and < 63 um) and suspended particulate matter (SPM) during the monsoon and dry season. Source-to-sink tracing of concentration and compositional variations in branched glycerol dialkyl glycerol tetraethers (brGDGTs) as soil-specific biomarkers allowed us to follow soil OC transport through the river basin. Spatial trends in weight-normalized GDGT patterns reveal marked changes during the monsoon and dry season from upstream tributaries towards the delta. Evolution of GDGT signatures along the course of the river shows that SPM during the monsoon carries a primarily soil-derived signal contributed by the northern headwaters. Dominance of the recently discovered 6-methyl isomer indicates a year-round aquatic contribution from the western tributaries. River water isotopic composition and GDGT signatures show that northern tributaries dominate modern OC export from the Godavari basin, providing new information for the interpretation of paleorecords derived from cores taken in the Bay of Bengal. More detailed insights in OC sources in the Godavari basin will derive from (bulk) δ13C and ultimately 14C analyses of soils and river sediments. Further research into provenance of the mineral fraction will reveal if sediment and OC transport is (de)coupled.

Biomarkers as Indicators of Respiration During Laboratory Incubations of Alaskan Arctic Tundra Permafrost Soils

NASA Astrophysics Data System (ADS)

Hutchings, J.; Schuur, E.; Bianchi, T. S.; Bracho, R. G.

2015-12-01

High latitude permafrost soils are estimated to store 1,330 - 1,580 Pg C, which account for ca. 40% of global soil C and nearly twice that of atmospheric C. Disproportionate heating of high latitude regions during climate warming potentially results in permafrost thaw and degradation of surficial and previously-frozen soil C. Understanding how newly-thawed soils respond to microbial degradation is essential to predicting C emissions from this region. Laboratory incubations have been a key tool in understanding potential respiration rates from high latitude soils. A recent study found that among the common soil measurements, C:N was the best predictor of C losses. Here, we analyzed Alaskan Arctic tundra soils from before and after a nearly 3-year laboratory incubation. Bulk geochemical values as well as the following biomarkers were measured: lignin, amino acids, n-alkanes, and glycerol dialkyl glycerol tetraethers (GDGT). We found that initial C:N did not predict C losses and no significant change in C:N between initial and final samples. The lignin acid to aldehyde (Ad:Al) degradation index showed the same results with a lack of C loss prediction and no significant change during the experiment. However, we did find that C:N and Ad:Al had a significant negative correlation suggesting behavior consistent with expectations. The failure to predict C losses was likely influenced by a number of factors, including the possibility that biomarkers were tracking a smaller fraction of slower cycling components of soil C. To better interpret these results, we also used a hydroxyproline-based amino acid degradation index and n-alkanes to estimate the contribution Sphagnum mosses to soil samples - known to have slower turnover times than vascular plants. Finally, we applied a GDGT soil temperature proxy to estimate the growing season soil temperatures before each incubation, as well as investigating the effects of incubation temperature on the index's temperature estimate.

Prenatal Exposure to Organophosphate Pesticides and Neurobehavioral Development of Neonates: A Birth Cohort Study in Shenyang, China

PubMed Central

Zhang, Ying; Han, Song; Liang, Duohong; Shi, Xinzhu; Wang, Fengzhi; Liu, Wei; Zhang, Li; Chen, Lixin; Gu, Yingzi; Tian, Ying

2014-01-01

Background A large amount of organophosphate pesticides (OPs) are used in agriculture in China every year, contributing to exposure of OPs through dietary consumption among the general population. However, the level of exposure to OPs in China is still uncertain. Objective To investigate the effect of the exposure to OPs on the neonatal neurodevelopment during pregnancy in Shenyang, China. Methods 249 pregnant women enrolled in the Central Hospital Affiliated to Shenyang Medical College from February 2011 to August 2012. A cohort of the mothers and their neonates participated in the study and information on each subject was obtained by questionnaire. Dialkyl phosphate (DAP) metabolites were detected in the urine of mothers during pregnancy to evaluate the exposure level to OPs. Neonate neurobehavioral developmental levels were assessed according to the standards of the Neonatal Behavioral Neurological Assessment (NBNA). Multiple linear regressions were utilized to analyze the association between pregnancy exposure to OPs and neonatal neurobehavioral development. Results The geometric means (GM) of urinary metabolites for dimethyl phosphate (DMP), dimethyl thiophosphate (DMTP), diethyl phosphate (DEP), and diethyl thiophosphate (DETP) in pregnant women were 18.03, 8.53, 7.14, and 5.64 µg/L, respectively. Results from multiple linear regressions showed that prenatal OP exposure was one of the most important factors affecting NBNA scores. Prenatal total DAP concentrations were inversely associated with scores on the NBNA scales.?Additionally, a 10-fold increase in DAP concentrations was associated with a decrease of 1.78 regarding the Summary NBNA (95% CI, −2.12 to −1.45). And there was an estimated 2.11-point difference in summary NBNA scores between neonates in the highest quintile of prenatal OP exposure and the lowest quintile group. Conclusion The high exposure of pregnant women to OPs in Shenyang, China was the predominant risk factor for neonatal neurobehavioral development. PMID:24551109

Transition from a warm and dry to a cold and wet climate in NE China across the Holocene

NASA Astrophysics Data System (ADS)

Zheng, Yanhong; Pancost, Richard D.; Naafs, B. David A.; Li, Qiyuan; Liu, Zhao; Yang, Huan

2018-07-01

Northeast (NE) China lies in the northernmost part of the East Asian Summer monsoon (EASM) region. Although a series of Holocene climatic records have been obtained from lakes and peats in this region, the Holocene hydrological history and its controls remain unclear. More specifically, it is currently debated whether NE China experienced a dry or wet climate during the early Holocene. Here we reconstruct changes in mean annual air temperature and peat soil moisture across the last ∼13,000 year BP using samples from the Gushantun and Hani peat, located in NE China. Our approach is based on the distribution of bacterial branched glycerol dialkyl glycerol tetraethers (brGDGTs) and the abundance of the archaeal isoprenoidal (iso)GDGT crenarchaeol. Using the recently developed peat-specific MAATpeat temperature calibration we find that NE China experienced a relatively warm early Holocene (∼5-7 °C warmer than today), followed by a cooling trend towards modern-day values during the mid- and late Holocene. Moreover, crenarchaeol concentrations, brGDGT-based pH values, and the distribution of 6-methyl brGDGTs, all indicate an increase in soil moisture content from the early to late Holocene in both peats, which is largely consistent with other data from NE China. This trend towards increasing soil moisture/wetter conditions across the Holocene in NE China records contrasts with the trends observed in other parts of the EASM region, which exhibit an early and/or mid-Holocene moisture/precipitation maximum. However, the Holocene soil moisture variations and temperature-moisture relationships (warm-dry and cold-wet) observed in NE China are similar to those observed in the core area of arid central Asia which is dominated by the westerlies. We therefore propose that an increase in the intensity of the westerlies across the Holocene, driven by increasing winter insolation, expanding Arctic sea ice extent and the enhanced Okhotsk High, caused an increase in moisture during the late Holocene in NE China.

A Micro and Mesocosm Approach to Understanding the Response of Branched GDGTs to Environmental Perturbation

NASA Astrophysics Data System (ADS)

Martínez-Sosa, P.; Tierney, J. E.; Castañeda, I. S.

2017-12-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids with 15 known structures. Thought to be synthesized by bacteria, they are found in peatlands, soils, near-shore marine sediments and lakes. Previous studies have reported a correlation between the number and position of methyl groups and cyclopentane moieties in these lipids with environmental factors such as pH and temperature, leading to the creation of the methylation and cyclisation indices (MBT and CBT respectively). Although an empirical relationship between these structural modifications and environmental conditions has been described, the source organism for these molecules remains unknown. Lacking pure cultures of brGDGT producing bacteria, a different approach is necessary to study their response to environmental perturbations under controlled conditions. To this end, we studied the production of brGDGTs in water from two fishing lakes in Arizona using a series of microcosms, comprised by 1L flasks filled with environmental water; and mesocosm experiments, where two 20L tanks were filled with either lake water or lake water and synthetic sediments. This experimental design allowed us to modify environmental factors while preserving the natural conditions of the sample. Our experiments point to a production of brGDGTs on the suspended particulate matter in the water column, which appears to contribute to some extent to the presence of this molecules on lake sediments. Furthermore, we observed a shift in the ratio between 5' and 6' isomers related to both the presence of a carbon source and temperature. Limited oxygen availability appears to correlate with higher brGDGT concentration. Notably, we find that methylation decreases with increasing temperature in our experiments at a rate that is roughly in agreement with empirical observations. To our knowledge, these experiments provide the first evidence of growth and alteration of brGDGTs under laboratory conditions, which could be used to build better models to interpret this paleoclimate proxy in lacustrine sediments.

A lacustrine GDGT-temperature calibration from the Scandinavian Arctic to Antarctic: Renewed potential for the application of GDGT-paleothermometry in lakes

NASA Astrophysics Data System (ADS)

Pearson, Emma J.; Juggins, Steve; Talbot, Helen M.; Weckström, Jan; Rosén, Peter; Ryves, David B.; Roberts, Stephen J.; Schmidt, Roland

2011-10-01

Quantitative climate reconstructions are fundamental to understand long-term trends in natural climate variability and to test climate models used to predict future climate change. Recent advances in molecular geochemistry have led to calibrations using glycerol dialkyl glycerol tetraethers (GDGTs), a group of temperature-sensitive membrane lipids found in Archaea and bacteria. GDGTs have been used to construct temperature indices for oceans (TEX 86 index) and soils (MBT/CBT index). The aim of this study is to examine GDGT-temperature relationships and assess the potential of constructing a GDGT-based palaeo-thermometer for lakes. We examine GDGT-temperature relationships using core top sediments from 90 lakes across a north-south transect from the Scandinavian Arctic to Antarctica including sites from Finland, Sweden, Siberia, the UK, Austria, Turkey, Ethiopia, Uganda, Chile, South Georgia and the Antarctic Peninsula. We examine a suite of 15 GDGTs, including compounds used in the TEX 86 and MBT/CBT indices and reflecting the broad range of GDGT inputs to small lake systems. GDGTs are present in varying proportions in all lakes examined. The TEX 86 index is not applicable to our sites because of the large relative proportions of soil derived and methanogenic components. Similarly, the MBT/CBT index is also not applicable and predicts temperatures considerably lower than those measured. We examine relationships between individual GDGT compounds and temperature, pH, conductivity and water depth. Temperature accounts for a large and statistically independent fraction of variation in branched GDGT composition. We propose a GDGT-temperature regression model with high accuracy and precision ( R2 = 0.88; RMSE = 2.0 °C; RMSEP = 2.1 °C) for use in lakes based on a subset of branched GDGT compounds and highlight the potential of this new method for reconstructing past temperatures using lake sediments.

Branched GDGT-based paleotemperature reconstruction of the last 30,000 years in humid monsoon region of Southeast China

NASA Astrophysics Data System (ADS)

Wang, M.

2017-12-01

The use of bacterial branched glycerol dialkyl glycerol tetraethers (brGDGTs) to reconstruct mean annual air temperatures (MAATs) and environmental pH from soils has sparked significant interest in the terrestrial paleoclimate community. However, the reconstruction of these climate proxies from peat bogs is rare in monsoonal regions of the East Asia. This research was carried out on a core from the Shuizhuyang (SZY) peat bog located in Fujian Province. Branched GDGT (brGDGT) indexes were used for reconstructing the paleoclimate of the last 30 cal ka. The aim was to evaluate quantitatively the MAAT and pH values since the Last Glacial Maximum (LGM) in the subtropical zone of China. Results show that the CBT-MBT'-derived MAAT at MIS 3 is about 15.6 °C on average, which is followed by a significant fall at the LGM (11.7-12.1 °C). The temperature difference between the LGM and the present-day value is as high as 5.8 °C. The synchronous variation of biomarker and pollen proxies indicates that replacement of subtropical evergreen broadleaved forests by coldtolerant, deciduous broadleaved forests was driven by the significant drop in air temperature. Our results also indicate that the Younger Dryas event lasted from about 12.9 to about 11.3 cal ka, and cooling event at 3.2 cal ka in the late Holocene was detected, showing the sensitivity of peat bogs to rapid cooling. Our pH reconstructions indicate that the pH of the bog rose during Heinrich 1 and Bølling-Allerød periods, probably due to low precipitation, and were lowest in the Holocene thermal maximum between 8 ka and 2.5 ka, probably due to higher precipitation. The decoupling of reconstructed MAAT and pH during particularly deglaciation and YD periods supports the hypothesis that the variations in temperature and precipitation are not always synchronous.

The Impact of Elevated Temperatures on Continental Carbon Cycling in the Paleogene

NASA Astrophysics Data System (ADS)

Pancost, R. D.; Handley, L.; Taylor, K. W.; Collinson, M. E.; Weijers, J.; Talbot, H. M.; Hollis, C. J.; Grogan, D. S.; Whiteside, J. H.

2010-12-01

Recent climate and biogeochemical modelling suggests that methane flux from wetlands and soils was greater during past greenhouse climates, due to a combination of higher continental temperatures, an enhanced hydrological cycle, and elevated primary production. Here, we examine continental environments in the Paleogene using a range of biomarker proxies (complemented by palaeobotanical approaches), including air temperatures derived from the distribution of soil bacterial glycerol dialkyl glycerol tetraethers (the MBT/CBT proxy), as well as evidence from wetland and lacustrine settings for enhanced methane cycling. Previously published and new MBT/CBT records parallel sea surface temperature records, suggesting elevated continental temperatures during the Eocene even at mid- to high latitudes (New Zealand, 20-28°C; the Arctic, 17°C; across the Sierra Nevada, 15-25°C; and SE England, 20-30°C). Such temperatures are broadly consistent with paleobotanical records and would have directly led to increased methane production via the metabolic impact of temperature on rates of methanogenesis. To test this, we have determined the distributions and carbon isotopic compositions of archaeal ether lipids and bacterial hopanoids in thermally immature Eocene lignites. In particular, the Cobham lignite, deposited in SE England and spanning the PETM, is characterised by markedly higher concentrations of both methanogen and methanotroph biomarkers compared to modern and Holocene temperate peats. Elevated temperatures, by fostering either stratification and/or decreased oxygen solubility, could have also led to enhanced methane production in Paleogene lakes. Both the Messel Shale (Germany) and Green River Formation, specifically the Parachute Creek oil shale horizons (Utah and Wyoming), are characterised by strongly reducing conditions (including euxinic conditions in the latter), as well as abundant methanogen and methanotroph biomarkers. Such results confirm model predictions of elevated Eocene methane levels relative to the Holocene (x10), but suggest that even these could be underestimates as they do not take into account lacustrine production and are generally characterised by lower high latitude temperatures than proxies suggest.

Introducing global peat-specific temperature and pH calibrations based on brGDGT bacterial lipids

NASA Astrophysics Data System (ADS)

Naafs, B. D. A.; Inglis, G. N.; Zheng, Y.; Amesbury, M. J.; Biester, H.; Bindler, R.; Blewett, J.; Burrows, M. A.; del Castillo Torres, D.; Chambers, F. M.; Cohen, A. D.; Evershed, R. P.; Feakins, S. J.; Gałka, M.; Gallego-Sala, A.; Gandois, L.; Gray, D. M.; Hatcher, P. G.; Honorio Coronado, E. N.; Hughes, P. D. M.; Huguet, A.; Könönen, M.; Laggoun-Défarge, F.; Lähteenoja, O.; Lamentowicz, M.; Marchant, R.; McClymont, E.; Pontevedra-Pombal, X.; Ponton, C.; Pourmand, A.; Rizzuti, A. M.; Rochefort, L.; Schellekens, J.; De Vleeschouwer, F.; Pancost, R. D.

2017-07-01

Glycerol dialkyl glycerol tetraethers (GDGTs) are membrane-spanning lipids from Bacteria and Archaea that are ubiquitous in a range of natural archives and especially abundant in peat. Previous work demonstrated that the distribution of bacterial branched GDGTs (brGDGTs) in mineral soils is correlated to environmental factors such as mean annual air temperature (MAAT) and soil pH. However, the influence of these parameters on brGDGT distributions in peat is largely unknown. Here we investigate the distribution of brGDGTs in 470 samples from 96 peatlands around the world with a broad mean annual air temperature (-8 to 27 °C) and pH (3-8) range and present the first peat-specific brGDGT-based temperature and pH calibrations. Our results demonstrate that the degree of cyclisation of brGDGTs in peat is positively correlated with pH, pH = 2.49 × CBTpeat + 8.07 (n = 51, R2 = 0.58, RMSE = 0.8) and the degree of methylation of brGDGTs is positively correlated with MAAT, MAATpeat (°C) = 52.18 × MBT5me‧ - 23.05 (n = 96, R2 = 0.76, RMSE = 4.7 °C). These peat-specific calibrations are distinct from the available mineral soil calibrations. In light of the error in the temperature calibration (∼4.7 °C), we urge caution in any application to reconstruct late Holocene climate variability, where the climatic signals are relatively small, and the duration of excursions could be brief. Instead, these proxies are well-suited to reconstruct large amplitude, longer-term shifts in climate such as deglacial transitions. Indeed, when applied to a peat deposit spanning the late glacial period (∼15.2 kyr), we demonstrate that MAATpeat yields absolute temperatures and relative temperature changes that are consistent with those from other proxies. In addition, the application of MAATpeat to fossil peat (i.e. lignites) has the potential to reconstruct terrestrial climate during the Cenozoic. We conclude that there is clear potential to use brGDGTs in peats and lignites to reconstruct past terrestrial climate.

Assessing the Origins of Aliphatic Amines in the Murchison Meteorite from their Compound-Specific Carbon Isotopic Ratios and Enantiomeric Composition

NASA Technical Reports Server (NTRS)

Aponte, Jose; Dworkin, Jason; Elsila, Jamie E.

2014-01-01

The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of L-enantiomeric excesses for alpha-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are chemically related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with delta C-13 values ranging from +21% to +129%, showing a decrease in C-13 with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an L-enantiomeric excess of 9.7; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential linkage to meteoritic amino acids.

Synthesis and self-organization of zinc β-(dialkoxyphosphoryl)porphyrins in the solid state and in solution.

PubMed

Vinogradova, Ekaterina V; Enakieva, Yulia Y; Nefedov, Sergey E; Birin, Kirill P; Tsivadze, Aslan Y; Gorbunova, Yulia G; Bessmertnykh Lemeune, Alla G; Stern, Christine; Guilard, Roger

2012-11-19

The first synthesis and self-organization of zinc β-phosphorylporphyrins in the solid state and in solution are reported. β-Dialkoxyphosphoryl-5,10,15,20-tetraphenylporphyrins and their Zn(II) complexes have been synthesized in good yields by using Pd- and Cu-mediated carbon-phosphorous bond-forming reactions. The Cu-mediated reaction allowed to prepare the mono-β-(dialkoxyphosphoryl)porphyrins 1 Zn-3 Zn starting from the β-bromo-substituted zinc porphyrinate ZnTPPBr (TPP = tetraphenylporphyrin) and dialkyl phosphites HP(O)(OR)(2) (R = Et, iPr, nBu). The derivatives 1 Zn-3 Zn were obtained in good yields by using one to three equivalents of CuI. When the reaction was carried out in the presence of catalytic amounts of palladium complexes in toluene, the desired zinc derivative 1 Zn was obtained in up to 72% yield. The use of a Pd-catalyzed C-P bond-forming reaction was further extended to the synthesis of β-poly(dialkoxyphosphoryl)porphyrins. An unprecedented one-pot sequence involving consecutive reduction and phosphorylation of H(2)TPPBr(4) led to the formation of a mixture of the 2,12- and 2,13-bis(dialkoxy)phosphorylporphyrins 5 H(2) and 6 H(2) in 81% total yield. According to the X-ray diffraction studies, 1 Zn and 3 Zn are partially overlapped cofacial dimers formed through the coordination of two Zn centers by two phosphoryl groups belonging to the adjacent molecules. The equilibrium between the monomeric and the dimeric species exists in solutions of 1 Zn and 3 Zn in weakly polar solvents according to spectroscopic data (UV/Vis absorption and NMR spectroscopy). The ratio of each form is dependent on the concentration, temperature, and traces of water or methanol. These features demonstrated that zinc β-phosphorylporphyrins can be regarded as new model compounds for the weakly coupled chlorophyll pair in the photosynthesis process. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tropical and high latitude forcing of enhanced megadroughts in Northern China during the last four terminations

NASA Astrophysics Data System (ADS)

Tang, Changyan; Yang, Huan; Pancost, Richard D.; Griffiths, Michael L.; Xiao, Guoqiao; Dang, Xinyue; Xie, Shucheng

2017-12-01

Understanding the origin and evolutionary history of drought events is of great significance, providing critical insight into future hydrological conditions under the changing climate. Due to the scarcity of drought proxies from northern China, the occurrence and underlying mechanisms of the drought events remains enigmatic on longer timescales. Here we utilize microbial lipid proxies to reconstruct significant drought events over the last four ice age terminations in the southernmost section (Weinan section) of the Chinese Loess Plateau. The abundance of archaeal isoprenoid GDGTs (glycerol dialkyl glycerol tetraethers) relative to bacterial branched GDGTs, measured by Ri/b and BIT indices, is diagnostic of enhanced drought conditions. The Ri/b (and BIT) indices are stable and low (high) throughout most of the loess section spanning the last 350 thousand years, but they do exhibit sharp transient peaks (valleys) during the intervals associated with the four ice age terminations, and especially Terminations II and IV. These enhanced drought events are, non-intuitively, associated with a significant decrease in the relative abundance of C4 plants, inferred by a decrease in the carbon isotope composition of bulk organic matter. Although the microbial records show some consistency with the Weinan grain size profiles, indicative of Eastern Asian winter monsoon variability, they also show some apparent difference. In fact, some features of the microbial records exhibit strong similarities with marine sediment planktonic foraminiferal δ13C records from the western Pacific warm pool, which reflect ENSO-like changes during glacial terminations. Therefore, enhanced droughts immediately before the interglacial warming in northern China could be explained, at least in part, by teleconnections in tropical ocean-atmosphere circulation via shifts in the Intertropical Convergence Zone (ITCZ) and associated Jet Stream over the Asian continent. According to our microbial biomarker data, these enhanced megadroughts are apparently different, both in terms of severity and causal mechanism, from the more commonly discussed dry conditions observed during glacial periods.

Early Holocene hydroclimate of Baffin Bay: Understanding the interplay between abrupt climate change events and ice sheet fluctuations

NASA Astrophysics Data System (ADS)

Corcoran, M. C.; Thomas, E. K.; Castañeda, I. S.; Briner, J. P.

2017-12-01

Understanding the causes of ice sheet fluctuations resulting in sea level rise is essential in today's warming climate. In high-latitude ice-sheet-proximal environments such as Baffin Bay, studying both the cause and the rate of ice sheet variability during past abrupt climate change events aids in predictions. Past climate reconstructions are used to understand ice sheet responses to changes in temperature and precipitation. The 9,300 and 8,200 yr BP events are examples of abrupt climate change events in the Baffin Bay region during which there were multiple re-advances of the Greenland and Laurentide ice sheets. High-resolution (decadal-scale) hydroclimate variability near the ice sheet margins during these abrupt climate change events is still unknown. We will generate a decadal-scale record of early Holocene temperature and precipitation using leaf wax hydrogen isotopes, δ2Hwax, from a lake sediment archive on Baffin Island, western Baffin Bay, to better understand abrupt climate change in this region. Shifts in temperature and moisture source result in changes in environmental water δ2H, which in turn is reflected in δ2Hwax, allowing for past hydroclimate to be determined from these compound-specific isotopes. The combination of terrestrial and aquatic δ2Hwax is used to determine soil evaporation and is ultimately used to reconstruct moisture variability. We will compare our results with a previous analysis of δ2Hwax and branched glycerol dialkyl glycerol tetraethers, a temperature and pH proxy, in lake sediment from western Greenland, eastern Baffin Bay, which indicates that cool and dry climate occurred in response to freshwater forcing events in the Labrador Sea. Reconstructing and comparing records on both the western and eastern sides of Baffin Bay during the early Holocene will allow for a spatial understanding of temperature and moisture balance changes during abrupt climate events, aiding in ice sheet modeling and predictions of future sea level rise.

Climatic and hydrologic perturbations in eastern North America during the Middle Miocene Climatic Optimum

NASA Astrophysics Data System (ADS)

Eley, Y.; Hren, M. T.; Super, J. R.

2017-12-01

The Middle Miocene Climatic Optimum (MMCO, 15-17 Ma) was the warmest period of the Neogene, punctuating the long-term Cenozoic cooling trend of the last 50 million years. Temperatures during the MMCO are thought to have reached 4-5 °C higher than modern, despite relatively modest atmospheric pCO2 concentrations of 300-500 ppm. Similarity between Miocene pCO2 levels and those forecast for the next century make the MMCO a key interval for understanding the potential impacts of anthropogenic pCO2 forcing. Evaluation of the climatic drivers and environmental consequences of this transient warming event is challenging, however, due to the limited number of high resolution proxy records of temperature and hydrologic change through the MMCO, particularly from terrestrial sites. Here, we present a new organic molecular record from the Calvert Cliffs formation in Maryland, to investigate terrestrial and near-shore environmental conditions during the MMCO. We observe small-scale fluctuations of 2 °C in isoprenoidal glycerol dialkyl glycerol tetraether (GDGT) TEX86-derived sea surface temperatures (SSTs), however these are superimposed on a long-term gradual warming trend that raises SSTs by 5 °C between 16.5 Ma and 14 Ma. In contrast, the MBT'-CBT soil temperature proxy, based on terrestrially sourced branched GDGTs, suggests mean annual temperatures rose by 3 °C between 16.5 and 15.9 Ma. Over the same interval, leaf wax n-alkane hydrogen isotopes show a rapid positive shift of 40‰, which we attribute to the influence of these warmer temperatures on the condensation of precipitation. A coeval negative excursion of 2‰ in carbon isotopes is indicative of an increase in rainfall during this mid-Miocene warming. The timing of biomarker-derived terrestrial climatic and hydrologic perturbations closely match reconstructed shifts in atmospheric pCO2, illustrating the tight coupling between terrestrial environmental change and carbon cycling during the middle Miocene.

