Chemotaxis of Pseudomonas to furans

USDA-ARS?s Scientific Manuscript database

Background: Furfural (2-furaldehyde) is a furan compound formed by dehydration of pentose sugars. Furan molecules occur naturally in the environment and are also used industrially as solvents and chemical precursors. Although furan aldehydes are microbial inhibitors, a number of microbes can utilize...

Trapping of cis-2-butene-1,4-dial to measure furan metabolism in human liver microsomes by cytochrome P450 enzymes.

PubMed

Gates, Leah A; Lu, Ding; Peterson, Lisa A

2012-03-01

Furan is a liver toxicant and carcinogen in rodents. It is classified as a possible human carcinogen, but the human health effects of furan exposure remain unknown. The oxidation of furan by cytochrome P450 (P450) enzymes is necessary for furan toxicity. The product of this reaction is the reactive α,β-unsaturated dialdehyde, cis-2-butene-1,4-dial (BDA). To determine whether human liver microsomes metabolize furan to BDA, a liquid chromatography/tandem mass spectrometry method was developed to detect and quantify BDA by trapping this reactive metabolite with N-acetyl-l-cysteine (NAC) and N-acetyl-l-lysine (NAL). Reaction of NAC and NAL with BDA generates N-acetyl-S-[1-(5-acetylamino-5-carboxypentyl)-1H-pyrrol-3-yl]-l-cysteine (NAC-BDA-NAL). Formation of NAC-BDA-NAL was quantified in 21 different human liver microsomal preparations. The levels of metabolism were comparable to that observed in F-344 rat and B6C3F1 mouse liver microsomes, two species known to be sensitive to furan-induced toxicity. Studies with recombinant human liver P450s indicated that CYP2E1 is the most active human liver furan oxidase. The activity of CYP2E1 as measured by p-nitrophenol hydroxylase activity was correlated to the extent of NAC-BDA-NAL formation in human liver microsomes. The formation of NAC-BDA-NAL was blocked by CYP2E1 inhibitors but not other P450 inhibitors. These results suggest that humans are capable of oxidizing furan to its toxic metabolite, BDA, at rates comparable to those of species sensitive to furan exposure. Therefore, humans may be susceptible to furan's toxic effects.

Trapping of cis-2-Butene-1,4-dial to Measure Furan Metabolism in Human Liver Microsomes by Cytochrome P450 Enzymes

PubMed Central

Gates, Leah A.; Lu, Ding

2012-01-01

Furan is a liver toxicant and carcinogen in rodents. It is classified as a possible human carcinogen, but the human health effects of furan exposure remain unknown. The oxidation of furan by cytochrome P450 (P450) enzymes is necessary for furan toxicity. The product of this reaction is the reactive α,β-unsaturated dialdehyde, cis-2-butene-1,4-dial (BDA). To determine whether human liver microsomes metabolize furan to BDA, a liquid chromatography/tandem mass spectrometry method was developed to detect and quantify BDA by trapping this reactive metabolite with N-acetyl-l-cysteine (NAC) and N-acetyl-l-lysine (NAL). Reaction of NAC and NAL with BDA generates N-acetyl-S-[1-(5-acetylamino-5-carboxypentyl)-1H-pyrrol-3-yl]-l-cysteine (NAC-BDA-NAL). Formation of NAC-BDA-NAL was quantified in 21 different human liver microsomal preparations. The levels of metabolism were comparable to that observed in F-344 rat and B6C3F1 mouse liver microsomes, two species known to be sensitive to furan-induced toxicity. Studies with recombinant human liver P450s indicated that CYP2E1 is the most active human liver furan oxidase. The activity of CYP2E1 as measured by p-nitrophenol hydroxylase activity was correlated to the extent of NAC-BDA-NAL formation in human liver microsomes. The formation of NAC-BDA-NAL was blocked by CYP2E1 inhibitors but not other P450 inhibitors. These results suggest that humans are capable of oxidizing furan to its toxic metabolite, BDA, at rates comparable to those of species sensitive to furan exposure. Therefore, humans may be susceptible to furan's toxic effects. PMID:22187484

Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

PubMed

De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

2005-01-21

Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

Furan in Thermally Processed Foods - A Review

PubMed Central

Seok, Yun-Jeong; Her, Jae-Young; Kim, Yong-Gun; Kim, Min Yeop; Jeong, Soo Young; Kim, Mina K.; Lee, Jee-yeon; Kim, Cho-il; Yoon, Hae-Jung

2015-01-01

Furan (C4H4O) is a volatile compound formed mostly during the thermal processing of foods. The toxicity of furan has been well documented previously, and it was classified as “possible human carcinogen (Group 2B)” by the International Agency for Research on Cancer. Various pathways have been reported for the formation of furan, that is, thermal degradation and/or thermal rearrangement of carbohydrates in the presence of amino acids, thermal degradation of certain amino acids, including aspartic acid, threonine, α-alanine, serine, and cysteine, oxidation of ascorbic acid at higher temperatures, and oxidation of polyunsaturated fatty acids and carotenoids. Owing to the complexity of the formation mechanism, a vast number of studies have been published on monitoring furan in commercial food products and on the potential strategies for reducing furan. Thus, we present a comprehensive review on the current status of commercial food monitoring databases and the possible furan reduction methods. Additionally, we review analytical methods for furan detection and the toxicity of furan. PMID:26483883

Diversity-oriented synthesis leads to an effective class of bifunctional linchpins uniting anion relay chemistry (ARC) with benzyne reactivity

PubMed Central

Smith, Amos B.; Kim, Won-Suk

2011-01-01

In conjunction with the construction of a diversity-oriented synthesis library of 10-membered ring “natural product-like” macrolides, the design, synthesis, and validation of a unique class of bifunctional linchpins, uniting benzyne reactivity initiated by type II anion relay chemistry (ARC) has been achieved, permitting access to diverse [2+2], [3+2], and [4+2] cycloadducts. PMID:21245309

Furan in roasted, ground and brewed coffee

PubMed

Gruczyńska, Eliza; Kowalska, Dorota; Kozłowska, Mariola; Majewska, Ewa; Tarnowska, Katarzyna

2018-01-01

Coffee is the most popular hot beverage in the world. The annual coffee production in 2010, 2014 and 2016 was 8.1, 9.0 and 9.3 million tons respectively. There are more than 100 coffee species, but only two of them: Arabica (Coffea arabica) and Robusta (Coffea canephora) have gained commercial importance. During roasting of green coffee beans not only desirable compounds are formed, that exert positive influence on the taste and flavour of coffee, but also small quantities of undesirable ones. Furan (C4H4O) is one of the latter. Furan is a volatile compound (boiling temp. of 31.4 oC) formed during thermal processing of food. The toxicity of furan has been well documented and it is classified as “possible human carcinogen” (Group 2B) by the International Agency for Research on Cancer. Various pathways have been reported for furan formation during food processing. It can be formed from carbohydrates, amino acids by their thermal degradation or thermal re-arrangement and by oxidation of ascorbic acid and polyunsaturated acids and carotenoids. High concentrations of furan have been reported in coffee, baked and roasted food and in food subjected to preserving in cans and jars. Furan levels in brewed coffee are typically near or below 120 μg/L, but it can approach thousands μg/kg in roasted whole beans or ground coffee. The highest concentration of furan in roasted coffee reaches the level of 7000 μg/kg. Taking into account that coffee is the most popular hot drink, it becomes the main contributor to furan exposure from dietary sources for adults. In this article the published scientific papers concerned with the presence of furan in roasted non-brewed and brewed coffee have been reviewed. The formation mechanisms and occurrence of furan in coffee and the harmful influence of furan on the consumer health have been discussed.

Polyamines are traps for reactive intermediates in furan metabolism

PubMed Central

Peterson, Lisa A.; Phillips, Martin B.; Lu, Ding; Sullivan, Mathilde M.