Identification of a novel lipid biomarker in lake sediments: Implications for the aquatic production of branched GDGTs

NASA Astrophysics Data System (ADS)

Weber, Yuki; De Jonge, Cindy; Rijpstra, W. Irene C.; Hopmans, Ellen C.; Stadnitskaia, Alina; Schubert, Carsten J.; Lehmann, Moritz F.; Sinninghe Damsté, Jaap S.; Niemann, Helge

2014-05-01

Branched dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids that occur ubiquitously in soils worldwide. Their relative abundances (which form the MBT and CBT indices) correlate with mean annual air temperature (MAAT) and pH, making them potential proxies for paleoenvironmental reconstructions in sedimentary archives with organic matter input of from terrestrial environments. In lake sediments, however, brGDGT distributions mostly relate differently to MAAT compared to soils. A likely cause for this discrepancy is in situ production of brGDGTs within the lake water column and/or -sediments by microorganisms possessing a membrane physiology that is different from soil bacteria. Until to date, existing analytical methods did not allow the distinction between soil-and lake-derived brGDGTs, complicating paleoclimate reconstructions in lacustrine settings. In order to decipher differences in the structure and the relative distribution of brGDGTs in lake deposits versus soils, we analysed samples from 35 Swiss alpine lakes and their catchments using an improved HPLC protocol. Our data revealed a novel isomer of the hexamethylated, non-cyclic brGDGT, which was previously co-eluting with the recently described 5- and 6-methyl isomers. About half of the 35 investigated lakes contained this compound where it accounted for 1 - 11 % of total brGDGTs. We were able to isolate the previously unknown isomer by multi-step preparative HPLC. The structure of the molecule was assessed by determining the identity of its alkyl chains by ether cleavage with HI and subsequent analysis with gas chromatography quadrupole mass spectrometry (GC-MS). In addition, the carbon isotopic composition of the fragments was determined to trace their biological source. In contrast to lake sediments, soil samples analysed from the watersheds of the studied lakes did not contain the newly discovered GDGT, providing evidence for in situ production in aquatic systems. This novel isomer is the first identified, lake specific brGDGT and we expect that its recognition can significantly improve the interpretation of lacustrine brGDGTs distributions.

A High-Resolution Lipid Biomarker Perspective on North Iceland Shelf Marine Climate over the Last Millennium

NASA Astrophysics Data System (ADS)

Harning, D.; Sepúlveda, J.; Andrews, J. T.; Cabedo-Sanz, P.; Belt, S. T.; Marchitto, T. M.; Stoner, J. S.; Geirsdóttir, Á.; Miller, G. H.

2017-12-01

Icelandic climate is vulnerable to variations in the dominance of competing Arctic and Atlantic ocean currents. The boundary between these water masses delineates the Polar Front, which today occupies the North Iceland Shelf (NIS). To date, Holocene oceanographic reconstructions along the NIS have employed a variety of proxies including Mg/Ca and δ18O of benthic and planktonic foraminifera, quartz and calcite wt%, the alkenone unsaturation index (Uk'37) and biotic species assemblages. Sea surface temperature (SST) proxies are primarily derived from phytoplankton resulting in a seasonal bias toward spring/summer SST. Furthermore, SST proxies can be influenced by additional confounding variables (e.g. salinity, nutrients, depth habitat of biota) resulting in markedly different Holocene temperature reconstructions between proxy datasets. To evaluate the similarities and discrepancies between various marine proxies, we investigate a high-resolution sediment core collected from the central North Iceland Shelf (B997-316GGC, 658 m depth). Sedimentation covers the last millennium, which captures the transition from the Medieval Warm Period to the Little Ice Age. Age control is constrained by 14C dates and paleomagnetic secular variation. To assess marine surface productivity and sea ice conditions, we analyze quartz and calcite wt% via XRD and a series of highly branched isoprenoid biomarkers. Quantitative paleotemperature estimates are derived from a novel combination of Mg/Ca of foraminifera and two lipid biomarker indices, Uk'37 from Prymnesiophyte alkenones and TEX86 from Thaumarchaeota glycerol dialkyl glycerol tetraethers (GDGTs). The latter TEX86 record is the first paleo application in Icelandic waters, which a recent local calibration study suggests may reflect annual or winter sub-surface (0-200 m) temperatures. Our paleotemperature records are bolstered by the analysis of additional sediment core tops, which expand the established Icelandic calibrations. Finally, we perform statistical analyses in an effort to extract a robust record of paleoceanographic change and to test the applicability of various proxies in high-latitude paleoclimate studies.

NMR spectroscopy and X-ray characterisation of cationic N-heteroaryl-pyridylamido Zr(IV) complexes: a further level of complexity for the elusive active species of pyridylamido olefin polymerisation catalysts.

PubMed

Li, Gang; Zuccaccia, Cristiano; Tedesco, Consiglia; D'Auria, Ilaria; Macchioni, Alceo; Pellecchia, Claudio

2014-01-03

New [(N(-),N,N(-))ZrR2] dialkyl complexes (N(-),N,N(-)=pyrrolyl-pyridyl-amido or indolyl-pyridyl-amido; R=Me or CH2Ph) have been synthesised and tested as pre-catalysts for ethene and propene polymerisation in combination with different activators, such as B(C6F5)3, [Ph3C][B(C6F5)4], [HNMe2Ph][B(C6F5)4] or solid AlMe3-depleted methylaluminoxane (DMAO). Polyethylene (M(w)>2 MDa and M(w)/M(n)= 1.3-1.6) has been produced if pre-catalysts were activated with 1000 equivalents of DMAO (based on Al) [activity >1000 kg(PE)(mol([Zr]) h mol atm)(-1)] or by using a higher pre-catalyst concentration and a mixture of [HNPhMe2][B(C6F5)4] (1 equiv) and AliBu2H (60 equiv). In the case of propene polymerisation, activity has been observed only if pre-catalysts were treated with an excess of AliBu2H prior to addition of DMAO, which led to highly isotactic polypropylene ([mmmm]>95%). Neutral pre-catalysts and ion pairs derived from their activation have been characterised in solution by using advanced 1D and 2D NMR spectroscopy experiments. The detection and rationalisation of intercationic NOEs clearly showed the formation of dimeric species in which some pyrrolyl or indolyl π-electron density of one unit is engaged in stabilising the metal centre of the other unit, which relegates the counterions in the second coordination sphere. The solid-state structure of the dimeric indolyl-pyridyl-amidomethylzirconium derivative, determined by X-ray diffraction studies, points toward a weak Zr···η(3)-indolyl interaction. It can be hypothesised that the formation of dimeric cationic species hampers monomer coordination (especially of less reactive α-olefins) and that addition of AliBu2H is crucial to split the homodimers. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using tetraether lipids archived in North Sea Basin sediments to extract North Western European Pliocene continental air temperatures

NASA Astrophysics Data System (ADS)

Dearing Crampton-Flood, Emily; Peterse, Francien; Munsterman, Dirk; Sinninghe Damsté, Jaap S.

2018-05-01

The Pliocene is often regarded as a suitable analogue for future climate, due to an overall warmer climate (2-3 °C) coupled with atmospheric CO2 concentrations largely similar to present values (∼400 ppmv). Numerous Pliocene sea surface temperature (SST) records are available, however, little is known about climate in the terrestrial realm. Here we generated a Pliocene continental temperature record for Northwestern Europe based on branched glycerol dialkyl glycerol tetraether (brGDGT) membrane lipids stored in a marine sedimentary record from the western Netherlands. The total organic carbon (TOC) content of the sediments and its stable carbon isotopic composition (δ13Corg) indicate a strong transition from primarily marine derived organic matter (OM) during the Pliocene, to predominantly terrestrially derived OM after the transition into the Pleistocene. This trend is supported by the ratio of branched and isoprenoid tetraethers (BIT index). The marine-terrestrial transition indicates a likely change in brGDGT sources in the core, which may complicate the applicability of the brGDGT paleotemperature proxy in this setting. Currently, the application of the brGDGT-based paleothermometer on coastal marine sediments has been hampered by a marine overprint. Here, we propose a method to disentangle terrestrial and marine sources based on the degree of cyclization of tetramethylated brGDGTs (#rings) using a linear mixing model based on the global soil calibration set and a newly developed coastal marine temperature transfer function. Application of this method on our brGDGT record resulted in a 'corrected' terrestrial temperature record (MATterr). This latter record indicates that continental temperatures were ∼12-14 °C during the Early Pliocene, and 10.5-12 °C during the Mid Pliocene, confirming other Pliocene pollen based terrestrial temperature estimates from Northern and Central Europe. Furthermore, two colder (Δ 5-7 °C) periods in the Pliocene MATterr record show that the influence of Pliocene glacials reached well into NW Europe.

An analytical approach to the forensic identification of different classes of new psychoactive substances (NPSs) in seized materials.

PubMed

Strano Rossi, Sabina; Odoardi, Sara; Gregori, Adolfo; Peluso, Giuseppe; Ripani, Luigi; Ortar, Giorgio; Serpelloni, Giovanni; Romolo, Francesco Saverio

2014-09-15

New psychoactive substances (NPSs) are rapidly spreading worldwide, and forensic laboratories are often requested to identify new substances for which no reference standards or analytical data are available. This article describes an analytical approach that was adopted in Italy by a few collaborative centres of the Italian Early Warning System for Drugs, which has contributed many alerts for the identification of different classes of NPSs in the last 24 months. Seized crystals and powders were initially analysed via single quadrupole gas chromatography/mass spectrometry (GC/MS), followed by liquid chromatography/high-resolution mass spectrometry (LC/HRMS) in the positive electrospray ionisation (ESI) mode at 100,000 full width at half maximum resolution (FWHM) without fragmentation to elucidate the elemental compositions of unknown molecules. Different fragmentation voltages during LC/HRMS were applied to study the accurate masses of the obtained characteristic fragments. Nuclear magnetic resonance (NMR) analyses were performed to identify specific isomers when necessary. Some interesting examples of unknown NPSs from seizures later identified in our laboratories are reported, with special focus on those cases where analytical standards were not available during analyses. These cases include cathinones, such as 3-methylmethcathinone (3-MMC), methylone, bk-MBDB (butylone), 4-methylethcathinone (4-MEC), flephedrone, methylenedioxypyrovalerone (MDPV) and pentedrone, methoxetamine, apinaca or AKB48, benzydamine, meta-chlorophenylpiperazine (m-CPP), 5-MeO-N,N-dialkyl tryptamines, such as 5-MeO-DALT and 5-MeOMIPT, benzofurans, such as 6-APB and 4-APB, and diphenidine (identified for the first time in Europe). The identification of NPSs in confiscated materials was successfully achieved via GC/MS coupled with LC/HRMS and, in a few cases, NMR analyses. The availability of GC/MS libraries is of great assistance in the identification of new drugs. Alternatively, the study of characteristic molecule fragments combined with the determination of their accurate masses can be a useful approach to identify unknown samples not previously analysed. Copyright © 2014 John Wiley & Sons, Ltd.

Impacts of autochthonous marine branched GDGTs on related paleo- environmental proxies: a preliminary study

NASA Astrophysics Data System (ADS)

Dong, L.; Li, L.; Li, Q.; Zhang, C.

2014-12-01

Two proxies derived from branched glycerol dialkyl glycerol tetraethers (brGDGTs)-, the methylation index of branched tetraethers (MBT) and the cyclization ratio of branched tetraethers (CBT), are often used to reconstruct paleo mean annual air temperature (MAAT) and soil pH on the belief of their terrestrial origin. However, mounting evidence indicates the existence of autochthonous brGDGTs in marine environments，which may affect MAAT reconstruction and the use of other related paleoenvironmental proxies. Here we provide high resolution profiles of brGDGTs in a sedimentary core (MD05-2896/7) from the southern South China Sea, which include MBT and CBT indices as well as the branched and isoprenoid tetraether (BIT) index. The BIT results varied systematically with glacial-interglacial cycles, with values distinctly lower (<0.1) during the interglacial periods (MIS 1 and MIS 5) than during the glacial periods (MIS 2, MIS, 3, MIS 4 and MIS 6). Also distinct is the MBT/CBT-derived temperature, which show lower values during the interglacial periods but higher values during the glacial periods. We hypothesize that the lower MBT/CBT-derived temperature during the interglacial periods reflects subsurface water column temperature registered by autochthonous brGDGTs produced in situ marine conditions, whereas the higher MBT/CBT derived-temperature during the glacial periods reflects terrestrial MAAT because of the overwhelming input of brGDGTs from land when sea level was low. Similarly, the CBT-derived pH appears to have been overprinted also by the sea water signal of the interglacials but affected mostly by precipitation during the glacial intervals, showing patterns similar to or as a positive response to the southern hemispheric climate oscillation due to teleconnection. Our study demonstrates the complexity of brGDGT occurrence in marine environments and suggests that the MBT/CBT proxy should not be directly employed for the reconstruction of terrestrial MAAT at marine settings when BIT value is lower than 0.1.

Signature Lipids and Stable Carbon Isotope Analyses of Octopus Spring Hyperthermophilic Communities Compared with Those of Aquificales Representatives

PubMed Central

Jahnke, Linda L.; Eder, Wolfgang; Huber, Robert; Hope, Janet M.; Hinrichs, Kai-Uwe; Hayes, John M.; Des Marais, David J.; Cady, Sherry L.; Summons, Roger E.

2001-01-01

The molecular and isotopic compositions of lipid biomarkers of cultured Aquificales genera have been used to study the community and trophic structure of the hyperthermophilic pink streamers and vent biofilm from Octopus Spring. Thermocrinis ruber, Thermocrinis sp. strain HI 11/12, Hydrogenobacter thermophilus TK-6, Aquifex pyrophilus, and Aquifex aeolicus all contained glycerol-ether phospholipids as well as acyl glycerides. The n-C20:1 and cy-C21 fatty acids dominated all of the Aquificales, while the alkyl glycerol ethers were mainly C18:0. These Aquificales biomarkers were major constituents of the lipid extracts of two Octopus Spring samples, a biofilm associated with the siliceous vent walls, and the well-known pink streamer community (PSC). Both the biofilm and the PSC contained mono- and dialkyl glycerol ethers in which C18 and C20 alkyl groups were prevalent. Phospholipid fatty acids included both the Aquificales n-C20:1 and cy-C21, plus a series of iso-branched fatty acids (i-C15:0 to i-C21:0), indicating an additional bacterial component. Biomass and lipids from the PSC were depleted in 13C relative to source water CO2 by 10.9 and 17.2‰, respectively. The C20–21 fatty acids of the PSC were less depleted than the iso-branched fatty acids, 18.4 and 22.6‰, respectively. The biomass of T. ruber grown on CO2 was depleted in 13C by only 3.3‰ relative to C source. In contrast, biomass was depleted by 19.7‰ when formate was the C source. Independent of carbon source, T. ruber lipids were heavier than biomass (+1.3‰). The depletion in the C20–21 fatty acids from the PSC indicates that Thermocrinis biomass must be similarly depleted and too light to be explained by growth on CO2. Accordingly, Thermocrinis in the PSC is likely to have utilized formate, presumably generated in the spring source region. PMID:11679343

Hydrologic controls on Congo River particulate organic carbon source and reservoir age

NASA Astrophysics Data System (ADS)

Hemingway, J. D.; Schefuß, E.; Spencer, R. G.; Dinga, B. J.; Eglinton, T. I.; McIntyre, C.; Galy, V.

2016-12-01

Tropical rivers are a major source of organic matter (OM) to the coastal ocean and play a large role in the global carbon cycle. As such, it is critical to understand the sources, sinks, and transformations of OM during fluvial transit over seasonal and inter-annual timescales. Here we present dissolved organic carbon (DOC) concentrations, particulate OM (POM) composition (δ13C, δ15N, Δ14C, N/C), and glycerol dialkyl glycerol tetraether (GDGT) biomarker distributions from a 34-month time-series near the mouth of the Congo River. An end-member mixing model based on δ13C and N/C indicates that exported POM is consistently dominated by C3 tropical rainforest soil inputs, with increasing contributions by C3 tropical plant vegetation and decreasing contributions by autochthonous phytoplankton at high discharge. Calculated Δ14C values of the C3-soil end member reveal significant and variable pre-aging prior to export, especially during the year 2011 when southern-hemisphere discharge reached record lows (mean = -176‰, standard deviation = 93‰). In contrast, Δ14C values were stable near -50‰ between January and June 2013 when southern-hemisphere discharge was highest. These results indicate that headwater POM is diluted and/or overprinted by pre-aged soils during transit through the Cuvette Congolaise swamp forest, while left-bank tributaries export significantly less pre-aged material. GDGT distributions are in agreement, as the methylation and cyclization of branched tetraethers and the GDGT-0/crenarchaeol ratio reflect a significant incorporation of compounds produced in permanently inundated Cuvette Congolaise swamp-forest soils when discharge through this region is high, especially in 2011. This study provides a mechanistic link between hydrology and carbon cycling in the world's second largest tropical river and suggests that, if recent observed decreases in springtime precipitation over the Congo basin persist, future hydrologic conditions will further bias toward export of protracted, swamp-forest-derived OM sources.

Characterising the transport and preservation of microbial tetraether membrane lipids in Karst Systems

NASA Astrophysics Data System (ADS)

Jex, C.; Blyth, A. J.; Baker, A.; Mcdonald, J. A.; Woltering, M.; Khan, S. J.

2013-12-01

Stalagmites have the potential to preserve organic biomarkers, proxies for changes in surface climate. Of particular interest is a class of microbial-derived lipids, the glycerol dialkyl glycerol tetraetheral (GDGT) lipids, which have been identified in cave deposits (Yang et al. 2011). Speleothem GDGT composition has been demonstrated to correlate with surface air temperature using the achaea derived isoprenoid ';(i)GDGT' index of TEX86 and the bacteria derived branched ';(b)GDGT' index of MBT/CBT of modern speleothem samples (Blyth & Schouten, 2013), indicating considerable potential for paleo-temperature reconstructions. These studies have suggested two competing sources for GDGTs in karst systems: 1) A soil derived microbial signal dominated by bGDGTs and 2) An in situ signal dominated by iGDGTs, representative of achaea existing within the cave or overlying bedrock, which dominates the speleothem signal. These findings are yet to be thoroughly tested by characterising the seasonal and spatial nature of GDGTs within caves to establish their sources and transport pathways within these complex fractured rock systems. We address this by presenting the preliminary results of a monitoring study of GDGTs within a single cave system, in South East Australia. Harrie Wood cave in Kosciusko national park is a high altitude, semi-arid site, dominated by discrete infiltration events throughout the year. Above the cave there are thin soils consisting of loose shallow scree, steep slopes and sparse shrub vegetation. We present data obtained from waters and soils immediately above and within Harrie Wood as well as in situ collection of GDGTs formed on filter papers left inside the cave throughout the year. A second cave within the same system provides contrasting surface conditions: thick red clays of moderate to no slope and Eucalypt dominated forest. As such these caves provide ideal test sites to characterise the variability in GDGT signals that may be a result of non-temperature related factors, including varying inputs (groundwater vs. in situ growth) or site specific hydrological conditions. Blyth, A.J., Schouten, S., 2013. Geochimica et Cosmochimica Acta 109, 312-328. Yang, H. et al. 2011. Organic Geochemistry 42, 108-115.

Lipid-based palaeotemperature reconstruction in lakes: New insights on the applicability of branched GDGTs in lacustrine sedimentary archives

NASA Astrophysics Data System (ADS)

Weber, Yuki; De Jonge, Cindy; Hopmans, Ellen C.; Sinninghe Damsté, Jaap S.; Gilli, Adrian; Lehmann, Moritz F.; Niemann, Helge

2014-05-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids that occur ubiquitously in soils worldwide. The relative abundances of nine structurally related brGDGTs (used in the MBT and CBT indices) have been shown to correlate with mean annual air temperature (MAAT) and soil pH, making them potential proxies in sediments that receive soil organic matter from terrestrial environments. The brGDGT distributions in lake deposits, however, mostly follow a different correlation with air temperature and (to a minor extent) lake water pH. This points to a substantial contribution of brGDGTs from in situ production within the lake water column and/or -sediments. It is also quite likely that the fractions of soil- and lake-derived brGDGTs vary considerably between sampling sites and with time, due to spatial and temporal changes in sediment input rates. Paleoclimate reconstructions using lacustrine brGDGT records thus remain challenging, especially because little is known about the environmental variables that control bacterial brGDGT production within aquatic environments. In order to decipher the impact of in situ production, we compared the brGDGT composition of surface sediments and corresponding catchment soils of 35 lakes from the Swiss alpine region, spanning an altitudinal gradient from 200 - 2000 m above mean sea level. We used an improved HPLC method to additionally quantify six recently discovered isomers, which vary in the position of their methyl branches. These 6-methyl compounds previously co-eluted with those brGDGTs used to calculate the MBT and CBT indices, obscuring any paleoenvironmental information they potentially yield. A principal component analysis suggests that the fractional abundances of the 6-methyl brGDGTs are primarily controlled by the surface water pH of the lakes. Notably, and in contrast to soils, the fractional abundance of the 5-methyl pentamethylated brGDGT in lake sediments does not show a correlation with MAAT (derived from the lapse rate model), possibly pointing to different source organisms in soils and lakes. Our results imply that in situ production of brGDGTs plays a mayor role. By further constraining the environmental controls on lake-derived brGDGTs, we aim to improve the future applicability of brGDGT-based proxies in lacustrine climate archives.

Distribution of tetraether lipids in agricultural soils - differentiation between paddy and upland management

NASA Astrophysics Data System (ADS)

Mueller-Niggemann, C.; Utami, S. R.; Marxen, A.; Mangelsdorf, K.; Bauersachs, T.; Schwark, L.

2015-10-01

Insufficient knowledge of the composition and variation of isoprenoid and branched glycerol dialkyl glycerol tetraethers (GDGTs) in agricultural soils exists, despite of the potential effect of different management types (e.g. soil/water and redox conditions, cultivated plants) on GDGT distribution. Here, we determined the influence of different soil management types on the GDGT composition in paddy (flooded) and adjacent upland (non-flooded) soils, and if available also forest, bushland and marsh soils. To compare the local effects on GDGT distribution patterns, we collected comparable soil samples in various locations from tropical (Indonesia, Vietnam and Philippines) and subtropical (China and Italy) sites. We found that differences in the distribution of isoprenoid GDGTs (iGDGTs) as well as of branched GDGTs (brGDGTs) are predominantly controlled by management type and only secondarily by climatic exposition. In general upland soil had higher crenarchaeol contents than paddy soil, which on the contrary was more enriched in GDGT-0. The GDGT-0 / crenarchaeol ratio was 3-27 times higher in paddy soil and indicates the enhanced presence of methanogenic archaea, which were additionally linked to the number of rice cultivation cycles per year (higher number of cycles was coupled with an increase in the ratio). The TEX86 values were 1.3 times higher in upland, bushland and forest soils than in paddy soils. In all soils brGDGT predominated over iGDGTs, with the relative abundance of brGDGTs increasing from subtropical to tropical soils. Higher BIT values in paddy soils compared to upland soils together with higher BIT values in soil from subtropical climates indicate effects on the amounts of brGDGT through differences in management as well as climatic zones. In acidic soil CBT values correlated well with soil pH. In neutral to alkaline soils, however, no apparent correlation but an offset between paddy and upland managed soils was detected, which may suggest that soil moisture may exert an additional control on the CBT in these soils. Lower MBT' values and calculated temperatures (TMC) in paddy soils compared to upland soils may indicate a management (e.g. enhanced soil moisture through flooding practises) induced effect on mean annual soil temperature (MST).

Synthesis and Mass Spectrometric Characterization of Organic Nitrates

NASA Astrophysics Data System (ADS)

Grünert, A.; Woidich, S.; Ballschmiter, K.

2003-04-01

Organic nitrates, as trace constituents in urban air, can be analyzed by adsorptive low volume sampling (LVS) as well as by adsorptive high volume sampling (HVS). Air samples ranging from 25 L to 100 L for the LVS and 100 m3 to 500 m3 for the (HVS) were collected, respectively. Analysis is performed by thermodesorption (LVS) or solvent elution combined with group separation (HVS) using normal-phase HPLC and high resolution capillary gas chromatography with electron capture detection (HRGC-ECD) and mass selective detection (HRGC-MSD). For identification and quantification available reference compounds are required for both methods (1;2). Following numbers of congeners of organic nitrate have been synthesized: 77 monoalkyl nitrates (C1-C16), 43 dialkyl nitrates (C2-C10), 37 hydroxy alkyl nitrates (C2-C8) and 41 carbonyl alkyl nitrates (C3-C12). Alkanes, alkenes, alcohols, ketones and halocarbons have been used as precursors. Characterisation of the reference compounds by retention-data and mass-spectra was performed by high resolution capillary gas chromatography with mass selective detection in the EI- and the NCI (CH4) mode (1-3). EI-ionization leads to the dominating indicator ion NO2+ for organic nitrates with m/z = 46 u. The characteristic fragments with NCI (CH4) show ions at m/z = 46 u and m/z = 62 u, corresponding to NO2- and NO3-. The use of flame ionisation detection (HRGC-FID) and the principle of the molar response for carbon allows the quantitation of reference solutions as the final tool for the determination of the levels and patterns of organic nitrates in urban air samples. (1) J. Kastler: "Analytik, Massenspektrometrie und Vorkommen multifunktioneller Alkylnitrate in belasteter und unbelasteter Atmosphäre" Dr.rer.nat.-Thesis, University of Ulm (1999) (2) G. Werner, J. Kastler, R. Looser, K. Ballschmiter: "Organic Nitrates of Isoprenes as Atmospheric Trace Compounds" Angew. Chem. Int. Ed. (1999) 38(11): 1634-1637 (3) S.Woidich, O. Froscheis, O. Luxenhofer, K. Ballschmiter: "EI- and NCI-mass spectrometry of aryl-alkyl nitrates and their occurrence in urban air" Fresenius J Anal Chem (1999) 364: 91-99

Mechanism of wear and tribofilm formation with ionic liquids and ashless antiwear additives

NASA Astrophysics Data System (ADS)

Sharma, Vibhu

Increasingly stringent government regulation on emissions (EPA Emissions Standard Reference Guide and latest CAFE standards requiring an average fuel economy of 54.5 mpg (combined cars and trucks) by 2025) impose significant challenges to the automotive and lubricant industries calling for the development and implementation of lower viscosity ILSAC GF-5&6 and API-CJ4&5 oils which further limit the amount of SAPS and deposits in engines. Development of additives that result in lower ash content, volatility and anti-wear property plays a crucial role in being able to reach these standards. The current industrial additive technology i.e. zinc dialkyldithiophosphate (ZDDP) forms harmful deposits on catalytic convertor due to the volatility of Zn, S and P which, impairs its functionality and consequently results in higher emission from vehicles. In this research work, ionic liquids (IL's) that are non-volatile have been studied as new generation environment friendly antiwear additives along with other ashless anti-wear additives including boron based additives to overcome the current challenges of improving the fuel efficiency and reducing the amount of hazardous emissions. The goal of this thesis work is to study the tribological performance of selected IL's and develop a comprehensive understating of IL's chemistry and its consequences to their friction and wear outcomes. As first approach, various P, S and F based ionic liquids are studied for their tribological properties by analyzing the friction and wear results generated using standard tribological experiments. Following this, advanced surface characterization techniques such as X-ray absorption near edge structure (XANES) spectroscopy, SEM, Nano-indentation, SPM techniques are used to investigate the chemical-mechanical properties of the antiwear films. Results indicate that the tribological properties of ionic liquids depend on their solubility in base oil (BO) as well as their chemical interaction with the rubbing surfaces. To address the solubility issue of IL's in BO, ILs with longer alkyl chain structure were carefully selected which helped enhance the van der waals interaction between strongly polar ILs and non-polar base oil. The interaction of IL's with the metal surfaces was examined by analyzing the chemical-mechanical properties of the antiwear films formed. Results indicate that ionic liquids do react with the steel surfaces and form a protective antiwear film composed of iron polyphosphates i.e. short to medium chain length which results in improved wear protection. In addition, soluble boron additive (SB) chemistries were blended with ionic liquids to study the synergism between these two ashless antiwear chemistries. Addition of soluble boron additive (SB) to phosphorous based IL (P_DEHP) reduces the incubation time for antiwear film formation by forming boron oxide/boron phosphate film as early as the rubbing starts and subsequently a more durable iron phosphate film is formed providing long lasting wear protection. The synergistic interaction of boron chemistry with phosphorous based ionic liquids provides superior antiwear properties while eliminating volatile elements such as Zn and S from the additive technology.

Shape-programmed nanofabrication: understanding the reactivity of dichalcogenide precursors.

PubMed

Guo, Yijun; Alvarado, Samuel R; Barclay, Joshua D; Vela, Javier

2013-04-23

Dialkyl and diaryl dichalcogenides are highly versatile and modular precursors for the synthesis of colloidal chalcogenide nanocrystals. We have used a series of commercially available dichalcogenide precursors to unveil the molecular basis for the outcome of nanocrystal preparations, more specifically, how precursor molecular structure and reactivity affect the final shape and size of II-VI semiconductor nanocrystals. Dichalcogenide precursors used were diallyl, dibenzyl, di-tert-butyl, diisopropyl, diethyl, dimethyl, and diphenyl disulfides and diethyl, dimethyl, and diphenyl diselenides. We find that the presence of two distinctively reactive C-E and E-E bonds makes the chemistry of these precursors much richer and interesting than that of other conventional precursors such as the more common phosphine chalcogenides. Computational studies (DFT) reveal that the dissociation energy of carbon-chalcogen (C-E) bonds in dichalcogenide precursors (R-E-E-R, E=S or Se) increases in the order (R): diallyl

Production rates of bacterial tetraether lipids and fatty acids in peatland under varying oxygen concentrations

NASA Astrophysics Data System (ADS)

Huguet, Arnaud; Meador, Travis B.; Laggoun-Défarge, Fatima; Könneke, Martin; Wu, Weichao; Derenne, Sylvie; Hinrichs, Kai-Uwe

2017-04-01

Interpretations of the abundance and distribution of branched glycerol dialkyl glycerol tetraether (brGDGT) lipids have been increasingly applied to infer changes in paleoenvironment and to estimate terrigenous organic matter inputs into estuarine and marine sediments. However, only preliminary information is known regarding the ecology and physiology of the source organisms of these biomarkers. We assessed the production rates of brGDGTs under different redox conditions in peat, where these lipids are found in high concentrations, particularly at greater depths below the fluctuating water table. The incorporation of hydrogen relative to carbon into lipids observed in our dual stable isotope probing assay indicates that brGDGTs were produced by heterotrophic bacteria. Unexpectedly, incubations with stable isotope tracers of the surface horizon (5-20 cm) initiated under oxic conditions before turning suboxic and eventually anoxic exhibited up to one order of magnitude higher rates of brGDGT production (16-87 ng cm-3 y-1) relative to the deeper, anoxic zone (20-35 cm; ca. 7 ng cm-3 y-1), and anoxic incubations of the surface horizon (<3 ng cm-3 y-1). Turnover times of brGDGTs in the surface horizon ranged between 8 and 41 years in the incubations initiated under oxic conditions, in contrast to 123-742 years in anoxic incubations. As brGDGTs were actively produced during both anoxic incubations and those exposed to oxygen, we conclude that their source organisms are likely facultative aerobic heterotrophs that are particularly active in the peat acrotelm. Production rates of bacterial fatty acids (ca. 2 μg cm-3 y-1) were roughly two orders of magnitude higher than those of brGDGTs, suggesting that brGDGT producers are a minor constituent of the microbial community or that brGDGTs are a small component of the microbial cell membrane in comparison to fatty acids, despite the typically high brGDGT concentrations observed in peat. Multivariate analysis identified two branched fatty acids that shared a similar production pattern as brGDGTs among the experimental treatments and may be associated with brGDGT biosynthesis.

The relationship between humans and climate across the North Atlantic: what can lacustrine biomarkers tell us?

NASA Astrophysics Data System (ADS)

de Wet, G.; Castañeda, I. S.; Bradley, R. S.; Small, G.; Barrasso, T.

2016-12-01

While climate change has been implicated in the colonization/population dynamics of the North Atlantic region, researchers in many cases are forced to compare archaeological data with distant paleoclimate records, making these linkages tenuous. Our research utilizes novel organic biomarkers in lacustrine sediments to produce paired paleoclimate and human occupancy reconstructions to better address questions surrounding human migration and climate change. Here we present preliminary results from two prominent locations in the history of the European colonization of the North Atlantic. The first, carried out on the Norse "Eastern Settlement" in Southern Greenland, attempts to answer the long-standing question of whether climate change caused the demise of the colony in the 1400s C.E. Second, we use similar techniques to search for evidence of the first peopling of the Faroe Islands, a highly debated topic. The use of lacustrine biomarkers allows for numerous aspects of both paleoclimate and human presence in a catchment to be reconstructed. We reconstruct paleotemperatures using branched glycerol dialkyl glycerol tetraethers (brGDGTs) and alkenones (the UK37 Index), when present. Additionally, will analyze the difference in the hydrogen isotopic composition of long and short-chain plant leaf waxes as a proxy for lake water balance. Human occupancy in the region is investigated using fecal sterols and stanols, primarily created by the breakdown of cholesterol. Some of these compounds, such as coprostanol (the dominant sterol in human waste), provide strong evidence of human settlements and have been identified in some of our lake records. Our preliminary results suggest that temperatures were increasing in SW Greenland during the period when the Norse are thought to have died out, potentially challenging the long-standing view of climate deterioration being the primary cause of their demise. Primary productivity biomarkers from lake Eidisvatnet, in the Faroe Islands, suggests humans may have been present and influencing the landscape hundreds of years earlier than previously thought. Overall, our work highlights the potential application of lacustrine biomarkers to answer longstanding questions about the relationship of humans and climate back through time.

Mononitrosyl tris(thiolate) iron complex [Fe(NO)(SPh)3]- and dinitrosyl iron complex [(EtS)2Fe(NO)2]-: formation pathway of dinitrosyl iron complexes (DNICs) from nitrosylation of biomimetic rubredoxin [Fe(SR)4]2-/1- (R = Ph, Et).

PubMed

Lu, Tsai-Te; Chiou, Show-Jen; Chen, Chun-Yu; Liaw, Wen-Feng

2006-10-16

Nitrosylation of the biomimetic reduced- and oxidized-form rubredoxin [Fe(SR)4]2-/1- (R = Ph, Et) in a 1:1 stoichiometry led to the formation of the extremely air- and light-sensitive mononitrosyl tris(thiolate) iron complexes (MNICs) [Fe(NO)(SR)3]- along with byproducts [SR]- or (RS)2. Transformation of [Fe(NO)(SR)3]- into dinitrosyl iron complexes (DNICs) [(RS)2Fe(NO)2]- and Roussin's red ester [Fe2(mu-SR)2(NO)4] occurs rapidly under addition of 1 equiv of NO(g) and [NO]+, respectively. Obviously, the mononitrosyl tris(thiolate) complex [Fe(NO)(SR)3]- acts as an intermediate when the biomimetic oxidized- and reduced-form rubredoxin [Fe(SR)4]2-/1- exposed to NO(g) were modified to form dinitrosyl iron complexes [(RS)2Fe(NO)2]-. Presumably, NO binding to the electron-deficient [Fe(III)(SR)4]- and [Fe(III)(NO)(SR)3]- complexes triggers reductive elimination of dialkyl/diphenyl disulfide, while binding of NO radical to the reduced-form [Fe(II)(SR)4]2- induces the thiolate-ligand elimination. Protonation of [Fe(NO)(SEt)3]- yielding [Fe(NO)(SPh)3]- by adding 3 equiv of thiophenol and transformation of [Fe(NO)(SPh)3]- to [Fe(NO)(SEt)3]- in the presence of 3 equiv of [SEt]-, respectively, demonstrated that complexes [Fe(NO)(SPh)3]- and [Fe(NO)(SEt)3]- are chemically interconvertible. Mononitrosyl tris(thiolate) iron complex [Fe(NO)(SPh)3]- and dinitrosyl iron complex [(EtS)2Fe(NO)2]- were isolated and characterized by X-ray diffraction. The mean NO bond distances of 1.181(7) A (or 1.191(7) A) in complex [(EtS)2Fe(NO)2]- are nearly at the upper end of the 1.178(3)-1.160(6) A for the anionic {Fe(NO)2}9 DNICs, while the mean FeN(O) distances of 1.674(6) A (or 1.679(6) A) exactly fall in the range of 1.695(3)-1.661(4) A for the anionic {Fe(NO)2}9 DNICs.

Signature lipids and stable carbon isotope analyses of Octopus Spring hyperthermophilic communities compared with those of Aquificales representatives

NASA Technical Reports Server (NTRS)

Jahnke, L. L.; Eder, W.; Huber, R.; Hope, J. M.; Hinrichs, K. U.; Hayes, J. M.; Des Marais, D. J.; Cady, S. L.; Summons, R. E.

2001-01-01

The molecular and isotopic compositions of lipid biomarkers of cultured Aquificales genera have been used to study the community and trophic structure of the hyperthermophilic pink streamers and vent biofilm from Octopus Spring. Thermocrinis ruber, Thermocrinis sp. strain HI 11/12, Hydrogenobacter thermophilus TK-6, Aquifex pyrophilus, and Aquifex aeolicus all contained glycerol-ether phospholipids as well as acyl glycerides. The n-C(20:1) and cy-C(21) fatty acids dominated all of the Aquificales, while the alkyl glycerol ethers were mainly C(18:0). These Aquificales biomarkers were major constituents of the lipid extracts of two Octopus Spring samples, a biofilm associated with the siliceous vent walls, and the well-known pink streamer community (PSC). Both the biofilm and the PSC contained mono- and dialkyl glycerol ethers in which C(18) and C(20) alkyl groups were prevalent. Phospholipid fatty acids included both the Aquificales n-C(20:1) and cy-C(21), plus a series of iso-branched fatty acids (i-C(15:0) to i-C(21:0)), indicating an additional bacterial component. Biomass and lipids from the PSC were depleted in (13)C relative to source water CO(2) by 10.9 and 17.2 per thousand, respectively. The C(20-21) fatty acids of the PSC were less depleted than the iso-branched fatty acids, 18.4 and 22.6 per thousand, respectively. The biomass of T. ruber grown on CO(2) was depleted in (13)C by only 3.3 per thousand relative to C source. In contrast, biomass was depleted by 19.7 per thousand when formate was the C source. Independent of carbon source, T. ruber lipids were heavier than biomass (+1.3 per thousand). The depletion in the C(20-21) fatty acids from the PSC indicates that Thermocrinis biomass must be similarly depleted and too light to be explained by growth on CO(2). Accordingly, Thermocrinis in the PSC is likely to have utilized formate, presumably generated in the spring source region.

An interlaboratory study of TEX86 and BIT analysis of sediments, extracts, and standard mixtures

NASA Astrophysics Data System (ADS)

Schouten, Stefan; Hopmans, Ellen C.; Rosell-Melé, Antoni; Pearson, Ann; Adam, Pierre; Bauersachs, Thorsten; Bard, Edouard; Bernasconi, Stefano M.; Bianchi, Thomas S.; Brocks, Jochen J.; Carlson, Laura Truxal; Castañeda, Isla S.; Derenne, Sylvie; Selver, Ayça. Doǧrul; Dutta, Koushik; Eglinton, Timothy; Fosse, Celine; Galy, Valier; Grice, Kliti; Hinrichs, Kai-Uwe; Huang, Yongsong; Huguet, Arnaud; Huguet, Carme; Hurley, Sarah; Ingalls, Anitra; Jia, Guodong; Keely, Brendan; Knappy, Chris; Kondo, Miyuki; Krishnan, Srinath; Lincoln, Sara; Lipp, Julius; Mangelsdorf, Kai; Martínez-García, Alfredo; Ménot, Guillemette; Mets, Anchelique; Mollenhauer, Gesine; Ohkouchi, Naohiko; Ossebaar, Jort; Pagani, Mark; Pancost, Richard D.; Pearson, Emma J.; Peterse, Francien; Reichart, Gert-Jan; Schaeffer, Philippe; Schmitt, Gaby; Schwark, Lorenz; Shah, Sunita R.; Smith, Richard W.; Smittenberg, Rienk H.; Summons, Roger E.; Takano, Yoshinori; Talbot, Helen M.; Taylor, Kyle W. R.; Tarozo, Rafael; Uchida, Masao; van Dongen, Bart E.; Van Mooy, Benjamin A. S.; Wang, Jinxiang; Warren, Courtney; Weijers, Johan W. H.; Werne, Josef P.; Woltering, Martijn; Xie, Shucheng; Yamamoto, Masanobu; Yang, Huan; Zhang, Chuanlun L.; Zhang, Yige; Zhao, Meixun; Damsté, Jaap S. Sinninghe

2013-12-01

Two commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 (TetraEther indeX of 86 carbon atoms) paleothermometer for sea surface temperature reconstructions and the BIT (Branched Isoprenoid Tetraether) index for reconstructing soil organic matter input to the ocean. An initial round-robin study of two sediment extracts, in which 15 laboratories participated, showed relatively consistent TEX86 values (reproducibility ±3-4°C when translated to temperature) but a large spread in BIT measurements (reproducibility ±0.41 on a scale of 0-1). Here we report results of a second round-robin study with 35 laboratories in which three sediments, one sediment extract, and two mixtures of pure, isolated GDGTs were analyzed. The results for TEX86 and BIT index showed improvement compared to the previous round-robin study. The reproducibility, indicating interlaboratory variation, of TEX86 values ranged from 1.3 to 3.0°C when translated to temperature. These results are similar to those of other temperature proxies used in paleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences in sediment extraction techniques. BIT values of the sediments and extracts were at the extremes of the index with values close to 0 or 1, and showed good reproducibility (ranging from 0.013 to 0.042). However, the measured BIT values for the two GDGT mixtures, with known molar ratios of crenarchaeol and branched GDGTs, had intermediate BIT values and showed poor reproducibility and a large overestimation of the "true" (i.e., molar-based) BIT index. The latter is likely due to, among other factors, the higher mass spectrometric response of branched GDGTs compared to crenarchaeol, which also varies among mass spectrometers. Correction for this different mass spectrometric response showed a considerable improvement in the reproducibility of BIT index measurements among laboratories, as well as a substantially improved estimation of molar-based BIT values. This suggests that standard mixtures should be used in order to obtain consistent, and molar-based, BIT values.

Prenatal Exposure to Organophosphorous Pesticides and Fetal Growth: Pooled Results from Four Longitudinal Birth Cohort Studies.

PubMed

Harley, Kim G; Engel, Stephanie M; Vedar, Michelle G; Eskenazi, Brenda; Whyatt, Robin M; Lanphear, Bruce P; Bradman, Asa; Rauh, Virginia A; Yolton, Kimberly; Hornung, Richard W; Wetmur, James G; Chen, Jia; Holland, Nina T; Barr, Dana Boyd; Perera, Frederica P; Wolff, Mary S

2016-07-01

Organophosphorous (OP) pesticides are associated with reduced fetal growth in animals, but human studies are inconsistent. We pooled data from four cohorts to examine associations of prenatal OP exposure with birth weight (n = 1,169), length (n = 1,152), and head circumference (n = 1,143). Data were from the CHAMACOS, HOME, Columbia, and Mount Sinai birth cohorts. Concentrations of three diethyl phosphate (ΣDEP) and three dimethyl phosphate (ΣDMP) metabolites of OP pesticides [summed to six dialkyl phosphates (ΣDAPs)] were measured in maternal urine. Linear regression and mixed-effects models were used to examine associations with birth outcomes. We found no significant associations of ΣDEP, ΣDMP, or ΣDAPs with birth weight, length, or head circumference overall. However, among non-Hispanic black women, increasing urinary ΣDAP and ΣDMP concentrations were associated with decreased birth length (β = -0.4 cm; 95% CI: -0.9, 0.0 and β = -0.4 cm; 95% CI: -0.8, 0.0, respectively, for each 10-fold increase in metabolite concentration). Among infants with the PON1192RR genotype, ΣDAP and ΣDMP were negatively associated with length (β = -0.4 cm; 95% CI: -0.9, 0.0 and β = -0.5 cm; 95% CI: -0.9, -0.1). This study confirms previously reported associations of prenatal OP exposure among black women with decreased infant size at birth, but finds no evidence of smaller birth weight, length, or head circumference among whites or Hispanics. Contrary to our hypothesis, we found stronger inverse associations of DAPs and birth outcome in infants with the less susceptible PON1192RR genotype. The large pooled data set facilitated exploration of interactions by race/ethnicity and PON1 genotype, but was limited by differences in study populations. Harley KG, Engel SM, Vedar MG, Eskenazi B, Whyatt RM, Lanphear BP, Bradman A, Rauh VA, Yolton K, Hornung RW, Wetmur JG, Chen J, Holland NT, Barr DB, Perera FP, Wolff MS. 2016. Prenatal exposure to organophosphorous pesticides and fetal growth: pooled results from four longitudinal birth cohort studies. Environ Health Perspect 124:1084-1092; http://dx.doi.org/10.1289/ehp.1409362.

Biomarker insights into microbial activity in the serpentinite-hosted ecosystem of the Semail Ophiolite, Oman

NASA Astrophysics Data System (ADS)

Newman, S. A.; Lincoln, S. A.; Shock, E.; Kelemen, P. B.; Summons, R. E.

2012-12-01

Serpentinization is a process in which ultramafic and mafic rocks undergo exothermic reactions when exposed to water. The products of these reactions, including methane, hydrogen, and hydrogen sulfide, can sustain microbially dominated ecosystems [1,2,3]. Here, we report the lipid biomarker record of microbial activity in carbonate veins of the Semail Ophiolite, a site currently undergoing serpentinization [4]. The ophiolite, located in the Oman Mountains in the Sultanate of Oman, was obducted onto the Arabian continental margin during the closure of the southern Tethys Ocean (~70 Ma) [5]. We detected bacterial and archaeal glycerol dialkyl glycerol tetraether (GDGT) lipids in Semail carbonates. In addition to archaeal isoprenoidal GDGTs with 0-3 cyclopentane moieties, we detected crenarchaeol, an iGDGT containing 4 cyclopentane and 1 cyclohexane moiety. Crenarchaeol biosynthesis is currently understood to be limited to thaumarchaea, representatives of which have been found to fix inorganic carbon in culture. We also analyzed isoprenoidal diether lipids, potentially derived from methanogenic euryarchaea, as well as non-isoprenoidal diether and monoether lipids that may be indicative of methane cycling bacteria. The stable carbon isotopic composition of these compounds is potentially useful in determining both their origin and the origin of methane detected in ophiolite fluids. We compare our results to those found at the Lost City Hydrothermal Field, a similar microbially-dominated ecosystem fueled by serpentinization processes [3]. Modern serpentinite-hosted ecosystems such as this can serve as analogs for environments in which ultramafic and mafic rocks were prevalent (e.g. early Earth and other early terrestrial planets). Additionally, an analysis of modern serpentinite systems can help assess conditions promoting active carbon sequestration in ultramafic rocks [6]. References [1] Russell et al. (2010). Geobiology 8: 355-371. [2] Kelley et al. (2005). Science 307: 1428-1434. [3] Bradley et al. (2009). Geochimica Et Cosmochimica Acta 73 (1): 102-118. [4] Barnes et al. (1978). Geochimica Et Cosmochimica Acta 42: 144-145. [5] Nasir et al. (2007). Chemie Der Erde-Geochemistry 67(3): 213-228. [6] Kelemen et al. (2008). Proceedings of the National Academy of Sciences of the United States of America 45: 17295-17300.

Sources and distributions of branched and isoprenoid tetraether lipids on the Amazon shelf and fan: Implications for the use of GDGT-based proxies in marine sediments

NASA Astrophysics Data System (ADS)

Zell, Claudia; Kim, Jung-Hyun; Hollander, David; Lorenzoni, Laura; Baker, Paul; Silva, Cleverson Guizan; Nittrouer, Charles; Sinninghe Damsté, Jaap S.

2014-08-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) in river fan sediments have been used successfully to reconstruct mean annual air temperature (MAAT) and soil pH of the Congo River drainage basin. However, in a previous study of Amazon deep-sea fan sediments the reconstructed MAATs were ca. 10 °C colder than the actual MAAT of the Amazon basin. In this study we investigated this apparent offset, by comparing the concentrations and distributions of brGDGTs in Amazon River suspended particulate matter (SPM) and sediments to those in marine SPM and surface sediments. The riverine brGDGT input was evident from the elevated brGDGT concentrations in marine SPM and surface sediments close to the river mouth. The distributions of brGDGTs in marine SPM and sediments varied widely, but generally showed a higher relative abundance of methylated and cyclic brGDGTs than those in the river. Since this difference in brGDGT distribution was also found in intact polar lipid (IPL)-derived brGDGTs, which were more recently produced, the change in the marine brGDGT distribution was most likely due to marine in situ production. Consequently, the MAATs calculated based on the methylation of branched tetraethers (MBT) and the cyclisation of branched tetraethers (CBT) were lower and the CBT-derived pH values were higher than those of the Amazon basin. However, SPM and sediments from stations close to the river mouth still showed MBT/CBT values that were similar to those of the river. Therefore, we recommend caution when applying the MBT/CBT proxy, it should only be used in sediment cores that were under high river influence. The influence of riverine derived isoprenoid GDGT (isoGDGT) on the isoGDGT-based TEX86 temperature proxy was also examined in marine SPM and sediments. An input of riverine isoGDGTs from the Amazon River was apparent, but its influence on the marine TEX86 was minor since the TEX86 of SPM in the Amazon River was similar to that in the marine SPM and sediments.

Contrasting Distributions of Bacterial Branched Tetraethers along a Soil-River-Lake Transect in the Arid Region of Northwestern China

NASA Astrophysics Data System (ADS)

Lu, J.

2016-12-01

Understanding the transport of branched glycerol dialkyl glycerol tetraethers (brGDGTs) along the soil-river-lake transect is of vital importance, which helps discriminate the autochthonous from allochthonous contribution of brGDGTs in lake and river environment and favors the application of brGDGT-based proxies in paleo-reconstruction. We collected the sediment samples from the Qinghai Lake, the largest saline lake in China, as well as the river sediments and catchment soils, to examine the difference in the distribution of 5- vs. 6-methyl brGDGTs along the soil-river-lake transect. The brGDGT distributions were found to show a large variation along the transect, which can be reflected by the MBT'-derived indices and IR (isomer ratio) indices. There is a considerable difference in brGDGT distributions between soil and the river sediment. The inflowing rivers likely receive terrestrial brGDGT input to a variable degree. BrGDGTs in the Buha river are primarily of autochthonous origin whereas other ephemeral streams, like the Heima river, exhibit a similar brGDGT distribution to the surrounding soils, reflecting that these compounds are likely derived from soils. A higher quantity of 6-methyl brGDGTs and brGDGT-Ia was observed in the lake than in the river sediments, pointing to a preferential degradation of 5-methyl brGDGTs and/or an increase of in situ production of 6-methyl brGDGTs in the lake. Besides the difference in brGDGT distributions caused by the transportation and in situ production along the transect, we also identified the difference caused by several driving factors in different environments. In arid and alkaline soils, both CBT' and IR indices have strong correlations with soil pH even within the narrow pH range. However, we find a clear relationship of CBT with water salinity in Buha river. The difference in soil and river leads to a complicated interpretation for the CBT (CBT') index. In the lake, the MBT' (specially represented by MBT'5ME and MBT'6ME), defined mainly by the fractional abundance of GDGT-Ia, increases with lake water depth, suggesting the maximum water depth is likely to impact the use of MBT'/CBT proxy in the Qinghai Lake.

Cumulative organophosphate pesticide exposure and risk assessment among pregnant women living in an agricultural community: a case study from the CHAMACOS cohort.

PubMed Central

Castorina, Rosemary; Bradman, Asa; McKone, Thomas E; Barr, Dana B; Harnly, Martha E; Eskenazi, Brenda

2003-01-01

Approximately 230,000 kg of organophosphate (OP) pesticides are applied annually in California's Salinas Valley. These activities have raised concerns about exposures to area residents. We collected three spot urine samples from pregnant women (between 1999 and 2001) enrolled in CHAMACOS (Center for the Health Assessment of Mothers and Children of Salinas), a longitudinal birth cohort study, and analyzed them for six dialkyl phosphate metabolites. We used urine from 446 pregnant women to estimate OP pesticide doses with two deterministic steady-state modeling methods: method 1, which assumed the metabolites were attributable entirely to a single diethyl or dimethyl OP pesticide; and method 2, which adapted U.S. Environmental Protection Agency (U.S. EPA) draft guidelines for cumulative risk assessment to estimate dose from a mixture of OP pesticides that share a common mechanism of toxicity. We used pesticide use reporting data for the Salinas Valley to approximate the mixture to which the women were exposed. Based on average OP pesticide dose estimates that assumed exposure to a single OP pesticide (method 1), between 0% and 36.1% of study participants' doses failed to attain a margin of exposure (MOE) of 100 relative to the U.S. EPA oral benchmark dose(10) (BMD(10)), depending on the assumption made about the parent compound. These BMD(10) values are doses expected to produce a 10% reduction in brain cholinesterase activity compared with background response in rats. Given the participants' average cumulative OP pesticide dose estimates (method 2) and regardless of the index chemical selected, we found that 14.8% of the doses failed to attain an MOE of 100 relative to the BMD(10) of the selected index. An uncertainty analysis of the pesticide mixture parameter, which is extrapolated from pesticide application data for the study area and not directly quantified for each individual, suggests that this point estimate could range from 1 to 34%. In future analyses, we will use pesticide-specific urinary metabolites, when available, to evaluate cumulative OP pesticide exposures. PMID:14527844

Origin and applicability of tetraether membrane lipids as temperature proxies in French peri-urban lakes

NASA Astrophysics Data System (ADS)

Mainié, François; Huguet, Arnaud; Breban, Alice; Lacroix, Gérard; Anquetil, Christelle; Derenne, Sylvie

2015-04-01

The Ile-de-France region is the most populated area in France, with ca. 12 million inhabitants, i.e. about 20 % of French population. The peri-urban aquatic ecosystems of this region are impacted by a large variety of environmental stressors, and especially high anthropogenic pressures (agricultural, industrial and urban pollutants), leading to the increased eutrophication of these water systems. The Ile-de-France lakes are therefore highly vulnerable ecosystems. Over the last years, several environmental markers have been developed to better understand the functioning of aquatic ecosystems, including the so-called GDGTs (glycerol dialkyl glycerol tetraethers). GDGTs are membrane lipids produced by archaea and some unknown bacteria, which are increasingly used to reconstruct mean annual air and surface water temperature as well as pH. These compounds are ubiquitous in terrestrial and aquatic environments, but their origin and applicability as temperature and pH proxies in lakes, especially highly polluted ones, need further investigation. In this study, GDGTs were analysed in 33 lakes from the Ile-de-France region, representing the diversity of the regional landscape and characterised by different levels of eutrophication. The abundance and distribution of GDGTs in lacustrine sediments and surrounding soils were compared. Bacterial GDGTs were systematically much more abundant in sediments than in soils and displayed different distributions in the two types of environments, showing that they are mainly produced in situ in lakes, in the water column and/or sediment. Similarly, the concentration in archaeal GDGTs was much higher in sediments than in soils and the distribution of these compounds differed between soils and sediments, implying that the predominant archaeal communities are not the same in the two environments. When the lakes are distinguished by their eutrophication level, the latter was shown for the first time to have an impact on the microorganisms producing GDGTs. Indeed, bacterial and archaeal GDGTs were observed to be significantly less abundant in sediments from oligotrophic lakes than in those from hypertrophic lakes. Nevertheless, the applicability of bacterial GDGTs as temperature proxies was not affected by the eutrophic status of the lakes, since temperature estimates derived from these compounds were consistent with both mean annual air temperature (11 °C) and mean summer air temperature (19 °C) recorded in the Ile-de-France region.

Temperature variations in the southern Great Lakes during the last deglaciation: Comparison between pollen and GDGT proxies

USGS Publications Warehouse

Watson, Benjamin I.; Williams, John W.; Russell, James M.; Jackson, Stephen T.; Shane, Linda; Lowell, Thomas V.

2018-01-01

Our understanding of deglacial climate history in the southern Great Lakes region of the United States is primarily based upon fossil pollen data, with few independent and multi-proxy climate reconstructions. Here we introduce a new, well-dated fossil pollen record from Stotzel-Leis, OH, and a new deglacial temperature record based on branched glycerol dialkyl glycerol tetraethers (brGDGTs) at Silver Lake, OH. We compare these new data to previously published records and to a regional stack of pollen-based temperature reconstructions from Stotzel-Leis, Silver Lake, and three other well-dated sites. The new and previously published pollen records at Stotzel-Leis are similar, but our new age model brings vegetation events into closer alignment with known climatic events such as the Younger Dryas (YD). brGDGT-inferred temperatures correlate strongly with pollen-based regional temperature reconstructions, with the strongest correlation obtained for a global soil-based brGDGT calibration (r2 = 0.88), lending confidence to the deglacial reconstructions and the use of brGDGT and regional pollen stacks as paleotemperature proxies in eastern North America. However, individual pollen records show large differences in timing, rates, and amplitudes of inferred temperature change, indicating caution with paleoclimatic inferences based on single-site pollen records. From 16.0 to 10.0ka, both proxies indicate that regional temperatures rose by ∼10 °C, roughly double the ∼5 °C estimates for the Northern Hemisphere reported in prior syntheses. Change-point analysis of the pollen stack shows accelerated warming at 14.0 ± 1.2ka, cooling at 12.6 ± 0.4ka, and warming from 11.6 ± 0.5ka into the Holocene. The timing of Bølling-Allerød (B-A) warming and YD onset in our records lag by ∼300–500 years those reported in syntheses of temperature records from the northern mid-latitudes. This discrepancy is too large to be attributed to uncertainties in radiocarbon dating, and correlation between pollen and brGDGT temperature reconstructions rules out vegetation lags as a cause. However, the YD termination appears synchronous among the brGDGT record, regional pollen stack, and Northern Hemisphere stack. The cause of the larger and lagged temperature changes in the southern Great Lakes relative to Northern Hemisphere averages remains unclear, but may be due to the effects of continentality and ice sheet extent on regional climate evolution.

Cultivation of a highly enriched ammonia-oxidizing archaeon of thaumarchaeotal group I.1b from an agricultural soil.

PubMed

Kim, Jong-Geol; Jung, Man-Young; Park, Soo-Je; Rijpstra, W Irene C; Sinninghe Damsté, Jaap S; Madsen, Eugene L; Min, Deullae; Kim, Jin-Seog; Kim, Geun-Joong; Rhee, Sung-Keun

2012-06-01

Nitrification of excess ammonia in soil causes eutrophication of water resources and emission of atmospheric N(2) O gas. The first step of nitrification, ammonia oxidation, is mediated by Archaea as well as Bacteria. The physiological reactions mediated by ammonia-oxidizing archaea (AOA) and their contribution to soil nitrification are still unclear. Results of non-culture-based studies have shown the thaumarchaeotal group I.1b lineage of AOA to be dominant over both AOA of group I.1a and ammonia-oxidizing bacteria in various soils. We obtained from an agricultural soil a highly enriched ammonia-oxidizing culture dominated by a single archaeal population [c. 90% of total cells, as determined microscopically (by fluorescence in situ hybridization) and by quantitative PCR of its 16S rRNA gene]. The archaeon (termed 'strain JG1') fell within thaumarchaeotal group I.1b and was related to the moderately thermophilic archaeon, Candidatus Nitrososphaera gargensis, and the mesophilic archaeon, Ca. Nitrososphaera viennensis with 97.0% and 99.1% 16S rRNA gene sequence similarity respectively. Strain JG1 was neutrophilic (growth range pH 6.0-8.0) and mesophilic (growth range temperature 25-40°C). The optimum temperature of strain JG1 (35-40°C) is > 10°C higher than that of ammonia-oxidizing bacteria (AOB). Membrane analysis showed that strain JG1 contained a glycerol dialkyl glycerol tetraether, GDGT-4, and its regioisomer as major core lipids; this crenarchaeol regioisomer was previously detected in similar abundance in the thermophile, Ca. N. gargensis and has been frequently observed in tropical soils. Substrate uptake assays showed that the affinity of strain JG1 for ammonia and oxygen was much higher than those of AOB. These traits may give a competitive advantage to AOA related to strain JG1 in oligotrophic environments. (13) C-bicarbonate incorporation into archaeal lipids of strain JG1 established its ability to grow autotrophically. Strain JG1 produced a significant amount of N(2) O gas - implicating AOA as a possible source of N(2) O emission from soils. Sequences of archaeal amoA and 16S rRNA genes closely related to those of strain JG1 have been retrieved from various terrestrial environments in which lineage of strain JG1 is likely engaged in autotrophic nitrification. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

FLUIDS, LUBRICANTS, FUELS AND RELATED MATERIALS. Quarterly Report for July, August, and September 1959. Sept. 30, 1959. Appendix I: SURVEY OF HYDRAULIC FLUIDS, LUBRICANTS, AND WORKING FLUIDS FOR AERONAUTIC AND ASTRONAUTIC APPLICATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fenske, M.R.; Klaus, E.E.

1959-11-01

Results obtained in a Vickers pump test program in which a prototype mineral oil designed for operation at -65 to +700 deg F are discussed. The fluid (MLO-7460) used in this program exhibits the same general high temperature lubricity and stability behavior as the low temperature fluid (MLO-7485). However, this fluid contains wax and does not have the same low temperature properties as those of MLO-7485. Preliminary evaluation of several fluids which were stored in an unheated building for 2 to 17 years was carried out. Included in the evaluation were esters, mineral oils, and hydrocarbons, as well as formulationsmore » using these materials as base stocks. Changes in properties were noted and evidence is presented to show that additives may adversely affect storage stability in some cases. Data from a series of oxidation tests involving esters at 400 deg F are presented along with a discussion of the effectiveness of additives. Assimilation data show a predictable oxygen absorption rate during the stable life period, which is affected by the use of additive combinations. Magnesium corrosion was encountered in the 400 deg F tests and data on oxidation behavior of this material are included. Effects of a dispersant acryloid and of a dialkyl acid phosphite lubricity additive on fluid dirtiness are discussed. A series of deposition tests was conducted in a controlled atmosphere panel coker. A comparison of paraffinic and naphthenic mineral oil formulations tested in the coker is presented. Decreasing coking tendencies with increasing boiling point is illustrated for a series of oxygen. Assimilation is lower for higher volatility fluids which also show excessive coking. The increased coke deposit caused by the presence of a dithiocarbamate in the test fluid is shown to be materially reduced by the addition of a dispersant acryloid to the formulation. Deposition type tests were conducted in a single-pass high temperature tube rig. The effect of such variables as storage time of flat fluid, acid phosphate additives, fluid volatility, test time, and type of metal deposition surface was determined. (For preceding period see PRL 5.27.) (J.R.D.)« less

A Multi-Biomarker Biogeochemical Investigation of a Permafrost Core from Interior Alaska Dating to 40,000 Years Before Present: Insight Into Millenial-Scale Carbon Accumulation and Degradation Status

NASA Astrophysics Data System (ADS)

Hutchings, J.; Bianchi, T. S.; Schuur, E.; Kaufman, D. S.; Kholodov, A. L.; Vaughn, D.

2017-12-01

High latitude regions that were not directly glaciated have accumulated permafrost organic C (OC) throughout and prior to the last glacial period. Climate warming is expected to thaw these relict soils through expansion of the seasonally frozen active layer and re-expose them to active C cycling. Past climate perturbations also expanded the active layer and their effects were subsequently recorded in the bulk and molecular character of the now-buried permafrost soils. Here, we analyze a 5.4 m long permafrost core taken from an interior Alaska tundra site to assess its deep OC stock and molecular composition. OC stocks were quantified using elemental analysis and accumulation rates were estimated using 14C dating of 11 plant macrofossil samples. Organic matter source was indicated using lignin (overall plant contribution), amino acids (microbial contributions), and n-alkanes (vascular to non-vascular plant contributions), degradation status was indicated using lignin acid to aldehyde ratios (Ad:Al) and amino acid composition, and temperature was estimated via the branched glycerol dialkyl glycerol (GDGT) thermometer. Soil ages extended to 40,000 years, although a gap in 14C ages spanning from about 33 to 13 ka coincides with a 1.5 m thick, low OC (< 1 %OC) section of the core. We estimated a Holocene accumulation rate of 2.9 g OC m-2 yr-1, while mid-Wisconsin (40-30 ka) soils had a rate of 20.4 g OC m-2 yr-1, driven in part by the seven-fold higher sedimentation rate of the latter (0.4 mm yr-1). Lignin vannilyl Ad:Al indicated that mid-Wisconsin OC (mean Ad:Al 0.37) is well preserved compared to the Holocene section (mean Ad:Al 0.60), consistent with the older soils experiencing shorter residence times within the active layer due to faster sedimentation as well as potentially cooler temperatures. GDGT-derived temperatures were complicated by anomalously warm values in mid-Wisconsin soils (average mean annual temperature of 5.3°C compared to -1°C currently) and highly variable temperatures within the contemporary active layer. We suspect the unusually warm mid-Wisconsin temperatures are derived from an uncalibrated microbial community. These results are bolstered using n-alkane and amino acid biomarkers.

Temperature variations in the southern Great Lakes during the last deglaciation: Comparison between pollen and GDGT proxies

NASA Astrophysics Data System (ADS)

Watson, Benjamin I.; Williams, John W.; Russell, James M.; Jackson, Stephen T.; Shane, Linda; Lowell, Thomas V.

2018-02-01

Our understanding of deglacial climate history in the southern Great Lakes region of the United States is primarily based upon fossil pollen data, with few independent and multi-proxy climate reconstructions. Here we introduce a new, well-dated fossil pollen record from Stotzel-Leis, OH, and a new deglacial temperature record based on branched glycerol dialkyl glycerol tetraethers (brGDGTs) at Silver Lake, OH. We compare these new data to previously published records and to a regional stack of pollen-based temperature reconstructions from Stotzel-Leis, Silver Lake, and three other well-dated sites. The new and previously published pollen records at Stotzel-Leis are similar, but our new age model brings vegetation events into closer alignment with known climatic events such as the Younger Dryas (YD). brGDGT-inferred temperatures correlate strongly with pollen-based regional temperature reconstructions, with the strongest correlation obtained for a global soil-based brGDGT calibration (r2 = 0.88), lending confidence to the deglacial reconstructions and the use of brGDGT and regional pollen stacks as paleotemperature proxies in eastern North America. However, individual pollen records show large differences in timing, rates, and amplitudes of inferred temperature change, indicating caution with paleoclimatic inferences based on single-site pollen records. From 16.0 to 10.0ka, both proxies indicate that regional temperatures rose by ∼10 °C, roughly double the ∼5 °C estimates for the Northern Hemisphere reported in prior syntheses. Change-point analysis of the pollen stack shows accelerated warming at 14.0 ± 1.2ka, cooling at 12.6 ± 0.4ka, and warming from 11.6 ± 0.5ka into the Holocene. The timing of Bølling-Allerød (B-A) warming and YD onset in our records lag by ∼300-500 years those reported in syntheses of temperature records from the northern mid-latitudes. This discrepancy is too large to be attributed to uncertainties in radiocarbon dating, and correlation between pollen and brGDGT temperature reconstructions rules out vegetation lags as a cause. However, the YD termination appears synchronous among the brGDGT record, regional pollen stack, and Northern Hemisphere stack. The cause of the larger and lagged temperature changes in the southern Great Lakes relative to Northern Hemisphere averages remains unclear, but may be due to the effects of continentality and ice sheet extent on regional climate evolution.

Discussion on the Regional Paleotemperature Evolution since the Late Pleistocene in the Loess Plateau with GDGT as an Index

NASA Astrophysics Data System (ADS)

Yingchun, S.

2017-12-01

It is an effective way to understand the modern climate and predict the future climate trend by using the geological substitute indicators to reconstruct the past climate. In recent years, scientists have begun to apply Glycerol dialkyl glycerol tetraethers (GDGTs) to reconstruct paleoclimate and many proxies about ancient air temperature based on GDGTs have been proposed, even the empirical formulas used for China have also been established. In this paper, five loess-paleosol sequences spanning the Late Pleistocene from the Loess Plateau have been used to examine the effectiveness of the formulas as well as to discuss the regional evolution of the ancient temperature of the plateau. The results are as follows: (1) The relative content of iGDGT is higher than that of bGDGT in all Loess sections, and that of each compound follows relatively fixed regularity. Seen from the geographical distribution, the relative content of GDGT in southernmost sections is the highest, which in the northernmost is the smallest. (2) In the last interglacial period, from the northern part to the southern part of the Loess Plateau, the mean annual air temperature (MAAT) of northern Jingbian was 14°, central Luochuan was up to 15°, and southern Weinan was nearly 18°. And at the end of the last glacial period the temperature, where LC and WN located, dropped to 13.5°. Along the east-west direction of the Plateau, in the last interglacial period, the MAAT of western Qin'an secion was 13°, and that of central Baoji and eastern Weinan was about 18°. To the end of the last glacial period, the MAAT decreased to the lowest, Weinan 13.5°, Baoji 14.5°, while Qin'an 10.8°. (3)In contrast to the magnetic susceptibility index, the curves of GDGT MAAT have great similarity with the magnetic susceptibility curve, but it is obvious that there are phase differences between them. That may be indicating that the temperature rise was before the onset of the East-Asian summer monsoon in the Plateau. Although the formula has been adjusted for China, the temperatures from GDGTs are relatively higher, which is consistent with the views of some researchers. Therefore, some researchers assumed that the GDGTs temperature should represent the average summer temperature. Hence, the interpretation still requires more research sections and scientific indicators for verification.

Provenance of tetraether membrane lipids in a large temperate lake (Loch Lomond, UK): implications for GDGT-based palaeothermometry

NASA Astrophysics Data System (ADS)

Buckles, L. K.; Weijers, J. W. H.; Tran, X.-M.; Waldron, S.; Sinninghe Damsté, J. S.

2014-03-01

The application of glycerol dialkyl glycerol tetraether (GDGT)-based palaeoenvironmental proxies, such as the BIT index, TEX86 and the MBT/CBT palaeothermometer, has lately been expanded to lacustrine sediments. Given recent research identifying the production of branched, bacterial GDGTs (brGDGTs) within lakes, it is necessary to ascertain the effect of this lacustrine production on GDGT-based proxies. This study profiles a temperate, monomictic lake (Loch Lomond, UK), analysing labile intact polar GDGT lipids (IPLs) and resilient core GDGT lipids (CLs) in catchment soils, small tributary rivers, lake water and lake sediments. Loch Lomond consists of two basins bisected by the Highland Boundary Fault, resulting in a mesotrophic to oligotrophic gradient from south to north. The north basin is fjord-like, while the south basin is shallow with a lowland catchment. Besides abundant influxes of allochthonous soil and peat-derived (CL) brGDGTs, brGDGTs are produced in a variety of settings in Loch Lomond. Rather than integrating a scattered soil signal, there is some evidence that small rivers may contribute to the brGDGT pool through addition of brGDGTs produced in situ in these streams. 300 days of settling particles and water column profiles of suspended particulate matter (SPM; March and September 2011) reveal brGDGT production throughout the water column, with (IPL and CL) brGDGT distributions varying by basin. In lake sediments, in situ brGDGT production affects the distributions of sedimentary brGDGTs despite high soil and peat-derived organic matter influxes from the catchment. MBT/CBT-derived mean annual air temperature (MAAT) estimates from soil, river and lake sediments vary widely. A strong bias towards higher MAATs in the south and lower MAATs in the north basin further complicates the application of the proxy. These results emphasise that caution must be exercised when applying the MBT/CBT palaeothermometer to individual lakes in which the use of the proxy has not been validated and therefore the factors affecting its application are not well understood. Despite elevated BIT indices, (partly) due to in situ brGDGT production, reliable TEX86 lake surface temperature (LST) estimates were obtained from SPM with BIT indices up to 0.9 but containing abundant crenarchaeol. Lower north basin sediments yielded accurate LST estimates but require further evaluation to properly constrain the application of the TEX86 proxy.

Patent literature on mosquito repellent inventions which contain plant essential oils--a review.

PubMed

Pohlit, Adrian Martin; Lopes, Norberto Peporine; Gama, Renata Antonaci; Tadei, Wanderli Pedro; Neto, Valter Ferreira de Andrade

2011-04-01

Bites Bites of mosquitoes belonging to the genera Anopheles Meigen, Aedes Meigen, Culex L. and Haemagogus L. are a general nuisance and are responsible for the transmission of important tropical diseases such as malaria, hemorrhagic dengue and yellow fevers and filariasis (elephantiasis). Plants are traditional sources of mosquito repelling essential oils (EOs), glyceridic oils and repellent and synergistic chemicals. A Chemical Abstracts search on mosquito repellent inventions containing plant-derived EOs revealed 144 active patents mostly from Asia. Chinese, Japanese and Korean language patents and those of India (in English) accounted for roughly 3/4 of all patents. Since 1998 patents on EO-containing mosquito repellent inventions have almost doubled about every 4 years. In general, these patents describe repellent compositions for use in topical agents, cosmetic products, incense, fumigants, indoor and outdoor sprays, fibers, textiles among other applications. 67 EOs and 9 glyceridic oils were individually cited in at least 2 patents. Over 1/2 of all patents named just one EO. Citronella [Cymbopogon nardus (L.) Rendle, C.winterianus Jowitt ex Bor] and eucalyptus (Eucalyptus LʼHér. spp.) EOs were each cited in approximately 1/3 of all patents. Camphor [Cinnamomum camphora (L.) J. Presl], cinnamon (Cinnamomum zeylanicum Blume), clove [Syzygium aromaticum (L.) Merr. & L.M. Perry], geranium (Pelargonium graveolens LʼHér.), lavender (Lavandula angustifolia Mill.), lemon [Citrus × limon (L.) Osbeck], lemongrass [Cymbopogon citratus (DC.) Stapf] and peppermint (Mentha × piperita L.) EOs were each cited in > 10% of patents. Repellent chemicals present in EO compositions or added as pure “natural” ingredients such as geraniol, limonene, p-menthane-3,8-diol, nepetalactone and vanillin were described in approximately 40% of all patents. About 25% of EO-containing inventions included or were made to be used with synthetic insect control agents having mosquito repellent properties such as pyrethroids, N,N-diethyl-m-toluamide (DEET), (±)-p-menthane-3,8-diol (PMD) and dialkyl phthalates. Synergistic effects involving one or more EOs and synthetic and/or natural components were claimed in about 10% of all patents. Scientific literature sources provide evidence for the mosquito repellency of many of the EOs and individual chemical components found in EOs used in patented repellent inventions. © Georg Thieme Verlag KG Stuttgart · New York.

Mid-Pliocene to Early Pleistocene land and sea surface temperature history of NW Australia based on organic geochemical proxies

NASA Astrophysics Data System (ADS)

Smith, R. A.; Castañeda, I. S.; Henderiks, J.; Christensen, B. A.; De Vleeschouwer, D.; Renema, W.; Groeneveld, J.; Bogus, K.; Gallagher, S. J.; Fulthorpe, C.; Expedition 356 Scientists, I.

2017-12-01

IODP Expedition 356 Site U1463 is located off the coast of NW Australia, and is sensitive to Indonesian Throughflow (ITF) variability. The ITF is a critical ocean gateway that affects global thermohaline circulation, and regulates the movement of water from the Pacific Ocean into the Indian Ocean. However, despite its importance to the global climate system, few SST reconstructions exist for this region that span the Plio-Pleistocene. Here we investigate both the land and sea-surface temperature (SST) history of NW Australia to constrain ITF variability across the Plio-Pleistocene interval. We apply multiple organic geochemical proxies to this site from 3.4-2.6 Ma, which includes the mid-Pliocene warm period, characterized by slightly higher (2-3°C) global temperatures and similar CO2 concentrations to modern values (e.g. Badger et al. 2013; Bartoli et al., 2011; Dowsett et al., 2009; Hönisch et al., 2009; Pagani et al. 2009; Raymo et al., 1996). SST was reconstructed using TEX86, based on isoprenoid glycerol dialkyl glycerol tetraethers (iGDGTs), and the long-chain diol index (LDI), based on the ratio of diols produced by marine diatoms (Rampen et al., 2012). The Uk'37 index, based on long-chain ketones, was analyzed but cannot be applied as a SST proxy at this site due to the influence of coastal alkenone producers. Additionally, a continental air temperature record was developed using the MBT'5ME proxy, based on branched GDGTs (De Jonge et al., 2014; Weijers et al., 2007). We find that TEX86, LDI and MBT'5Me exhibit similar trends and show relatively warm and stable temperatures from 3.5-2.4 Ma followed by a gradual cooling of 3-4°C from 2.4-1.5 Ma. This cooling corresponds with an arid interval previously identified on the same core by Christensen et al. (2017). Furthermore, we find that the TEX86 record agrees closely with the LR04 global benthic δ18O stack (Lisiecki and Raymo, 2005) and captures glacial/interglacial periods including Marine Isotope Stage M2. Our results help to constrain climatic changes across the mid-Pliocene warm period and aim to improve future climate models and elucidate the role of the ITF in driving global climate variability.

The C1 domain-targeted isophthalate derivative HMI-1b11 promotes neurite outgrowth and GAP-43 expression through PKCα activation in SH-SY5Y cells.

PubMed

Talman, Virpi; Amadio, Marialaura; Osera, Cecilia; Sorvari, Salla; Boije Af Gennäs, Gustav; Yli-Kauhaluoma, Jari; Rossi, Daniela; Govoni, Stefano; Collina, Simona; Ekokoski, Elina; Tuominen, Raimo K; Pascale, Alessia

2013-07-01

Protein kinase C (PKC) is a family of serine/threonine phosphotransferases ubiquitously expressed and involved in multiple cellular functions, such as proliferation, apoptosis and differentiation. The C1 domain of PKC represents an attractive drug target, especially for developing PKC activators. Dialkyl 5-(hydroxymethyl)isophthalates are a novel group of synthetic C1 domain ligands that exhibit antiproliferative effect in HeLa cervical carcinoma cells. Here we selected two isophthalates, HMI-1a3 and HMI-1b11, and characterized their effects in the human neuroblastoma cell line SH-SY5Y. Both of the active isophthalates exhibited significant antiproliferative and differentiation-inducing effects. Since HMI-1b11 did not impair cell survival even at the highest concentration tested (20μM), and supported neurite growth and differentiation of SH-SY5Y cells, we focused on studying its downstream signaling cascades and effects on gene expression. Consistently, genome-wide gene expression microarray and gene set enrichment analysis indicated that HMI-1b11 (10μM) induced changes in genes mainly related to cell differentiation. In particular, further studies revealed that HMI-1b11 exposure induced up-regulation of GAP-43, a marker for neurite sprouting and neuronal differentiation. These effects were induced by a 7-min HMI-1b11 treatment and specifically depended on PKCα activation, since pretreatment with the selective inhibitor Gö6976 abolished the up-regulation of GAP-43 protein observed at 12h. In parallel, we found that a 7-min exposure to HMI-1b11 induced PKCα accumulation to the cytoskeleton, an effect that was again prevented by pretreatment with Gö6976. Despite similar binding affinities to PKC, the isophthalates had different effects on PKC-dependent ERK1/2 signaling: HMI-1a3-induced ERK1/2 phosphorylation was transient, while HMI-1b11 induced a rapid but prolonged ERK1/2 phosphorylation. Overall our data are in accordance with previous studies showing that activation of the PKCα and ERK1/2 pathways participate in regulating neuronal differentiation. Furthermore, since PKC has been classified as one of the cognitive kinases, and activation of PKC is considered a potential therapeutic strategy for the treatment of cognitive disorders, our findings suggest that HMI-1b11 represents a promising lead compound in research aimed to prevent or counteract memory impairment. Copyright © 2013 Elsevier Ltd. All rights reserved.

Lead-Lag relationships? Asynchrounous and Abrupt Shifts in Atmospheric Circulation, Temperature, and Vegetation during the 8.2 ka Event in the Eastern Mediterranean at Tenaghi Philippon, Greece

NASA Astrophysics Data System (ADS)

Niedermeyer, E. M.; Mulch, A.; Pross, J.

2017-12-01

The "8.2 ka event" has been an abrupt and prominent climate perturbation during the Holocene, and is characterized by an episode of generally colder and dryer conditions in the Northern Hemisphere realm. However, evidence to what extent this event has had an impact on climate in the Mediterranean region is ambiguous, in particular with respect to rainfall, temperature and vegetation change on land. Here we present a new, high-resolution record (ø 15 years during the event) of paleotemperatures from the Tenaghi Philippon peat deposit, Eastern Macedonia, Greece, using the MBT'/CBT index based on brGDGTs (branched Glycerol-Dialkyl-Glycerol-Tetraethers). Our data show fairly stable temperatures before the event, which is initiated at 8.1 ka by an abrupt and continuous cooling during the first 35 years of the event. After a short, 10-year episode of minimum temperatures, the event is ended by a similarly abrupt and continuous warming within 38 years. Comparison of our record with a previous study of the stable hydrogen isotopic composition of higher-plant waxes (δDwax) on the same core1 shows that changes in temperature occurred simultaneously with shifts in atmospherics moisture sources (Mediterranean vs Atlantic). Interestingly, further comparison of our data with a previous palynological study of the same core2 reveals that changes in vegetation associated with the 8.2 ka event precede shifts in hydrology and temperature by 100 years. This suggests either pronounced changes in seasonality of temperature and rainfall after the onset of the 8.2 ka event, i.e. at the peak of the event, or that changes in local atmospheric circulation (moisture sources) and temperature where not the initial trigger of changes in vegetation. References: Pross, J., Kotthoff, U., Müller, U.C., Peyron, O., Dormoy, I., Schmiedl, G., Kalaitzidis, S. and Smith, A.M. (2009): Massive perturbation in terrestrial ecosystems of the Eastern Mediterranean region associated with the 8.2 kyr B.P. climatic event. Geology 37, 887-890. Schemmel, F., Niedermeyer, E.M., Schwab, V.F., Gleixner, G., Pross, J. and Mulch, A. (2016): Plant wax δD values record changing Eastern Mediterranean atmospheric circulation patterns during the 8.2 kyr B.P. climatic event. Quaternary Science Reviews 133, 96-107.

Friction Reduction in Powertrain Materials: Role of Tribolayers

NASA Astrophysics Data System (ADS)

Banerji, Anindya

This study aims at understanding the micromechanisms responsible for reduction in friction and wear in the engine cylinder bore/liner materials when tested under lubricated and unlubricated conditions. The tribolayers formed in-situ during sliding contact are unique to each tribosystem and a detailed study of these tribolayers will shed light on the friction reduction mechanisms in powertrain materials. Boundary lubricated tribological performance of grey cast iron (CI) tested against non-hydrogenated diamond-like carbon coating (NH-DLC) resulted in 21% lower coefficient of friction (COF) and an order of magnitude lower volumetric wear compared to CI and steel counterfaces. Dilution of the engine oil by ethanol containing E85 biofuel, consisting of 85% ethanol and 15% gasoline, was beneficial as COF and volumetric wear losses were further reduced. TEM/EELS studies of the NH-DLC counterface provided evidence for OH adsorption of the dangling carbon bonds at the coating surface leading to low friction. Advantage of E85/engine oil blend was also evident during boundary lubricated sliding of eutectic Al-12.6% Si alloy against AISI 52100 steel. The oil residue layer (ORL) formed during boundary lubricated sliding incorporated nanocrystalline regions of Al, Si, ZnS, AlPO4 and ZnO surrounded by amorphous carbon regions. Higher proportions of Zn, S, and P antiwear compounds formed in the ORL when tested using the E85/oil (1:1) blend compared to the unmixed engine oil as the hydroxyl groups in ethanol molecules facilitated ZDDP degradation. Mico-Raman spectroscopy indicated two types of tribolayers formed during unlubricated sliding of thermally sprayed low carbon steel 1010 coating deposited on linerless Al 380 cylinder bore: i) Fe2O3 layer transformed from FeO during dry sliding and ii) Fe2O3 layer with a top amorphous carbon transfer layer when run against H-DLC coated TCR with COF of 0.18. The NH- and H-DLC coatings, that provide low friction under room temperature conditions, fail at temperatures > 200 °C. It was shown that W containing DLC (W-DLC) coatings offered low and stable COF of 0.07 at 400 °C while a Ti incorporated multilayer MoS2 (Ti-MoS2) coating maintained COF between 0.11 at 25 °C to 0.13 at 350 °C. The low friction provided by these coatings was attributed to formation of high temperature lubricious oxides: tungsten trioxide (WO3) in case of W-DLC and MoO3 in case of MoS2, as revealed by Raman analyses of the tribolayers formed on counterface surfaces. Tribolayer formation during sliding friction of multuilayered graphene (MLG), a potential lubricant, depended on the material transfer and relative humidity (RH). Sliding friction tests performed on MLG in air (10- 45% RH) and under a dry N2 atmosphere showed that progressively lower friction values were observed when the RH was increased, with maximum COF of 0.52 in dry N2 and lowest COF of about 0.10 at 45% RH. Microstructural studies including cross-sectional FIB/HR-TEM determined that sliding induced defects which comprised of edge fracture, fragmented/bent graphene stacks compared to pristine graphene and disordered regions between them. In summary, this work shows that delineating the micromechanisms responsible for reduction in friction and wear is critical for development of appropriate materials and coatings for powertrain components.

Can leaf wax n-alkane δ²H and GDGTs be used conjointly to reconstruct past environmental changes along altitudinal transects in East Africa?

NASA Astrophysics Data System (ADS)

Coffinet, Sarah; Huguet, Arnaud; Pedentchouk, Nikolai; Omuombo, Christine; Williamson, David; Bergonzini, Laurent; Wagner, Thomas; Derenne, Sylvie

2016-04-01

Leaf wax n-alkanes (C27-C31) and branched glycerol dialkyl glycerol tetraethers (br GDGTs) are increasingly being used as molecular proxies to investigate past environmental conditions. Indices were previously developed to relate the br GDGT distribution to temperature and pH in soils. Furthermore, the δ²Hwax of leaf wax n-alkanes in soils was shown to track the 'altitude effect', suggesting it could be used to reconstruct paleoelevation. Combination of these two proxies could bring information on both past uplift elevation and past temperature changes, as illustrated by the pioneer paleostudy of Hren et al. (2010) in the Sierra Nevada. In the present study, δ²Hwax and br GDGTs were analysed in ca. 60 surface soils collected along Mt. Rungwe (Southwest Tanzania) and Mt. Kenya (Central Kenya). A weak link was identified between δ²Hwax and altitude (R² = 0.33) along Mt. Kenya, whereas no trend was observed along Mt. Rungwe, as also previously shown by Peterse et al. (2009) for Mt. Kilimanjaro. This shows that the strength of the relationship between soil δ²Hwax and elevation depends on which mountain is considered in East Africa and can be overprinted by numerous poorly understood environmental and/or physiological parameters. In contrast, br GDGT-derived mean annual air temperature (MAAT) and temperature lapse rate (5 °C/1000 m) were in agreement with values recorded along both Mt. Rungwe and Mt. Kenya, highlighting the robustness of this proxy for paleotemperature reconstruction in East Africa. Moreover, the combination of these br GDGT data with previous results obtained from East African surface soils (along Mts. Kilimanjaro (Tanzania), Sinninghe Damsté et al., 2008; Rwenzori (Uganda), Loomis et al., 2011; Rungwe (Tanzania), Coffinet et al., 2014), allowed the establishment of a regional soil calibration between br GDGT distribution and MAAT. This new East African calibration, based on 105 samples, leads to a substantial improvement of both the R2 (0.75) and RMSE (2.4 °C) of brGDGT-derived MAAT with respect to the global soil calibration by Peterse et al. (2012; R2 0.61 and RMSE 5° C). References: Coffinet, S. et al., 2014. Org. Geochem. 68, 82-89. Hren, M.T. et al., 2010. Geology 38, 7-10. Loomis, S.E., et al., 2011. Org. Geochem. 42, 739-751. Peterse, F. et al., 2009. Biogeosciences 6, 2799-2807. Peterse, F. et al., 2012. Geochim. Cosmochim. Acta 96, 215-229. Sinninghe Damsté, J.S. et al., 2008. Org. Geochem. 39, 1072-1076.

Isomorphous rare-earth bis[bis(2,6-diisopropylphenyl)phosphate] complexes and their self-assembly into two-dimensional frameworks by intramolecular hydrogen bonds.

PubMed

Minyaev, Mikhail E; Nifant'ev, Ilya E; Tavtorkin, Alexander N; Korchagina, Sof'ya A; Zeynalova, Shadana Sh; Ananyev, Ivan V; Churakov, Andrei V

2017-10-01

The crystal structures of rare-earth diaryl- or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]chloridotetrakis(methanol-κO)neodymium methanol disolvate, [Nd(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (1), and of the lutetium, [Lu(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (2), and yttrium, [Y(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (3), analogues have been obtained by reactions between lithium bis(2,6-diisopropylphenyl)phosphate and LnCl 3 (H 2 O) 6 (in a 2:1 ratio) in methanol. Compounds (1)-(3) crystallize in the C2/c space group. Their crystal structures are isomorphous. The molecule possesses C 2 symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6-diisopropylphenyl)phosphate ligands all display a κ 1 O-monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O 2 P(O-2,6- i Pr 2 C 6 H 3 ) 2 } 2 Cl(CH 3 OH) 4 ] molecular unit exhibits two intramolecular O-H...O hydrogen bonds, forming six-membered rings, and two intramolecular O-H...Cl interactions, forming four-membered rings. Intermolecular O-H...O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two-dimensional hydrogen-bond network. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]tetrakis(methanol-κO)(nitrato-κ 2 O,O')neodymium methanol disolvate, [Nd(C 24 H 34 O 4 P)(NO 3 )(CH 4 O) 4 ]·2CH 3 OH, (4), have been obtained in an analogous manner from NdCl 3 (H 2 O) 6 . Compound (4) also crystalizes in the C2/c space group. Its crystal structure is similar to those of (1)-(3). The κ 2 O,O'-bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CN Nd = 8). Unlike (1)-(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the phosphate ligand and the NO 3 - ligand. The structure of (4) displays intra- and intermolecular O-H...O hydrogen bonds similar to those in (1)-(3). Compounds (1)-(4) represent the first reported mononuclear bis[bis(diaryl/dialkyl)phosphate] rare-earth complexes.

ProPhenol-Catalyzed Asymmetric Additions by Spontaneously Assembled Dinuclear Main Group Metal Complexes

PubMed Central

2016-01-01

Conspectus The development of catalytic enantioselective transformations has been the focus of many research groups over the past half century and is of paramount importance to the pharmaceutical and agrochemical industries. Since the award of the Nobel Prize in 2001, the field of enantioselective transition metal catalysis has soared to new heights, with the development of more efficient catalysts and new catalytic transformations at increasing frequency. Furthermore, catalytic reactions that allow higher levels of redox- and step-economy are being developed. Thus, alternatives to asymmetric alkene dihydroxylation and the enantioselective reduction of α,β-unsaturated ketones can invoke more strategic C–C bond forming reactions, such as asymmetric aldol reactions of an aldehyde with α-hydroxyketone donors or enantioselective alkynylation of an aldehyde, respectively. To facilitate catalytic enantioselective addition reactions, including the aforementioned aldol and alkynylation reactions, our lab has developed the ProPhenol ligand. In this Account, we describe the development and application of the ProPhenol ligand for asymmetric additions of both carbon- and heteroatom-based nucleophiles to various electrophiles. The ProPhenol ligand spontaneously forms chiral dinuclear metal complexes when treated with an alkyl metal reagent, such as Et2Zn or Bu2Mg. The resulting complex contains both a Lewis acidic site to activate an electrophile and a Brønsted basic site to deprotonate a pronucleophile. Initially, our research focused on the use of Zn-ProPhenol complexes to facilitate the direct aldol reaction. Fine tuning of the reaction through ligand modification and the use of additives enabled the direct aldol reaction to proceed in high yields and stereoselectivities with a broad range of donor substrates, including acetophenones, methyl ynones, methyl vinyl ketone, acetone, α-hydroxy carbonyl compounds, and glycine Schiff bases. Additionally, an analogous magnesium ProPhenol complex was used to facilitate enantioselective diazoacetate aldol reactions with aryl, α,β-unsaturated, and aliphatic aldehydes. The utility of bimetallic ProPhenol catalysts was extended to asymmetric additions with a wide range of substrate combinations. Effective pronucleophiles include oxazolones, 2-furanone, nitroalkanes, pyrroles, 3-hydroxyoxindoles, alkynes, meso-1,3-diols, and dialkyl phosphine oxides. These substrates were found to be effective with a number of electrophiles, including aldehydes, imines, nitroalkenes, acyl silanes, vinyl benzoates, and α,β-unsaturated carbonyls. A truly diverse range of enantioenriched compounds have been prepared using the ProPhenol ligand, and the commercial availability of both ligand enantiomers makes it ideally suited for the synthesis of complex molecules. To date, enantioselective ProPhenol-catalyzed reactions have been used in the synthesis of more than 20 natural products. PMID:25650587

1,3-dialkyl- and 1,3-diaryl-3,4,5,6-tetrahydropyrimidin-2-ylidene rhodium(i) and palladium(II) complexes: synthesis, structure, and reactivity.

PubMed

Mayr, Monika; Wurst, Klaus; Ongania, Karl-Hans; Buchmeiser, Michael R

2004-03-05

The synthesis of novel 1,3-diaryl- and 1,3-dialkylpyrimidin-2-ylidene-based N-heterocyclic carbenes (NHCs) and their rhodium(i) and palladium(II) complexes is described. The rhodium compounds bromo(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (7), bromo(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (8) (cod=eta(4)-1,5-cyclooctadiene, mesityl=2,4,6-trimethylphenyl), chloro(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (9), and chloro(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (10) were prepared by reaction of [[Rh(cod)Cl](2)] with lithium tert-butoxide followed by addition of 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium bromide (3), 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate (4), 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium bromide (6), and 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate, respectively. Complex 7 crystallizes in the monoclinic space group P2(1)/n, and 8 in the monoclinic space group P2(1). Complexes 9 and 10 were used for the synthesis of the corresponding dicarbonyl complexes dicarbonylchloro(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (11), and dicarbonylchloro[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (12). The wavenumbers nu(CO I)/nu(CO II) for 11 and 12 were used as a quantitative measure for the basicity of the NHC ligand. The values of 2062/1976 and 2063/1982 cm(-1), respectively, indicate that the new NHCs are among the most basic cyclic ligands reported so far. Compounds 3 and 6 were additionally converted to the corresponding cationic silver(i) bis-NHC complexes [Ag(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]AgBr(2) (13) and [Ag[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene](2)]AgBr(2) (14), which were subsequently used in transmetalation reactions for the synthesis of the corresponding palladium(II) complexes Pd(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2) (2+)(Ag(2)Br(2)Cl(4) (4-))(1/2) (15) and Pd[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]Cl(2) (16). Complex 15 crystallizes in the monoclinic space group P2(1)/c, and 16 in the monoclinic space group C(2)/c. The catalytic activity of 15 and 16 in Heck-type reactions was studied in detail. Both compounds are highly active in the coupling of aliphatic and aromatic vinyl compounds with aryl bromides and chlorides with turnover numbers (TONs) up to 2000000. Stabilities of 15 and 16 under Heck-couplings conditions were correlated with their molecular structure. Finally, selected kinetic data for these couplings are presented.

Regional Comparison of Organophosphate Flame Retardant (PFRs) Urinary Metabolites and Tetrabromobenzoic Acid (TBBA) In Mother-Toddler Pairs from California and New Jersey

PubMed Central

Butt, Craig M.; Hoffman, Kate; Chen, Albert; Lorenzo, Amelia; Congleton, Johanna; Stapleton, Heather M.

2016-01-01

The use of alternative chemical flame retardants in consumer products is increasing as the result of the phase-out of polybrominated diphenyl ethers. Today, the most commonly detected alternatives in residential furniture include the organophosphate flame retardants (PFRs) and the Firemaster 550® mixture (FM550). Urinary levels of dialkyl and diaryl phosphate esters, and 2-ethylhexyl tetrabromobenzoate (EH-TBB) have been used as biomarkers of human exposure to PFRs and FM550, respectively. In a previous study, we demonstrated that toddlers had significantly higher levels of PFRs relative to their mothers in a cohort from New Jersey; however, it is unclear if there are regional differences in exposure. It is possible that exposure to PFRs may be higher in California relative to other US States due to the California flammability standard, as was seen previously observed for PBDEs. In the current study, we examined urinary levels of PFR metabolites and TBBA in 28 mother-child pairs from California, USA, collected in 2015, and compared them with levels measured in our previous study from New Jersey. Urine samples were extracted using solid-phase extraction and analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS). Diphenyl phosphate (DPHP), isopropyl-phenyl phenyl phosphate (ip-PPP), bis(1,3-dichloro-2propyl) phosphate (BDCIPP) and BCIPHIPP conjugates were detected in 100% of mother and child urine samples, while bis(1-chloro-2-propyl) phosphate (BCIPP), tert-butyl-phenyl phenyl phosphate (tb-PPP) and TBBA were detected in <50% of samples. Interestingly, BCIPHIPP conjugates were detected in 100% of the urine samples, suggesting ubiquitous exposure to the parent compound, tris(1-chloro-2-propyl) phosphate (TCIPP). The current study found significantly higher BDCIPP levels in California toddlers and higher and ip-PPP levels in mothers as compared to the New Jersey cohort, which may be reflective of California’s furniture flammability standard. For example, BDCIPP levels in California children were 2.4 times higher than those in New Jersey children. Consistent with our previous work, the current study showed higher PFR and EH-TBB exposure in children, likely due to increased hand-mouth behavior. Children’s DPHP and BDCIPP levels, on average, were 5.9 times and 15 times those of their mothers. Positive correlations between paired mothers and their children were shown for DPHP and BCIPHIPP conjugates but not BDCIPP or ip-PPP. In the children, several predictors of hand-mouth behavior were associated with BDCIPP, DPHP and ip-PPP urine levels, but no associations were observed with BCIPHIPP conjugates. PMID:27397928

Conformational preferences for some 2-substituted N-methoxy- N-methylacetamides through spectroscopic and theoretical studies

NASA Astrophysics Data System (ADS)

Olivato, Paulo R.; da Silva Gomes, Roberto; Rodrigues, Alessandro; Reis, Adriana K. C. A.; Domingues, Nelson L. C.; Rittner, Roberto; Dal Colle, Maurizio

2010-08-01

The analysis of the IR carbonyl band of the 2-substituted N-methoxy- N-methylacetamides Y-CH 2C(O)N(OMe)Me (Y = F 1, OMe 2, OPh 3, Cl 4), supported by B3LYP/6-311++G(3df, 3pd) calculations along with the NBO analysis for 1- 4, indicated the existence of cis- gauche conformers i.e. ( c) and ( g) for 1 and 3, ( c1,c2) and ( g1,g2) for 2, and ( c) and ( g1,g2) for 4. In the gas phase, the g conformer population prevails over the c one, for 1 and 3, the ( c1 + c2) population prevails over the ( g1 + g2) one for 2, and the ( g1 + g2) conformer population is more abundant than ( c) one for 4. In n-hexane solution, the cis conformer is more abundant for 1- 3. The occurrence of Fermi resonance in the νCO region, in n-hexane, precludes the estimative of relative populations of the ( c, g1, g2) conformers for 4. The SCI-PCM calculations agree with the solvent effect on the νCO band component relative intensities for 1- 3. NBO analysis showed that the nN → πco∗ orbital interaction is the main factor which stabilizes the gauche ( g, g1, g2) conformers for 1- 4 into a larger extent relative to the cis ( c, c1, c2) ones. The nY → πco∗, σCsbnd Y → πco∗, πco → σC sbnd Y ∗ and πco∗ → σC sbnd Y ∗ orbital interactions still contribute, but into a minor extent for the stabilization of the gauche conformers relative to the cis ones. The existence of some pyramidalization at the nitrogen atom of the Weinreb amides 1- 4 is responsible for the occurrence of Y δ-(4)···O δ-(9) and Y δ-(4)···N δ-(7) short contacts in the gauche ( g, g1, g2) conformers, which originates strong repulsive Coulombic interactions, acting in opposition to the large orbital stabilization of the gauche conformer with respect to the cis one. Therefore, a delicate balance of the Coulombic and orbital interactions seems to be responsible for the observed stabilization of the gauche ( g, g1, g2) and cis ( c, c1, c2) conformers, both in the gas phase and in the solution for 1- 4. However, the cis conformer predominance, in non polar solvents, for the 2-substituted N-methoxy- N-methyl acetamides 1- 3, bearing in α first raw (fluorine and oxygen) atoms, is in the opposite direction to the gauche conformer preference for the corresponding 2-substituted N, N-dialkyl-acetamides.

Occurrence and distribution of GDGTs in the free and bound lipid fractions from podzols: implications for the reconstruction of mean air temperature

NASA Astrophysics Data System (ADS)

Huguet, A.; Fosse, C.; Metzger, P.; Derenne, S.

2009-12-01

Glycerol dialkyl glycerol tetraethers (GDGTs) are complex lipids of high molecular weight, present in cell membranes of archaea and some bacteria. Archaeal membranes are formed predominantly by isoprenoid GDGTs with acyclic or ring-containing biphytanyl chains. Another type of GDGTs with branched instead of isoprenoid alkyl chains was recently discovered in soils. Branched tetraethers were suggested to be produced by anaerobic bacteria and can be used to reconstruct past air temperature and soil pH. Lipids preserved in soils can take two broad chemical forms: "free" lipids, recoverable after solvent extraction, and "bound" lipids, linked to the organic or mineral matrix of soils. The "free" and "bound" lipid fractions may respond to environmental changes in different ways and the information derived from these two pools may differ. The aim of the present work was therefore to compare the abundance and distribution of "free" and "bound" GDGTs in two contrasted podzols: a temperate podzol located 40 km north of Paris and a tropical podzol from the upper Amazon Basin. Five samples were collected from the whole profile of the temperate podzol including the litter layer. Five additional samples were obtained from three profiles of the tropical soil sequence, representative of the transition between a latosol and a well-developed podzol. Vertical and/or lateral variations in GDGT content and composition were highlighted. In particular, in the tropical sequence, GDGTs were present at relatively low concentrations in the early stages of podzolisation and were more abundant in the well-developed podzolic horizons, where higher acidity and increased bacterial activity may favour their stabilization. Concerning the temperate podzol, GDGT distribution was shown to vary greatly with depth in the soil profile, the methylation degree of bacterial GDGTs being notably higher in the surficial than in the deep soil horizons. Bacterial GDGTs were also detected in the litter layer of the temperate podzol, suggesting the presence of branched-GDGT producing bacteria in the litter, probably in anoxic microenvironments. Last, we showed for the first time that substantial amounts of "bound" GDGTs could be released after acid hydrolysis of solvent-extracted soils, since "bound" lipids represented between 10 and 60% of total (i.e. "free" + "bound") bacterial GDGTs and between 15 and 60% of total archaeal GDGTs in podzol samples. In addition, we observed that "free" and "bound" GDGTs could present different distribution patterns. Thus, the average methylation degree of bacterial GDGTs was higher in the "free" than in the "bound" lipid fraction in 3 soil horizons of the temperate podzol. Consequently, different mean air temperature values could be derived from "free" and "bound" bacterial GDGT distributions, suggesting that data obtained from the "free" lipid fraction have to be interpreted with care.

Combination of branched GDGTs and testate amoebae for the reconstruction of past climate change in a French peatland

NASA Astrophysics Data System (ADS)

Huguet, Arnaud; Jassey, Vincent E. J.; Laggoun-Défarge, Fatima; Derenne, Sylvie; Gilbert, Daniel; Delarue, Frédéric; Payne, Richard; Buttler, Alexandre; Mitchell, Edward A. D.

2013-04-01

Peatlands are important archives for the reconstruction of past environmental changes because of their high rates of peat accumulation due to the low rate of plant litter decomposition. Branched glycerol dialkyl glycerol tetraethers (GDGTs) are complex lipids of high molecular weight, recently discovered in soils and suggested to be produced by anaerobic bacteria. The relative distribution of branched GDGTs in soils correlates with environmental variables: the degree of methylation, expressed in the methylation index of branched tetraethers (MBT), depends on mean annual air temperature (MAAT) and to a lesser extent on soil pH, whereas the relative abundance of cyclopentyl rings of branched GDGTs, expressed in the cyclisation ratio of branched tetraethers (CBT), is related to soil pH. The MBT/CBT proxies are increasingly used for the reconstruction of past air temperatures, but have rarely been applied in peatlands. Testate amoebae are common and diverse unicellular eukaryotes in peatlands. They build shells that are preserved in peat. They are good indicators of changing environmental conditions in peatlands and are thus used in both ecological and paleoecological studies, especially for reconstructing surface moisture. The aim of this study was to examine the applicability of branched GDGTs and testate amoebae as indicators of environmental changes (temperature and moisture) in temperate peatlands. Within the PEATWARM project, both GDGTs and testate amoebae were studied at high resolution in a 4 m peat core collected in Frasne mire (French Jura Mountains) and covering the last 7,400 years BP. GDGT-inferred temperatures ranged between 8 and 12 °C until 250 cm depth and were higher than present measured mean annual air temperature (ca. 6 °C). Temperature estimates in the top part of the bog were most consistent with spring and summer mean air temperatures recorded in the peatland (ca. 11.5 °C), suggesting that branched GDGT-producing bacteria might be more active during the warmest months of the year. At 250 cm depth, reconstructed temperature showed a pronounced shift, likely reflecting both a change in climatic conditions but also in the composition of the peat. Indeed, drier conditions were indicated by testate amoebae at the bottom of the peat core, whereas wetter conditions occurred at the top. Interestingly, temperature variations inferred from MBT/CBT proxies were weakly linked with moisture variations inferred from testate amoebae until 150 cm depth (r = -0.41, p = 0.06). Therefore, the distribution of branched GDGTs might also depend on peat moisture level, in addition to air temperature and pH. Our data suggest that the joint use of MBT/CBT and testate amoebae is a promising approach to estimate past climate change, but that more research is required to calibrate and apply with confidence these proxies in peatlands.

Organic semiconductors based on [1]benzothieno[3,2-b][1]benzothiophene substructure.

PubMed

Takimiya, Kazuo; Osaka, Itaru; Mori, Takamichi; Nakano, Masahiro

2014-05-20

The design, synthesis, and characterization of organic semiconductors applicable to organic electronic devices, such as organic field-effect transistors (OFETs) and organic photovoltaics (OPVs), had been one of the most important topics in materials chemistry in the past decade. Among the vast number of materials developed, much expectation had been placed on thienoacenes, which are rigid and planar structures formed by fusing thiophenes and other aromatic rings, as a promising candidate for organic semiconductors for high-performance OFETs. However, the thienoacenes examined as an active material in OFETs in the 1990s afforded OFETs with only moderate hole mobilities (approximately 0.1 cm(2) V(-1) s(-1)). We speculated that this was due to the sulfur atoms in the thienoacenes, which hardly contributed to the intermolecular orbital overlap in the solid state. On the other hand, we have focused on other types of thienoacenes, such as [1]benzothieno[3,2-b][1]benzothiophene (BTBT), which seem to have appropriate HOMO spatial distribution for effective intermolecular orbital overlap. In fact, BTBT derivatives and their related materials, including dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT), have turned out to be superior organic semiconductors, affording OFETs with very high mobilities. To illustrate some examples, we have developed 2,7-diphenyl BTBT (DPh-BTBT) that yields vapor-deposited OFETs having mobilities of up to 2.0 cm(2) V(-1) s(-1) under ambient conditions, highly soluble dialkyl-BTBTs (Cn-BTBTs) that afford solution-processed OFETs with mobilities higher than 1.0 cm(2) V(-1) s(-1), and DNTT and its derivatives that yield OFETs with even higher mobilities (>3.0 cm(2) V(-1) s(-1)) and stability under ambient conditions. Such high performances are rationalized by their solid-state electronic structures that are calculated based on their packing structures: the large intermolecular orbital overlap and the isotropic two-dimensional electronic structure are the key regardless of the molecular size and substituents on the BTBT and its related thienoacene cores. Along with the discovery of such attracting performances, versatile and practical methods for the synthesis of BTBT and its derivatives, and the π-extended derivatives including DNTT, dianthra[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DATT), and the thienoacenes with two thieno[3,2-b]thiophene moieties, have been developed. In addition, the materials have been recently utilized in sophisticated devices and circuits, including all-printed transistor arrays, flexible circuits on ultrathin plastic substrates, and biomedical applications, underscoring their promise as practical semiconductors for electronic device applications. These exciting results of the present BTBT-based materials are expected to open doors to new horizons of organic semiconductors in terms of practical application and the design and synthesis of far more superior materials.

Potential of Gdgts as Temperature Proxies Along Altitudinal Transects in East Africa

NASA Astrophysics Data System (ADS)

Coffinet, Sarah; Huguet, Arnaud; Omuombo, Christine; Williamson, David; Fosse, Céline; Anquetil, Christine; Derenne, Sylvie

2014-05-01

Glycerol dialkyl glycerol tetraethers (GDGTs) are lipids of high molecular weight and include the isoprenoid GDGTs (iGDGTs) produced by Archaea and the branched GDGTs (brGDGTs) produced by unknown bacteria. Several indices were developed to describe the relationship between GDGT distribution and environmental parameters: the TEX86 (tetraether index of tetraethers consisting of 86 carbons), based on the relative abundances of iGDGTs in sediments, and the MBT (methylation index of branched tetraethers) and CBT (cyclisation ratio of branched tetraethers), based on the relative abundance of brGDGTs in soils. The TEX86 was shown to correlate well with water surface temperature, and the MBT and CBT with mean annual air temperature (MAAT) and soil pH. The GDGTs are increasingly used as temperature proxies. In this study, 41 surface soils were sampled along two altitudinal transects, from 500 to 2800 meters in Mount Rungwe (South western, Tanzania) and from 1897 to 3268 meters in Mount Kenya (Central Kenya). MAAT was reconstructed along the two transects using the MBT/CBT proxies. A linear correlation between the MBT/CBT-derived temperatures and the altitude (R2=0.83) was obtained by combining results of the two transects. The reconstructed temperature lapse rate (0.5 ° C/100 m) was consistent with the one determined from temperature measurements at six altitudes. These results show that the MBT/CBT is a suitable and robust temperature proxy in East Africa. In Mt. Rungwe soil samples, the TEX86 index, which was mainly used to reconstruct water surface temperatures until now, was found to vary linearly with altitude (R2=0.50). Such a relationship between TEX86 and altitude in organic soils has also been recently noticed in Mt. Xiangpi, China (Liu et al., 2013; R2=0.68). The adiabatic cooling of air with altitude could explain the TEX86 variation with altitude. If such a relationship is confirmed, the use of the TEX86 as a temperature proxy could be extended to soil environments. However, a lower correlation between TEX86 and altitude was observed for Mt. Kenya samples, implying that the environmental factors affecting the TEX86 values should be further investigated. Moreover, a given TEX86 value was shown to correspond to a much higher altitude (ca. 1800 m higher) for Mt. Xiangpi soils (Liu et al., 2013) than for Mt. Rungwe samples, suggesting that the geographical origin of the soils could also impact the TEX86 values. Therefore, a better understanding of the environmental mechanisms controlling the iGDGTs distribution in soils is needed prior any application of the TEX86 as a temperature proxy in these environments. REFERENCES Liu, W., Wang, H., Zhang, C.L., Liu, Z., He, Y., 2013. Organic Geochemistry 57, 76-83.

High-elevation amplification of warming since the Last Glacial Maximum in East Africa: New perspectives from biomarker paleotemperature reconstructions

NASA Astrophysics Data System (ADS)

Loomis, S. E.; Russell, J. M.; Kelly, M. A.; Eggermont, H.; Verschuren, D.

2013-12-01

Tropical lapse rate variability on glacial/interglacial time scales has been hotly debated since the publication of CLIMAP in 1976. Low-elevation paleotemperature reconstructions from the tropics have repeatedly shown less warming from the Last Glacial Maximum (LGM) to present than reconstructions from high elevations, leading to widespread difficulty in estimating the true LGM-present temperature change in the tropics. This debate is further complicated by the fact that most paleotemperature estimates from high elevations in the tropics are derived from pollen- and moraine-based reconstructions of altitudinal shifts in vegetation belts and glacial equilibrium line altitudes (ELAs). These traditional approaches rely on the assumption that lapse rates have remained constant through time. However, this assumption is problematic in the case of the LGM, when pervasive tropical aridity most likely led to substantial changes in lapse rates. Glycerol dialkyl glycerol tetraethers (GDGTs) can be used to reconstruct paleotemperatures independent of hydrological changes, making them the ideal proxy to reconstruct high elevation temperature change and assess lapse rate variability through time. Here we present two new equatorial paleotemperature records from high elevations in East Africa (Lake Rutundu, Mt. Kenya and Lake Mahoma, Rwenzori Mountains, Uganda) based on branched GDGTs. Our record from Lake Rutundu shows deglacial warming starting near 17 ka and a mid-Holocene thermal maximum near 5 ka. The overall amplitude of warming in the Lake Rutundu record is 6.8×1.0°C from the LGM to the present, with mid-Holocene temperatures 1.6×0.9°C warmer than modern. Our record from Lake Mahoma extends back to 7 ka and shows similar temperature trends to our record from Lake Rutundu, indicating similar temporal resolution of high-elevation temperature change throughout the region. Combining these new records with three previously published GDGT temperature records from different elevations in East Africa (Sacred Lake, Lake Tanganyika, and Lake Malawi), we are able to reconstruct a continuous record of lapse rates and freezing level heights (FLHs) back to the LGM. We find that tropical lapse rates have varied widely over the last 22 ky, with the largest (lowest) lapse rate (FLH) around the LGM, while the smallest (highest) lapse rate (FLH) occurs during the mid-Holocene, confirming the amplification of warming at high altitudes between the LGM and present. These lapse rate and FLH reconstructions match records of regional hydrological variability, confirming the importance of glacial/interglacial humidity variations on altitudinal temperature gradients in the tropics. Furthermore, the FLH record largely matches records of tropical glacier ELA changes, indicating that warming from LGM-present was likely amplified at high altitudes throughout the tropics.

Near-infrared optical-absorption behavior in high-beta nonlinear optical chromophore-polymer guest-host materials. II. Dye spacer length effects in an amorphous polycarbonate copolymer host

NASA Astrophysics Data System (ADS)

Barto, Richard R.; Frank, Curtis W.; Bedworth, Peter V.; Ermer, Susan; Taylor, Rebecca E.

2005-06-01

In the second of a three-part series, spectral absorption behavior of nonlinear optical (NLO) dyes incorporated into amorphous polycarbonate, comprised of a homologous series of dialkyl spacer groups extending from the midsection of the dye molecule, is characterized by UV-Vis and photothermal deflection spectroscopy. The dyes are structural analogs of the NLO dye FTC [2-(3-cyano-4-{2-[5-(2-{4-[ethyl-(2-methoxyethyl)amino]phenyl}vinyl)-3,4-diethylthiophen-2-yl]vinyl}-5,5-dimethyl-5H-furan-2-ylidene)malononitrile]. Previous Monte Carlo calculations [B. H. Robinson and L. R. Dalton, J. Phys. Chem. A 104, 4785 (2000)] predict a strong dependence of the macroscopic nonlinear optical susceptibility on the chromophore waist: length aspect ratio in electric-field-poled films arising from interactions between chromophores. It is expected that these interactions will play a role in the absorption characteristics of unpoled films, as well. The spacer groups range in length from diethyl to dihexyl, and each dye is studied over a wide range of concentrations. Among the four dyes studied, a universal dependence of near-IR loss on inhomogeneous broadening of the dye main absorption peak is found. The inhomogeneous width and its concentration dependence are seen to vary with spacer length in a manner characteristic of the near-IR loss-concentration slope at transmission wavelengths of 1.06 and 1.3μm, but not at 1.55μm. The lower wavelength loss behavior is assigned to purely Gaussian broadening, and is described by classical mixing thermodynamic quantities based on the Marcus theory of inhomogeneous broadening [R. A. Marcus, J. Chem. Phys. 43, 1261 (1965)], modeled as a convolution of dye-dye dipole broadening and dye-polymer van der Waals broadening. The Gaussian dipole interactions follow a Loring dipole-broadening description [R. F. Loring, J. Phys. Chem. 94, 513 (1990)] dominated by the excited-state dipole moment, and have a correlated homogeneous broadening contribution. The long-wavelength loss behavior has a non-Gaussian dye-dye dipole contribution which follows Kador's broadening analysis [L. Kador, J. Chem. Phys. 95, 5574 (1991)], with a net broadening described by a convolution of this term with a Gaussian van der Waals interaction given by Obata et al. [M. Obata, S. Machida, and K. Horie, J. Polym. Sci. B 37, 2173 (1999)], with each term governed by the dye spacer length. A minimum in broadening and loss-concentration slope at a spacer length of four carbons per alkyl at all wavelengths has important consequences for practical waveguide devices, and is of higher aspect ratio than the spherical limit shown by Robinson and Dalton to minimize dipole interactions under a poling field.

Worker exposure and a risk assessment of malathion and fenthion used in the control of Mediterranean fruit fly in South Australia.

PubMed

Edwards, John W; Lee, Su-Gil; Heath, Linda M; Pisaniello, Dino L

2007-01-01

In 2001, an outbreak of Mediterranean fruit fly in Adelaide was controlled by South Australian Government workers applying organophosphorus insecticides (OPs) to domestic gardens. Residents made claims of adverse effects associated with allegations that worker application practices were poor and led to contamination of homes, residents and pets. The concerns led to a Parliamentary enquiry, the suspension of OP applications for fruit fly control, and the investigation of alternative methods of combating fruit fly in metropolitan Adelaide. The extent of exposure of workers and residents was not estimated. This paper describes a simulated application of the OPs concerned (fenthion and malathion) with measurements of potential exposure through inhalation, dermal contact and deposition of pesticides on surfaces. The data were used as part of a toxicological risk assessment to determine the likely impact of the use of these insecticides. Malathion, used as a 1% suspension in a protein bait mixture, was found to have little potential for airborne exposure, although some workers were found to have up to 0.315 microg/cm(2) malathion deposited on overalls (principally on forearms) and over 500 microg deposited on liner gloves and hats, respectively. Risks to workers and residents were low, with exposures likely to be a small fraction of the acceptable daily intake. Fenthion, used as a 0.05% foliar cover spray, was found between 0.02 and 0.23 mg/m(3) in air 10 m downwind from spray activity and was unlikely to pose a significant risk to residents, since exposures were of short durations of up to 20 min. Personal air samples of spray workers averaged 0.55 mg/m(3) (Workplace Exposure Standard 0.20mg/m(3)). Since workers were usually engaged in spraying for a large proportion of the day, this demonstrates the need for respiratory protective equipment. Maximum deposition of fenthion on workers overalls ranged from 0.06 to over 0.20 microg/cm(2), although little was found on gloves and hats, suggesting workers were skilled in avoiding the plume of overspray. Dialkyl phosphates (metabolites of OP insecticides) were not detected in urine of workers, and there were no changes observed in serum cholinesterase (SChE) enzyme activities 24h following the simulation. These data suggest absorption of OP insecticides by workers was negligible. Deposition on surfaces 5 and 10 m downwind ranged from none detected to 145 microg/cm(2), suggesting that exposure of residents and children in contact with contaminated surfaces (such as garden furniture or play equipment) is possible. Estimates of the potential dermal intake of fenthion by children from contaminated surfaces suggested that risks of acute and chronic effects are slight, since exposures may occur for short periods at intervals of approximately 10 days during fruit fly outbreaks.

A re-evaluation of the use of branched GDGTs as terrestrial biomarkers: Implications for the BIT Index

NASA Astrophysics Data System (ADS)

Smith, Richard W.; Bianchi, Thomas S.; Li, Xinxin

2012-03-01

This study examines estimates of soil organic matter content (%OMsoil) in marine sediments based on the branched/isoprenoid tetraether (BIT) Index, and suggests a new calculation method based on branched GDGT (brGDGT) concentrations. Four sediment cores were collected in 2008 at the 20 m isobath of the Louisiana Continental Shelf. Glycerol dialkyl glycerol tetraether (GDGTs) and cupric oxide (CuO) oxidation products were analyzed down to ˜20 cm depth to examine terrestrially-derived organic matter. BIT Indices ranged from 0.50 to 0.03, and correlated poorly with lignin (mg S, V, and C phenols 10 g-1 sediment; ∑810) and 3,5-dihydroxybenzoic acid (μg 3,5-Bd g-1 sediment; 3,5:g) concentrations, which ranged from 0.01 to 0.87 mg g-1 and 0.00 (below detection limit) to 1.39 μg g-1, respectively. By calculating mass normalized core-lipid branched GDGT (brGDGT) and crenarchaeol mass abundances with the assistance of a surrogate standard, it was shown that overall, large variations in sedimentary crenarchaeol concentrations were responsible for vertical distributions of BIT Indices, due to the relatively smaller range of brGDGT concentrations. brGDGT concentrations produced stronger correlations with terrestrial CuO oxidation products than the BIT Index, which correlated strongly with crenarchaeol concentrations. Variations in the BIT Index may therefore reflect changes in the delivery of marine-derived organic matter to sediments in regions with large seasonal or decadal shifts in productivity, such as stratified continental shelves. An in depth look at conversions of the BIT Index to percent soil organic matter using a binary mixing model with a marine BIT value of 0 and a terrestrial BIT value of 1 (%OMsoil = BIT Index * 100) used in recent literature reveals that this method results in non-linear mixing of marine and terrestrial end-members, and the shape of the mixing line is based on sedimentary crenarchaeol concentrations. An alternative approach is to use sedimentary brGDGT yields as a OMsoil proxy, rather than normalizing them to crenarchaeol. %OMsoil could then be calculated using brGDGT concentrations in a two end-member mixing model as follows:%OMsoil = ([brGDGT]sample * 100)/[brGDGT]soil, where [brGDGT]sample and [brGDGT]soil represent the concentrations of branched GDGTs in the given sediment sample and in the average soil end-member, respectively. However, due to the wide range of brGDGT concentrations found in soils both regionally and globally, assigning a terrestrial end-member may not always be possible. While this method may in some instances also be a misrepresentation of %OMsoil in sediments, both estimation methods should be used with regard to their individual strengths and weaknesses.

Elevation-dependent changes in n-alkane δD and soil GDGTs across the South Central Andes

NASA Astrophysics Data System (ADS)

Nieto-Moreno, Vanesa; Rohrmann, Alexander; van der Meer, Marcel T. J.; Sinninghe Damsté, Jaap S.; Sachse, Dirk; Tofelde, Stefanie; Niedermeyer, Eva M.; Strecker, Manfred R.; Mulch, Andreas

2016-11-01

Surface uplift of large plateaus may significantly influence regional climate and more specifically precipitation patterns and temperature, sometimes complicating paleoaltimetry interpretations. Thus, understanding the topographic evolution of tectonically active mountain belts benefits from continued development of reliable proxies to reduce uncertainties in paleoaltimetry reconstructions. Lipid biomarker-based proxies provide a novel approach to stable isotope paleoaltimetry and complement authigenic or pedogenic mineral proxy materials, in particular outside semi-arid climate zones where soil carbonates are not abundant but (soil) organic matter has a high preservation potential. Here we present δD values of soil-derived n-alkanes and mean annual air temperature (MAT) estimates based on branched glycerol dialkyl glycerol tetraether (brGDGT) distributions to assess their potential for paleoelevation reconstructions in the southern central Andes. We analyzed soil samples across two environmental and hydrological gradients that include a hillslope (26-28°S) and a valley (22-24°S) transect on the windward flanks of Central Andean Eastern Cordillera in NW Argentina. Our results show that present-day n-alkane δD values and brGDGT-based MAT estimates are both linearly related with elevation and in good agreement with present-day climate conditions. Soil n-alkanes show a δD lapse rate (Δ (δD)) of - 1.64 ‰ / 100 m (R2 = 0.91, p < 0.01) at the hillslope transect, within the range of δD lapse rates from precipitation and surface waters in other tropical regions in the Andes like the Eastern Cordillera in Colombia and Bolivia and the Equatorial and Peruvian Andes. BrGDGT-derived soil temperatures are similar to monitored winter temperatures in the region and show a lapse rate of ΔT = - 0.51 °C / 100 m (R2 = 0.91, p < 0.01), comparable with lapse rates from in situ soil temperature measurements, satellite-derived land-surface temperatures at this transect, and weather stations from the Eastern Cordillera at similar latitude. As a result of an increasing leeward sampling position along the valley transect lapse rates are biased towards lower values and display higher scatter (Δ (δD) = - 0.95 ‰ / 100 m, R2 = 0.76, p < 0.01 and ΔT = - 0.19 °C / 100 m, R2 = 0.48, p < 0.05). Despite this higher complexity, they are in line with lapse rates from stream-water samples and in situ soil temperature measurements along the same transect. Our results demonstrate that both soil n-alkane δD values and MAT reconstructions based on brGDGTs distributions from the hillslope transect (Δ (δD) = - 1.64 ‰ / 100 m, R2 = 0.91, p < 0.01 and ΔT = - 0.51 °C / 100 m, R2 = 0.91, p < 0.01) track the direct effects of orography on precipitation and temperature and hence the combined effects of local and regional hydrology as well as elevation.

Distribution of tetraether lipids in agricultural soils - differentiation between paddy and upland management

NASA Astrophysics Data System (ADS)

Mueller-Niggemann, Cornelia; Rahayu Utami, Sri; Marxen, Anika; Mangelsdorf, Kai; Bauersachs, Thorsten; Schwark, Lorenz

2016-03-01

Rice paddies constitute almost a fifth of global cropland and provide more than half of the world's population with staple food. At the same time, they are a major source of methane and therewith significantly contribute to the current warming of Earth's atmosphere. Despite their apparent importance in the cycling of carbon and other elements, however, the microorganisms thriving in rice paddies are insufficiently characterized with respect to their biomolecules. Hardly any information exists on human-induced alteration of biomolecules from natural microbial communities in paddy soils through varying management types (affecting, e.g., soil or water redox conditions, cultivated plants). Here, we determined the influence of different land use types on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs), which serve as molecular indicators for microbial community structures, in rice paddy (periodically flooded) and adjacent upland (non-flooded) soils and, for further comparison, forest, bushland and marsh soils. To differentiate local effects on GDGT distribution patterns, we collected soil samples in locations from tropical (Indonesia, Vietnam and Philippines) and subtropical (China and Italy) sites. We found that differences in the distribution of isoprenoid GDGTs (iGDGTs) as well as of branched GDGTs (brGDGTs) are predominantly controlled by management type and only secondarily by climatic exposition. In general, upland soil had higher crenarchaeol contents than paddy soil, which by contrast was more enriched in GDGT-0. The GDGT-0 / crenarchaeol ratio, indicating the enhanced presence of methanogenic archaea, was 3-27 times higher in paddy soils compared to other soils and increased with the number of rice cultivation cycles per year. The index of tetraethers consisting of 86 carbons (TEX86) values were 1.3 times higher in upland, bushland and forest soils than in paddy soils, potentially due to differences in soil temperature. In all soils brGDGT predominated over iGDGTs with the relative abundance of brGDGTs increasing from subtropical to tropical soils. Higher branched vs. isoprenoid tetraether (BIT) values in paddy soils compared to upland soils together with higher BIT values in soils from subtropical climates indicated effects on the amounts of brGDGT induced by differences in management as well as climate. In acidic soils cyclization ratio of branched tetraethers (CBT) values correlated well with soil pH. In neutral to alkaline soils, however, no correlation but an offset in CBT between paddy and upland managed soils was detected. This is interpreted as indicating soil moisture exerting an additional control on the CBT in these soils. Lower modified methylation index of branched tetraether (MBT') values and temperatures calculated from this (TMC) in paddy soils compared to upland soils are attributed to a management-induced (e.g. enhanced soil moisture via flooding) effect on mean annual soil temperature (MST).

Climatic record of the Iberian peninsula from lake Moncortes' sediments

NASA Astrophysics Data System (ADS)

Cao, Min; Huguet, Carme; Rull, Valenti; Valero, Blas; Rosell-Mele, Antoni

2014-05-01

Climatic record of the Iberian peninsula from lake Moncortes' sediments Min Cao1, Carme Huguet1, Valenti Rull2, Blas L. Valero-Garces3, Antoni Rosell-Melé1,4 1Institut de Ciència i Tecnologia Ambientals (ICTA), Universitat Autònoma de Barcelona, 08193 Cerdanyola del Vallès, Catalonia, Spain; 2Institut de Botanic de Barcelona (CSIC), Passeig del Migdia s/n, 08038, Barcelona, Spain, 3 Instituto Pirenaico de Ecologıa (CSIC), Avda. Montañana 1005, 50059 Zaragoza, Spain, 4Institució Catalana de Recerca i Estudis Avançats (ICREA), 08010 Barcelona, Catalonia, Spain. The continuing buildup of industrial greenhouse gases in the atmosphere and concomitant increase in global temperatures has made much of the world's society aware that decades to centuries of environmental change lie ahead, and that these will have profound economic, political and societal impacts. The Iberian Peninsula lies in the boundary between tropical and subtropical climates and seems to amplify the climatic signals form the northern hemisphere through both atmospheric and water circulation feedbacks, making it an ideal site to monitor Northern hemisphere climate changes. This extreme sensitivity to climatic changes also makes the Iberian Peninsula extremely vulnerable to future climate changes. This is why understanding sensitivity to climate change and the consequences it will have on both climate and the hydrological cycle is key to implement preventive measures. The aim of our study is to come up with a high resolution quantitative reconstruction of climate variability (temperature, production and precipitation) in the Iberian Peninsula from lake sediments. We also want to establish the relation between those changes and the ones observed in both ice cores from Greenland and paleotemperature records from marine sediments of the continental Iberian margin. For these reasons we sampled a core in Moncortes (42.3N, 0.99E), a lake of karstic origin with an average depth of 25m and an area of 0.19km2. Lake Moncortes is situated at 1065 m above sea level, has an average temperature of 10ºC (minimum 3 and maximum 16ºC) and a mean annual precipitation of 770mm. We used the MBT/CBT (Weijers et al. 2007) proxy of pH and terrestrial temperature and the TEX86 temperature proxy (Schouten et al. 2002) to estimate changes in and around the lake. Both proxies are based on the glycerol dialkyl glycerol tetraethers (GDGTs) of archaea (isoprenoid GDGTs) and bacteria (branched GDGTs) origin. We also measured soils surrounding the lake (Menges et al. 2013) in order to establish end-members for the proxies as well as organic matter transport. Data on n-alkane isotopes will help establish hydrographic regime changes. We observe changes in temperature and humidity consistent with those on teh northern hemisphere. J. Menges, C. Huguet, J.M. Alcañiz, S. Fietz, D. Sachse, A. Rosell-Melé Biogechemistry discussions (2013), BGD bg-2013-198. S. Schouten, E.C. Hopmans, E. Schefuss, J.S.S. Damste, Earth and Planetary Science Letters 204(2002) 265-274 J.W.H. Weijers, S. Schouten, J.S.S. Damste, Geochimica Et Cosmochimica Acta 71(2007) A1098-A1098.

Long Island Sound Water Temperatures During the Last Two Thousand Years

NASA Astrophysics Data System (ADS)

Warren, C. E.; Varekamp, J. C.; Thomas, E.

2010-12-01

The Long Island Sound (LIS), sometimes called the “urban sea”, is a large estuary in the heavily populated coastal zone between New York City and the Connecticut - Rhode Island border. LIS has seen dramatic environmental shifts since colonial times, including major changes in aquatic food extraction, land use, contaminant and nutrient inputs, and climate change. Annual seasonal hypoxic/anoxic events, especially common in westernmost LIS, have been identified as potentially severe stressors for LIS biota including valuable fisheries species such as lobsters and shellfish. These conditions develop when the Sound becomes stratified in midsummer and oxygen consumption from the oxidation of organic matter exceeds oxygen resupply from the atmosphere or photosynthesis. Severity, lateral extent and frequency of hypoxia/anoxia is influenced by the amount of organic matter available for oxidation, both marine organic matter (produced by algal blooms in response to influx of N-rich effluents from waste water treatment plants) and terrestrial organic matter. These events are also influenced by the severity of stratification, determined by differences in density from temperature and salinity gradients of surface and bottom waters. Studies of cores in western and central LIS, dated using Hg-pollution profiles, 210Pb - 137Cs, and 14C, indicate that eutrophication and hypoxia have occurred in LIS only over the last ~150 years, with the possible exception of the Narrows (closest to NY) where it may have occurred before colonial times. Salinity decreased as well over the last 150 years, possibly due to changes in land use or deflection of fresh water from the Hudson River. Temperature variability in LIS over the last few thousand years has not been clearly documented, as several paleotemperature proxies are difficult to use in estuarine settings. Oxygen isotope values of carbonate microfossils are influenced by salinity fluctuations, and Mg/Ca values in these shells may be influenced by the carbonate saturation state of the water. The tetraether index (TEX86) temperature proxy is based on the number of cyclopentane rings in the glycerol dialkyl glycerol tetraethers (GDGTs) from the membrane lipids of marine Crenarchaeota, which changes in response to temperature. Crenarcheota are one of the three major groups of non-thermophilic Archaea, a widely distributed, abundant and ecologically diverse group. This proxy can be used in organic-rich sediments deposited in many different settings. We analyzed samples for TEX86 in LIS cores in order to generate a 2,000 year temperature record. We compare the TEX86 paleotemperature record data (dominantly reflecting surface water temperatures) with a Mg/Ca record based on benthic foraminifera (reflecting bottom water temperatures), and an oxygen isotope record based on benthic foraminifera and corrected for salinity changes by using the Mg/Ca record. The Mg/Ca record appears to show evidence for the Little Ice Age and Medieval Warm Period. Preliminary TEX86 data indicate that temperatures of LIS waters, as averaged over the part of the year that the proxy organisms are biologically active, generally fluctuated between 12-14°C.

Branched tetraether membrane lipids: A versatile group of molecular fossils as testimony of past climate change (Outstanding Young Scientist Lecture)

NASA Astrophysics Data System (ADS)

Weijers, J. W. H.

2009-04-01

Studying fossils of any kind provides a small window into past times and could learn us why the world around us is as it is today (and might become in the near future). Like paleontologists studying bone remains and palaeobotanists studying fossil plant remains, many organic geochemists study fossil molecules to learn about geochemical cycles, evolution, ecology and climate. Branched Glycerol Dialkyl Glycerol Tetraether (GDGT) membrane lipids are an example of such molecular fossils and have been the core subject of my research. These molecules were initially detected a decade ago in near coastal marine sediments and structurally resemble isoprenoid GDGTs, a group of membrane lipids synthesised by Archaea, a Domain of life separate from Bacteria and Eukarya. With nuclear magnetic resonance techniques we showed, however, that branched GDGTs are of bacterial rather than archaeal origin and analysis of soils, peat bogs and marine surface sediments pointed to a terrestrial origin. As isoprenoid GDGTs are mainly produced by marine archaea the ratio between the two groups, the Branched vs. Isoprenoid Tetraether (BIT) index, could be used to trace the input of soil organic matter into marine sediments. In this lecture I will provide examples of applications of this BIT index in the Channel River during the last Glacial Maximum and the Congo deep sea fan over the last deglaciation. Meanwhile, it appeared that in soils the distribution of individual branched GDGTs, which differ in their content of methyl branches and cyclopentane rings, was different from place to place. Analysis of over 100 soils at different locations revealed that the distribution of the branched GDGTs is most strongly related to both soil pH and annual mean air temperature. This is explained by the fact that bacteria have to adapt the composition of their cell membrane to ambient conditions in order to keep it properly functioning. This empirical relation opened opportunities to reconstruct past annual mean air temperatures (and soil pH) from the branched GDGT distribution in sedimentary archives. I will present examples of such reconstructions from central tropical Africa during the last deglaciation, the southern North Sea basin during the Miocene cooling period (~17-5Ma), and the Arctic Ocean during the Palaeocene-Eocene thermal maximum (~55.5 Ma). So far, the applications of these proxies have shown to be rather successful. However, as with every new proxy, several questions and uncertainties remain. In part this is due to the fact that the bacteria that synthesise these lipids are as yet still unknown. My future research will therefore be dedicated to searching for the biological precursor organism and to further validation of these molecular proxies. In addition, the potential of this new continental temperature proxy for application in lake sediments will be investigated, initially focusing on the last deglaciation. Alongside the improvement of analytical techniques, this hopefully results in some more secrets of this fascinating and versatile group of molecular fossils to be revealed.

Occurrence and distribution of extractable and non-extractable GDGTs in podzols: implications for the reconstruction of mean air temperature

NASA Astrophysics Data System (ADS)

Huguet, Arnaud; Fosse, Céline; Metzger, Pierre; Derenne, Sylvie

2010-05-01

Glycerol dialkyl glycerol tetraethers (GDGTs) are complex lipids of high molecular weight, present in cell membranes of archaea and some bacteria. Archaeal membranes are formed predominantly by isoprenoid GDGTs with acyclic or ring-containing biphytanyl chains. Another type of GDGTs with branched instead of isoprenoid alkyl chains was recently discovered in soils. Branched tetraethers were suggested to be produced by anaerobic bacteria and can be used to reconstruct past air temperature and soil pH. Lipids preserved in soils can take two broad chemical forms: extractable lipids, recoverable upon solvent extraction, and non-extractable lipids, linked to the organic or mineral matrix of soils. Moreover, within the extractable pool, core (i.e. "free") lipids and intact polar (i.e. "bound") lipids can be distinguished. These three lipid fractions may respond to environmental changes in different ways and the information derived from these three pools may differ. The aim of the present work was therefore to compare the abundance and distribution of the three GDGT pools in two contrasted podzols: a temperate podzol located 40 km north of Paris and a tropical podzol from the upper Amazon Basin. Five samples were collected from the whole profile of the temperate podzol including the litter layer. Five additional samples were obtained from three profiles of the tropical soil sequence, representative of the transition between a latosol and a well-developed podzol. Vertical and/or lateral variations in GDGT content and composition were highlighted. In particular, in the tropical sequence, GDGTs were present at relatively low concentrations in the early stages of podzolisation and were more abundant in the well-developed podzolic horizons, where higher acidity and increased bacterial activity may favour their stabilization. Concerning the temperate podzol, GDGT distribution was shown to vary greatly with depth in the soil profile, the methylation degree of bacterial GDGTs being notably higher in the surficial than in the deep soil horizons. Bacterial GDGTs were also detected in the litter layer of the temperate podzol, suggesting the presence of branched-GDGT producing bacteria in the litter, probably in anoxic microenvironments. Last, we showed for the first time that substantial amounts of non-extractable GDGTs could be released after acid hydrolysis of solvent-extracted soils, since non-extractable lipids represented in average ca. 25% of total (i.e. extractable + non-extractable) bacterial GDGTs and ca. 30% of total archaeal GDGTs in podzol samples. In addition, we observed that extractable and non-extractable GDGTs could present different distribution patterns. Thus, the average methylation degree of bacterial GDGTs was higher in the extractable than in the non-extractable lipid fraction in three soil horizons of the temperate podzol. Consequently, different mean air temperature values could be derived from extractable and non-extractable bacterial GDGT distributions, suggesting that data obtained from the extractable lipid fraction have to be interpreted with care. MAT values derived from non-extractable GDGTs were shown to be more consistent with MAT records, implying that MAT estimates obtained from the non-extractable pool might be more reliable.

Microbial life in continental salt pan sediments and their response to climate variability in Northern South Africa

NASA Astrophysics Data System (ADS)

Genderjahn, Steffi; Mangelsdorf, Kai; Alawi, Mashal; Belz, Lukas; Kallmeyer, Jens; Wagner, Dirk

2016-04-01

The environmental history of southwestern African mainland is largely unknown. Since there are no lacustrine systems with constant water coverage in this area, we investigated a continental salt pan as a terrestrial geoarchive with the potential to preserve climate signals. Within the frame of the research project "GeoArchives" (part of the SPACES program, funded by the German Federal Ministry of Education and Research, BMBF) we aimed to reconstruct climate variabilities during the late Pleistocene to Holocene. The presented study is focused on variations within the microbial community structure and abundance of key organisms in a salt pan with special regards to sediment age and geochemical parameters. A combined approach of a 16S rDNA-based quantification method and lipid biomarker analysis was used to demonstrate the response of the microbial communities with respect to environmental changes. The phospholipid derived fatty acids (PLFAs) in sedimentary deposits are characteristic markers for living Bacteria, whereby their side chain represents a fingerprint of the community structure on a broad taxonomic level. Archaeol and isoprenoid glycerol dialkyl glycerol tetraethers (iGDGTs) were used as characteristic makers for Archaea whereas branched GDGTs (brGDGTs) are typical biomarkers for Bacteria. In contrast to PLFAs, they represent dead microbial biomass and thus the past microbial communities in older sediments, since they are already partly degraded. Samples from the Witpan, located in the northwest of South Africa and representing a depths profile from the Late Pleistocene to Holocene, were gathered. Despite the extreme environment with rather low TOC values, restricted availability of water and high salt concentration markers for Bacteria and Archaea were observed. A series of saturated, branched and unsaturated PLFAs were identified. The diversity and concentration of PLFAs were highest in the top layers (up to 30000 ng gsed-1, 0-10 cm) and characteristic markers for cyanobacteria were most abundant. The community composition changed with depths and both the copy numbers of 16S rDNA genes of bacteria (varied from 102 to 105 cell gsed-1) and the amount of PLFAs (up to 3000 ng gsed-1) reflected a low abundance of microorganisms despite increasing feedstock in deeper sediments. Thus, the actual salt pan microbial community is mainly located in the top layers and decreases with depth. In contrast archaeol and GDGTs increased at the transition from Holocene to deeper Late Pleistocene sediments (from 40 up to 3400 ng gsed-1) indicating a higher past microbial abundance during the Late Pleistocene. The increase of GDGTs, TOC, acetate and formate suggested a higher supply of organic matter and a higher microbial activity in this period. Therefore, we assumed an increased precipitation during the Late Pleistocene compared to the arid Holocene in southwestern Africa. We could show the potential of continental salt pans to preserve climate signals during deposition and we demonstrated their potential as a Late Quaternary geoarchive by means of lipid biomarker studies. To describe the environmental habitat, a detailed analysis of diversity and abundance of microorganisms using Next Generation Sequencing is planned.

Molecular multiproxy analysis of ancient root systems suggests strong alteration of deep subsoil organic matter by rhizomicrobial activity

NASA Astrophysics Data System (ADS)

Gocke, Martina; Huguet, Arnaud; Derenne, Sylvie; Kolb, Steffen; Wiesenberg, Guido L. B.

2013-04-01

Roots have a high potential capacity to store large amounts of CO2 in the subsoil. However, associated with rooting, microorganisms enter the subsoil and might contribute to priming effects of carbon mineralisation in the microbial hotspot rhizosphere. Although these processes are well known for recent surface soils, it remains questionable, if and how microorganisms contribute to priming effects in the subsoil and if these effects can be traced after the roots' lifetime. The current study implies several state-of-the-art techniques like DNA and lipid molecular proxies to trace remains of microbial biomass in ancient root systems. These can provide valuable information if parts of the root and rhizomicrobial biomass are preserved, e.g. by encrustation with secondary carbonate during the root's lifespan or shortly thereafter. At the Late Pleistocene loess-paleosol sequence near Nussloch (SW Germany), rhizoliths (calcified roots) occur highly abundant in the deep subsoil from 1 to 9 m depth and below. They were formed by Holocene woody vegetation. Their size can account for up to several cm in diameter and up to > 1 m length. Rhizoliths and surrounding sediment with increasing distances of up to 10 cm, as well as reference loess without visible root remains were collected at several depth intervals. Samples were analysed for n-fatty acids (FAs) and glycerol dialkyl glycerol tetraethers (GDGTs; membrane lipids from Archaea and some Bacteria), as well as structural diversity based on the RNA gene of the prokaryotic ribosome subunit 16S (16S rRNA). GDGT represent organic remains from microbial biomass, whereas FA comprise both microbial remains and degradation products. 16S rRNA indicates the presence of both living cells and/or cell fragments. Despite the general low RNA contents in the sample set, results pointed to a much higher abundance of bacterial compared to archaeal RNA. The latter occured in notable amounts only in some rhizoliths. This was in part enforced by decreasing contents of archeal GDGTs from rhizolith via rhizosphere towards root-free loess. Furthermore, the bacterial fingerprint revealed - similar to modern root systems - higher taxonomic diversity in rhizosphere compared to rhizoliths and reference loess. This argues for microorganisms benefiting from root deposits and exudates. Highest concentrations of branched GDGTs in rhizoliths suggest that their source organisms feed on root remains. Incorporation of rhizomicrobial remains as represented by RNA and GDGTs usually affected the sediment at maximum to a distance of 2-3 cm from the former root. FA contents in rhizosphere showed strong scatter and were in part depleted compared to reference loess or, especially in deeper transects, enriched. This indicates the presence of degradation products originating from former rhizosphere processes. Especially at larger depth not affected by modern pedogenic processes, portions of mainly microbial derived C16 homologues were higher in rhizosphere loess up to distances of 10 cm, revealing that the possible extension of the rhizosphere was underestimated so far. In Corg poor subsoil, the occurence of diverse rhizosphere microorganisms and degradation processes even in several centimeters distant from roots point to a strong alteration of OM, possibly contributing to carbon mineralisation.

Investigating the use of paired Uk'37 and TEX86 measurements to reconstruct past sea surface and subsurface (thermocline) temperatures (Invited)

NASA Astrophysics Data System (ADS)

Castaneda, I. S.; Urann, B.; Phu, V.

2013-12-01

Two organic geochemical temperature proxies widely applied to marine sediments are the Uk'37 Index, based on long-chain alkenones produced by haptophyte algae, and TEX86, based on isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs), produced by Thaumarchaeota. At some locations, temperature reconstructions based on Uk'37 and TEX86 are in agreement within the calibration errors of each proxy, while at other sites absolute Uk'37 and TEX86 reconstructed temperatures differ but both proxies reveal similar overall trends (e.g. Caley et al., 2011). In contrast, at other locations Uk'37 and TEX86 temperature reconstructions from the same samples yield dramatically different overall trends. Differences observed between Uk'37 and TEX86 temperature reconstructions have been attributed to a variety of factors including seasonal production biases, differences in preservation and lateral transport, and differences related to the depth habitat of the source organisms. An increasing number of studies have provided evidence that TEX86 likely reflects a subsurface water temperature in certain areas of the world's oceans and have used paired Uk'37 and TEX86 measurements to simultaneously examine sea surface and subsurface (in some cases thermocline) temperature variability (e.g. Lopes dos Santos et al., 2010; Rommerskirchen et al., 2011; Li et al., 2013). In the tropical N Atlantic, a distinctive signature of Atlantic Meridional Overturning Circulation (AMOC) slowdown is anticorrelated variation between surface and subsurface water temperatures (e.g. Chang et al., 2008; Zhang et al., 2007) where sea surface temperature (SST) cooling is accompanied by shallow subsurface warming (e.g. Chang et al., 2008). Lopes dos Santos et al. (2010) examined a site in the tropical NE Atlantic where they showed that in the modern Uk'37 reflects SST while TEXH86 likely reflects a thermocline temperature. The authors noted several periods during the past 200 kyr when surface cooling and subsurface warming occurred, which they attributed to AMOC slowdown. In this study, we examine sediments from ODP site 660 (NE Atlantic), located near the site studied by Lopes dos Santos et al. (2010), and use paired Uk'37-TEXH86 temperature measurements to investigate changes in sea surface and thermocline temperature variability over the past 4 Ma. We find that following Pliocene warmth, the Uk'37 record indicates an overall cooling trend since ~2.2 Ma, superimposed on glacial-interglacial temperature fluctuations. In contrast, the TEX86 record, which yields consistently cooler temperatures in comparison to Uk'37, does not exhibit an overall cooling trend during the Pleistocene nor elevated warmth during the Pliocene. In portions of the record, anticorrelated variability between Uk'37 and TEX86 temperatures is observed, likely reflecting differences in SST and thermocline temperatures related to AMOC variability. In addition, we examine the carbon (δ13C) and deuterium (δD) isotopic composition of plant leaf waxes, proxies for vegetation type (C3 vs. C4) and precipitation amount, respectively, as several studies have demonstrated close ties between AMOC variability and hydrological conditions in N Africa during the late Pleistocene and Holocene.

Testing the potential of bacterial branched tetraether membrane lipids as temperature proxy in peat and immature coal deposits

NASA Astrophysics Data System (ADS)

Weijers, J. W. H.; Steinmann, P.; Hopmans, E. C.; Basiliko, N.; Finkelstein, S. A.; Johnson, K. R.; Schouten, S.; Sinninghe Damsté, J. S.

2012-04-01

Branched glycerol dialkyl glycerol tetraether (brGDGT) membrane lipids occur ubiquitously in peat and soil. In soil, the degree of methylation and cyclisation of branched tetraethers (MBT index and CBT ratio, respectively) has shown to relate to both soil pH and annual mean air temperature (MAT). Using this relation, past annual MATs can be reconstructed by analysing brGDGTs in marine sediment records near large river outflows. More recently, the potential of this MBT/CBT proxy is also being explored in lakes. Despite being more abundant in peat than soils, however, the utility of the proxy has not yet been fully explored in peat records. Present day peat records generally extent back to the early Holocene, but if the MBT/CBT proxy were shown to be applicable in peat deposits, there is also potential to apply it to immature coal deposits like lignites, which could provide valuable snapshots of continental climate back to the early Cenozoic. Here results are presented of analyses of different peats in south eastern Canada, showing that the pH of peat along a nutrient gradient is rather well reflected by the CBT. Annual MAT reconstructions based on the MBT/CBT soil calibration, however, tend to overestimate measured MAT. This is also the case for peat analysed from the surface of Etang de la Gruère peat bog in the Swiss Jura Mountains. Along the 6m depth profile of this bog (~13ka), CBT-reconstructed pH is compared with in-situ measured pore water pH showing that the brGDGT composition does not reflect present-day in-situ conditions. Instead, it reflects a stratigraphic boundary between Carex and Sphagnum dominated peat at 4 m depth that is not present in the pore water profile, testifying to a 'fossil' nature of the brGDGTs down the peat bog. Analyses of three immature coals of the Argonne Premium Coal Series reveal that branched GDGTs are present in the most immature coal, the Beulah Zap lignite (Ro = 0.25%), and only just above detection limit in the Wyodak Anderson coal (Ro = 0.32%), both of about the same age (Late Palaeocene). In the more mature Illinois #6 coal (Ro = 0.46%), brGDGTs are completely absent. In the Denver Basin, a comparison is made between outcrop and drilled core samples of Palaeocene lignites. BrGDGTs are preserved in the core samples, although in low quantities compared to peat. Outcrop samples are clearly overprinted by modern soil derived brGDGTs, despite digging a meters deep trench, which shows the need to obtain fresh non-weathered samples by coring. Reconstructed annual MAT for both the Beulah Zap and the Denver Basin lignites are several degrees higher than estimates based on leaf margin and oxygen isotope analyses from the same sites. Both reconstructions do testify, nevertheless, to the warm continental conditions during the early Cenozoic of the central U.S.A.. Although further validation is required, potentially in the form of a specific peat calibration, these results do show potential for application of the MBT/CBT temperature proxy in peat and lignite deposits.

Pushing open-ocean organic paleo-environmental proxies to the margin: Narragansett Bay, RI

NASA Astrophysics Data System (ADS)

Salacup, J. M.; Herbert, T.; Prell, W. L.

2010-12-01

Estuarine sediment deposits provide an under-utilized opportunity to reconstruct high-resolution records of environmental change from the highly sensitive intersection of oceanic and terrestrial systems. Previous applications of both well-established and novel organic geochemical proxies to estuaries have met with mixed success. Compared to oceanic settings, the large dynamic range of tidal currents, water temperature, salinity, nutrients, and productivity both enrich and complicate estuarine sedimentary records. Here, we present the results of monthly samples of water-column particulate organic matter and compare them to a suite of sediment cores in an effort to elucidate how the environmental signal produced in the water-column is translated to the sediment. Specifically, we measured alkenones and glycerol dialkyl glycerol tetraethers (GDGTs), the bases for the Uk’37 sea-surface temperature (SST) and C-37total primary productivity proxies, and the TEX86 SST and BIT Index proxies, respectively. Alkenones, produced by haptophyte algae, are present in most of our water-column samples; however, concentrations in many samples are too low to reliably calculate temperature. When reliable, water-column alkenones infer SSTs between 13-16°C, consistent with sediment core-top Uk’37 SST estimates. These correlate to May and Oct SSTs, coinciding with the terminations of the summer-fall and winter-spring algal blooms in Narragansett Bay. In contrast to alkenone fingerprints reported from the much lower salinity Chesapeake Bay, Narragansett Bay samples lack significant contributions of the C37:4 ketone, consistent with production by open-ocean haptophytes. Notably, sedimentary records of Uk’37-inferred SST show strong inter-core centennial-to-decadal coherence. The structure and absolute values of inferred SSTs correlate well with instrumental mean Sept-Oct air temperatures back to 1895, and contain structure consistent with the late Little Ice Age and 20th century warming. Our record indicates that the past 100 in Narragansett Bay are the warmest in at least the last 500. Water-column values of the GDGT-based BIT Index, a proxy for the delivery of terrestrial organic matter (TOM), decrease down-Bay with distance from the major rivers. However, absolute values of the index, exceeding 0.8-0.9 in the upper half of the Bay, are more consistent with soil samples than water and are hard to reconcile with high level of marine productivity. Sedimentary values of the BIT Index are also high, between ~0.4 and 0.8, and their profiles suggest that Colonization (~1700) and Industrialization (~1850) altered terrestrial sediment delivery to the Bay. Such high values of the BIT Index suggest the utility of TEX86 may be complicated by terrestrial GDGT contributions. Indeed, sedimentary values for TEX86 are highly variable and show little correlation with Uk’37 or instrumental records. Our results confirm the utility of organic geochemical proxies in estuarine settings while advocating the application of more than one. In Narragansett Bay, this approach has allowed the reconstruction of local historically and climatically important events such as the impacts of European settlement, the Industrial Revolution, and 20th century warming.

Constraints on the sources of branched GDGTs in open ocean sediments: dust transport or in situ production?

NASA Astrophysics Data System (ADS)

Weijers, J.; Schefuss, E.; Kim, J.; Sinninghe Damsté, J. S.; Schouten, S.

2012-12-01

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids synthesized by soil bacteria that, upon soil erosion, are transported by rivers to the ocean where they accumulate in the near shore sedimentary archive. The degrees of cyclisation (CBT) and methylation (MBT) of these compounds have been shown to relate to soil pH and annual mean air temperature [1]. Therefore, brGDGTs in near shore sedimentary archives can be used to estimate past continental air temperatures and enable a direct comparison of these to marine sea surface temperature estimates obtained from the same samples. In addition, brGDGT abundance relative to crenarchaeol, an isoprenoid GDGT synthesized by marine pelagic Thaumarchaeota, quantified in the branched vs. isoprenoid tetraether (BIT) index, is an indicator of the relative input of soil organic matter in near shore sediments [2]. High BIT values near river outflows testify of relative strong soil organic matter input and generally the BIT index will decrease off shore to values near 0, the marine end-member value. Even in remote open ocean sediments, however, the BIT index will rarely reach 0 as small amounts of brGDGTs are often present. The occurrence of these brGDGTs in open marine settings might be a result of i) dust input, ii) sediment dispersion from near coastal areas, or iii) in situ production in marine sediments. In order to constrain the origin of branched GDGTs in open marine sediments we analyzed i) atmospheric dust samples taken along an equatorial African coastal transect, ii) marine surface waters near and away of the Congo river outflow, iii) a series of surface sediments at and around the Congo deep sea fan, and iv) a series of open marine surface sediments from different oceans with BIT values < 0.08. Our results show that brGDGTs are present, though in relative low amounts, in dust. Their distribution resembles that of soil input as also found in the Congo deep sea fan, with MBT and CBT values that could be representative of tropical African soils. Strikingly, BIT indices are much lower than expected for soils (0.15-0.42), likely as a result of sea spray on the dust filters. Open ocean sediments, on the contrary, are typically characterized by relative high amounts of cyclopentane containing brGDGTs resulting in low CBT values ranging from -0.4 - 0.8. These values are similarly low as reported earlier in marine sediments near Svalbard [3] and in the East China Sea [4], for which in situ production was invoked. Thus, brGDGT transport by dust does seem possible, though quantities are low. Since open ocean brGDGT distributions are markedly different from those in soils and dust, the latter is most likely not a significant source. Our results indicate that production of brGDGTs in ocean sediments, though in relative low amounts, is much more widespread than previously thought. This emphasizes that the MBT-CBT proxy for continental air temperature should only be used at locations where soil organic matter input is significant as evidenced by high BIT indices. References: [1] Weijers J.W.H. et al. (2007) Geochmim. Cosmochim. Acta 71, 703-713. [2] Hopmans E.C. et al. (2004) Earth Planet. Sci. Lett. 224, 107-116. [3] Peterse F. et al. (2009) Org. Geochem. 40, 692-699. [4] Zhu C. Et al. (2011) Org. Geochem. 42, 376-386.

Fluorinated arene, imide and unsaturated pyrrolidinone based donor acceptor conjugated polymers: Synthesis, structure-property and device studies

NASA Astrophysics Data System (ADS)

Liyanage, Arawwawala Don Thilanga

After the discovery of doped polyacetylene, organic semiconductor materials are widely studied as high impending active components in consumer electronics. They have received substantial consideration due to their potential for structural tailoring, low cost, large area and mechanically flexible alternatives to common inorganic semiconductors. To acquire maximum use of these materials, it is essential to get a strong idea about their chemical and physical nature. Material chemist has an enormous role to play in this novel area, including development of efficient synthetic methodologies and control the molecular self-assembly and (opto)-electronic properties. The body of this thesis mainly focuses on the substituent effects: how different substituents affect the (opto)-electronic properties of the donor-acceptor (D-A) conjugated polymers. The main priority goes to understand, how different alkyl substituent effect to the polymer solubility, crystallinity, thermal properties (e.g.: glass transition temperature) and morphological order. Three classes of D-A systems were extensively studied in this work. The second chapter mainly focuses on the synthesis and structure-property study of fluorinated arene (TFB) base polymers. Here we used commercially available 1,4-dibromo-2,3,5,6-tetrafluorobenzene (TFB) as the acceptor material and prepare several polymers using 3,3'-dialkyl(3,3'-R2T2) or 3,3'-dialkoxy bithiophene (3,3'-RO2T2) units as electron donors. A detail study was done using 3,3'-bithiophene donor units incorporating branched alkoxy-functionalities by systematic variation of branching position and chain length. The study allowed disentangling the branching effects on (i) aggregation tendency, intermolecular arrangement, (iii) solid state optical energy gaps, and (iv) electronic properties in an overall consistent picture, which might guide future polymer synthesis towards optimized materials for opto-electronic applications. The third chapter mainly focused on the structure-property study of imide functionalized D-A polymers. Here we used thiophene-imide (TPD) as the acceptor moiety and prepare several D-A polymers by varying the donor units. When selecting the donor units, more priority goes to the fused ring systems. One main reason to use imide functionality is due to the, open position of the imide nitrogen, which provides an attaching position to alkyl substituent. Through this we can easily manipulate solubility and solid state packing arrangement. Also these imide acceptors have low-lying LUMOs due to their electron deficient nature and this will allow tuning the optical energy gap by careful choice of donor materials with different electron donating ability. The fourth chapter mainly contribute to the synthesis and structure property study of a completely novel electron acceptor moiety consist of a unsaturated pyrrolidinone unit known as Pechmann dye (PD) core. Pechmann dyes are closely related to the Indigo family. This can refer as 3-butenolide dimer connected via an alkene bridge, containing a benzene ring at the 5 and 5' positions of the lactone rings. We have prepared several D-A polymers using this PD system with benzodithiophene (BDT) as the donor unit. Different to common D-A polymers the HOMO and LUMO of the PD acceptor moiety are energetically located within the gap of the BDT, so that the electronic and optical properties (HOMO-LUMO transition) are dictated by the PD properties. The promising electronic properties, band gaps, high absorption coefficients and broad absorption suggest this new D-A polymers as an interesting donor material for organic solar cell (OSC) applications. KEY WORDS: Organic semiconductor materials, Self assembly, (opto)-electronic properties, Donor-Acceptor conjugated polymers, Fluorinated arene, 3,3'-bithiophene donors, Thiophene-imide (TPD), Pechmann dye, benzodithiophene, organic solar cell.

Half-sandwich rare-earth-catalyzed olefin polymerization, carbometalation, and hydroarylation.

PubMed

Nishiura, Masayoshi; Guo, Fang; Hou, Zhaomin

2015-08-18

The search for new catalysts for more efficient, selective chemical transformations and for the synthesis of new functional materials has been a long-standing research subject in both academia and industry. To develop new generations of catalysts that are superior or complementary to the existing ones, exploring the potential of untapped elements is an important strategy. Rare-earth elements, including scandium, yttrium, and the lanthanides (La-Lu), constitute one important frontier in the periodic table. Rare-earth elements possess unique chemical and physical properties that are different from those of main-group and late-transition metals. The development of rare-earth-based catalysts by taking the advantage of these unique properties is of great interest and importance. The most stable oxidation state of rare-earth metals is 3+, which is difficult to change under many reaction conditions. The oxidative addition and reductive elimination processes often observed in catalytic cycles involving late transition metals are generally difficult in the case of rare-earth complexes. The 18-electron rule that is applicable to late-transition-metal complexes does not fit rare-earth complexes, whose structures are mainly governed by the sterics (rather than the electron numbers) of the ligands. In the lanthanide series (La-Lu), the ionic radius gradually decreases with increasing atomic number because of the influence of the 4f electrons, which show poor shielding of nuclear charge. Rare-earth metal ions generally show strong Lewis acidity and oxophilicity. Rare-earth metal alkyl and hydride species are highly reactive, showing both nucleophilicity and basicity. The combination of these features, such as the strong nucleophilicity and moderate basicity of the alkyl and hydride species and the high stability, strong Lewis acidity, and unsaturated C-C bond affinity of the 3+ metal ions, can make rare-earth metals unique candidates for the formation of excellent single-site catalysts. This Account is intended to give an overview of our recent studies on organo rare-earth catalysis, in particular the synthesis and application of half-sandwich rare-earth alkyl complexes bearing monocyclopentadienyl ligands for olefin polymerization, carbometalation, and hydroarylation. Treatment of half-sandwich rare-earth dialkyl complexes having the general formula CpMR2 with an equimolar amount of an appropriate borate compound such as [Ph3C][B(C6F5)4] can generate the corresponding cationic monoalkyl species, which serve as excellent single-site catalysts for the polymerization and copolymerization of a wide range of olefin monomers such as ethylene, 1-hexene, styrene, conjugated and nonconjugated dienes, and cyclic olefins. The cationic half-sandwich rare-earth alkyl complexes can also catalyze the regio- and stereoselective alkylative alumination of alkenes and alkynes through insertion of the unsaturated C-C bond into the metal-alkyl bond followed by transmetalation between the resulting new alkyl or alkenyl species and an alkylaluminum compound. Moreover, a combination of deprotonative C-H bond activation of appropriate organic compounds such as anisoles and pyridines by the rare-earth alkyl species and insertion of alkenes into the resulting new metal-carbon bond can lead to catalytic C-H bond alkylation of the organic substrates. Most of these transformations are unique to the rare-earth catalysts with selectivity and functional group tolerance different from those of late-transition-metal catalysts.

Structure and chemistry of model catalysts in ultrahigh vacuum

NASA Astrophysics Data System (ADS)

Walker, Joshua D.

The study of catalysis is a key area of focus not only in the industrial sector but also in the nature and biological systems. The market for catalysis is a multi-billion dollar industry. Many of the materials and products we use on a daily basis are formed through a catalytic process. The quest to understanding and improving catalytic mechanisms is ongoing. Many model catalysts use transition metals as a support for chemical reactions to take place due to their selectivity and activity. Palladium, gold, and copper metals are studied in this work and show the ability to be catalytically reactive. It is important to understand the characteristics and properties of these surfaces. A well-known example of catalysis is the conversion of carbon monoxide (CO), a very harmful gas to carbon dioxide (CO2) which is less harmful. This reaction is mainly seen in the automotive industry. This reaction is investigated in this work on a Au(111) single crystal, which is normally inert but becomes reactivity with the adsorption of oxygen on the surface. Temperature Programmed Desorption (TPD) is used to understand some of the chemistry and effects with and without the addition of H2O. The oxidation of CO is shown to be enhanced by the addition of water, but warrants further analysis too fully understand the different mechanisms and reaction pathways existing. The field of nano-electronics is rapidly growing as technology continues to challenge scientists to create innovative ideas. The trend to produce smaller electronic products is increasing as consumer demands persist. It has been shown previously that 1,4-phenlyene diisocyanobenzene (1,4-PDI) on Au(111) react to form one-dimensional oligomer chains comprising alternating gold and 1,4-PDI units on the Au(111) surface. A similar compound 1,3-phenlyene diisocyanobenzene (1,3-PDI) was studied in order to investigate whether the oligomerization found for 1,4-PDI is a general phenomenon and to ultimately explore the effect of molecular geometry on electron transport using a range of surface-sensitive techniques. Sulfur-containing molecules, in particular those with sulfur-sulfur linkages, are used as lubricant additives for ferrous surfaces [1-14] so that dialkyl disulfides have been used as simple model compounds to explore the surface and tribological chemistry on iron [15,16] where they react at the high temperatures attained at the interface during rubbing to deposit a ferrous sulfide film. However, the tribological chemistry can depend critically on the nature of the substrate so that a good lubricant additive for one type of surface may not be applicable to another. In particular, the lubrication of sliding copper-copper interfaces in electrical motors [17-20] provides a particular challenge. To study this system surface sensitive techniques Low energy electron diffraction (LEED) and TPD surface analysis was employed. LEED experiments suggest that tribological experiments can be conducted on copper foils rather than copper single crystals and produce comparable results. The ability to produce ideal model catalysts is very important in the Surface science field. To enhance catalytic performance of these catalysts, various strategies can be used in the preparation process. One approach in this quest is to produce an alloy surface that increases the activity of the surface. The process of developing and understanding the chemistry of AuPd alloys was probed in detail using TPD, LEED and Density Functional Theory (DFT).

Palladium-Catalyzed Oxidative Couplings and Applications to the Synthesis of Macrocycles and Strained Cyclic Dienes

NASA Astrophysics Data System (ADS)

Boon, Byron Adrian

The palladium(II)-catalyzed oxidative macrocyclization of bis(vinylboronate esters) is demonstrated as an efficient method for the synthesis of macrocyclic dienes. The macrocyclization reactions feature mild conditions due to a palladium(II) catalytic cycle which obviates the need for a high energy oxidative addition step of standard palladium(0) catalytic cycles. Instead, this oxidative coupling is promoted by chloroacetone as a terminal re-oxidant in the catalytic cycle. An extension of the oxidative coupling/macrocyclization strategy is highlighted where molecular oxygen may be used in place of chloroacetone as the terminal re-oxidant. Homocoupling reactions of vinylboronate esters served as a template to screen reaction conditions for this method. From these experiments, multiple reaction conditions gave the oxidative homocoupling product in high yield. These reaction conditions were successfully applied to the oxidative macrocyclization of a bis(vinylboronate ester) using molecular oxygen as a re-oxidant. Syntheses of strained cyclic dienes were accomplished via the palladium(II)-catalyzed oxidative cyclizations of terminal bis(vinylboronate esters). The reactions generated strained (E,E)-1,3-dienes that underwent spontaneous 4?-electrocyclizations to form bicyclic cyclobutenes. Formation of the cyclobutenes is driven by strain in the medium-ring (E,E)-1,3-diene intermediates. Thermal ring openings of the cyclobutenes give (Z,Z)-1,3-diene products, again for thermodynamic reasons. These results are in contrast with typical acyclic trans-3,4-dialkyl cyclobutenes, which favor outward torquoselective ring-openings to give (E,E)-1,3-dienes. DFT calculations verified the thermodynamic versus kinetic control of the reactions and kinetic studies are in excellent agreement with the calculated energy changes. Investigations on the transannular Pauson-Khand reaction are also highlighted. The Pauson-Khand reaction is a powerful tool for the synthesis of cyclopentenones through the efficient [2+2+1] cycloaddition of dicobalt alkyne complexes with alkenes. While intermolecular and intramolecular variants are widely known, transannular versions of this reaction are unknown and the basis of this study. Our successful transannular Pauson-Khand reaction required a cyclic enyne incorporating one short three-membered linker chain and a rigid aryl linker in the backbone of the long linker chain. This rigidity of the aryl linker is proposed to facilitate the transannular [2+2+1] cyclization. Computational studies revealed that transannular Pauson-Khand reactions are thermodynamically favored for cyclic enynes featuring a long linker of at least 5 carbons, but with smaller chains the reactions are thermodynamically disfavored. Experimental studies show that long linking chains with more than 5 members are required to prevent to steric interactions between the dicobalt hexacarbonyl moiety and the linking chain to allow the reaction to be kinetically favored. The final part of this work highlights progress towards the total synthesis of (+)-kingianin A. This natural product was isolated as a racemic mixture from the bark of Endiandra kingiana and is an inhibitor of antiapoptotic protein Bcl-Xl, highlighting its potential use in cancer treatments. Its structure is proposed to arise from an intermolecular Diels-Alder dimerization reaction of bicyclo[4.2.0]octadiene fragments derived from an 8pi/6pi-electrocyclization cascade. Although two total syntheses of (+/-)-kingianin A have been reported, an enantioselective synthesis has not been achieved and is the purpose of this study. This synthetic route begins from L-(+)-dimethyl tartrate, a cheap and commercially available starting material, and aims to follow a biomimetic synthetic pathway featuring a substrate controlled diastereoselective palladium(II)-catalyzed oxidative cyclization and 8pi/6pi-electrocyclization cascade. Although the feasibility of this cascade pathway has not yet been realized, key synthetic transformations to install the requisite carbocyclic framework of (+)-kingianin A have been discovered, paving the way for future investigations on the palladium(II)-catalyzed coupling/electrocyclization cascade and completion of the synthesis.

Seasonal and spatial contrasts of sedimentary organic carbon in floodplain lakes of the central Amazon basin.

NASA Astrophysics Data System (ADS)

Sobrinho, Rodrigo; Kim, Jung-Hyun; Abril, Gwenaël; Zell, Claudia; Moreira-Turcq, Patricia; Mortillaro, Jean-Michel; Meziane, Tarik; Damsté, Jaap; Bernardes, Marcelo

2014-05-01

Three-quarters of the area of flooded land in the world are temporary wetlands (Downing, 2009), which play a significant role in the global carbon cycle(Einsele et al., 2001; Cole et al., 2007; Battin et al., 2009; Abril et al., 2013). Previous studies of the Amazonian floodplain lakes (várzeas), one important compartment of wetlands, showed that the sedimentation of organic carbon (OC) in the floodplain lakes is strongly linked to the periodical floods and to the biogeography from upstream to downstream(Victoria et al., 1992; Martinelli et al., 2003). However, the main sources of sedimentary OC remain uncertain. Hence, the study of the sources of OC buried in floodplain lake sediments can enhance our understanding of the carbon balance of the Amazon ecosystems. In this study, we investigated the seasonal and spatial pattern of sedimentary organic matter in five floodplain lakes of the central Amazon basin (Cabaliana, Janauaca, Canaçari, Miratuba, and Curuai) which have different morphologies, hydrodynamics and vegetation coverage. Surface sediments were collected in four hydrological seasons: low water (LW), rising water (RW), high water (HW) and falling water (FW) in 2009 and 2010. We investigated commonly used bulk geochemical tracers such as C:N ratio and stable isotopic composition of organic carbon (δ13COC). These results were compared with lignin-phenol parameters as an indicator of vascular plant detritus (Hedges and Ertel, 1982) and branched glycerol dialkyl glycerol tetraethers (brGDGTs) to trace the soil OC from land to the aquatic settings (Hopmans et al., 2004). Our data showed that during the RW and FW seasons, the concentration of lignin and brGDGTs were higher in comparison to other seasons. Our study also indicated that floodplain lake sediments primarily consisted of a mixture of C3 plant detritus and soil OC. However, a downstream increase in C4 plant-derived OC contribution was observed along the gradient of increasingly open waters, i.e. from upstream to downstream. We also identify the OC contribution from the seasonally flooded forests, i.e. temporary wetlands as the most important source of sedimentary OC in floodplain lakes. Accordingly, we attribute temporal and spatial difference in sedimentary OC composition to the hydrological connectivity between the Amazon River and its floodplain lakes and thus between the surrounding forests and the floodplain lakes. References: Abril, G., J.-M.Martinez, Artigas, L.F., Moreira-Turcq, P., Benedetti, M.P., Vidal, L., Meziane, T., Kim, J.-H., Bernardes, M.C., Savoye, N., Deborde, J., Albéric, P., Souza, M.F.L., Souza, E.L., Roland, F. Amazon River carbon dioxide outgassing fuelled by wetlands. Nature accepted (2013). Battin, T.J., Luyssaert, S., Kaplan, L.A., Aufdenkampe, A.K., Richter, A., Tranvik, L.J., 2009. The boundless carbon cycle. Nature Geoscience 2, 598 - 600 (2009). Cole, J.J., Prairie, Y.T., Caraco, N.F., McDowell, W.H., Tranvik, L.J., Striegl, R.G., Duarte, C.M., Kortelainen, P., Downing, J.A., Middelburg, J.J., Melack, J. Plumbing the Global Carbon Cycle: Integrating Inland Waters into the Terrestrial Carbon Budget. Ecosystems 10, 171 - 184 (2007). Downing, J. A. Global limnology: up-scaling aquatic services and processes to planet Earth. Verh Internat Verein Limnol 30, 1149.-1166 (2009). Einsele, G., Yan, J., Hinderer, M. Atmospheric carbon burial in modern lake basins and its significance for the global carbon budget. Global and Planetary Change 30, 167 - 195 (2001). Hedges, J.I., Ertel, J.R. Characterization of Lignin by Gas Capillary Chromatography of Cupric Oxide Oxidation Products. Analitical Chemistry 54, 174-178 (1982). Hopmans, E.C., Weijers, J.W.H., Schefu, E., Herfort, L., Damste, J.S.S., Schouten, S.,. A novel proxy for terrestrial organic matter in sediments based on branched and isoprenoid tetraether lipids. Earth and Planetary Science Letters 224, 107 - 116 (2004). Martinelli, L.A., Victoria, R.L., Camargo, P.B.d., Piccolo, M.d.C., Mertes, L., Richey, J.E., Devol, A.H., Forsberg, B.R.. Inland variability of carbon-nitrogen concentrations and d13C in Amazon floodplain (várzea) vegetation and sediment. Hydrol. Process. 17, 1419-1430 (2003). Victoria, R.L., Martinelli, L.A., Trivelin, P.C.O., Matsui, E., Forsberg, B.R., Richey, J.E., Devol, A.H.. The use of stable isotopes in studies of nutrient cycling: Carbon Isotope composition of Amazon varzea sediments. Biotropica 24, 240-249 (1992).