2011-01-01

Furan is toxic and carcinogenic in rodents. Because of the large potential for human exposure, furan is classified as a possible human carcinogen. The detailed mechanism by which furan causes toxicity and cancer is not yet known. Since furan toxicity requires cytochrome P450-catalyzed oxidation of furan, we have characterized the urinary and hepatocyte metabolites of furan to gain insight into the chemical nature of the reactive intermediate. Previous studies in hepatocytes indicated that furan is oxidized to the reactive α,β-unsaturated dialdehyde, cis-2-butene-1,4-dial (BDA), which reacts with glutathione (GSH) to form 2-(S-glutathionyl)-succinaldehyde (GSH-BDA). This intermediate forms pyrrole cross-links with cellular amines such as lysine and glutamine. In this report, we demonstrate that GSH-BDA also forms cross-links with ornithine, putrescine and spermidine when furan is incubated with rat hepatocytes. The relative levels of these metabolites are not completely explained by hepatocellular levels of the amines or by their reactivity with GSH-BDA. Mercapturic acid derivatives of the spermidine cross-links were detected in the urine of furan-treated rats, which indicates that this metabolic pathway occurs in vivo. Their detection in furan-treated hepatocytes and in urine from furan-treated rats indicates that polyamines may play an important role in the toxicity of furan PMID:21842885

An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.

PubMed

DeKorver, Kyle A; Hsung, Richard P; Song, Wang-Ze; Wang, Xiao-Na; Walton, Mary C

2012-06-15

A cascade of Pd-catalyzed N-to-C allyl transfer-intramolecular ketenimine-[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines.

Furan

Integrated Risk Information System (IRIS)

Furan ; CASRN 110 - 00 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects ) a

An Intramolecular [2 + 2] Cycloaddition of Ketenimines via Palladium-Catalyzed Rearrangements of N-Allyl-Ynamides

PubMed Central

DeKorver, Kyle A.; Song, Wang-Ze; Wang, Xiao-Na; Walton, Mary C.

2012-01-01

A cascade of Pd-catalyzed N-to-C allyl transfer–intramolecular ketenimine–[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines. PMID:22667819

Effect of consumer cooking on furan in convenience foods.

PubMed

Roberts, D; Crews, C; Grundy, H; Mills, C; Matthews, W

2008-01-01

The effect of domestic preparation regimes on the level of the heat-formed toxicant furan was studied to provide useful information for exposure assessment and advice for manufacturers and consumers. Foods were cooked in a saucepan on a gas hob or microwaved and furan was determined by headspace sampling with gas chromatography-mass spectrometry. In general, furan levels did not decrease as much when foods were cooked in a microwave oven when compared with the same foods cooked in a saucepan. Furan levels decreased in most canned and jarred foods after heating in a saucepan. Low levels of furan in soups in cartons were not changed by any procedure. Furan decreased slightly in foods on standing before consumption, but did so more rapidly on stirring. The levels also decreased slightly when foods were left to stand on plates; this observation is attributed to the volatility of furan.

Solvent-dependent reactions for the synthesis of β-keto-benzo-δ-sultone scaffolds via DBU-catalyzed O-sulfonylation/intramolecular Baylis-Hillman/1,3-H shift or dehydration tandem sequences.

PubMed

Ghandi, Mehdi; Bozcheloei, Abolfazl Hasani; Nazari, Seyed Hadi; Sadeghzadeh, Masoud

2011-12-16

We have developed a solvent-dependent method for the synthesis of novel benzo-δ-sultone scaffolds. A variety of benzylbenzo[e][1,2]oxathiin-4(3H)-one-2,2-dioxides were obtained in high yields in DMF using a one-pot, DBU-catalyzed condensation of 2-hydroxybenzaldehydes with a number of (E)-2-phenylethenesulfonyl chlorides. On the other hand, the initially prepared 2-formylphenyl-(E)-2-phenylethenesulfonate derivatives underwent DBU-catalyzed reactions to a series of 3-[methoxy(phenyl)methyl]benzo[e][1,2]oxathiine-2,2-dioxides in moderate to good yields in MeOH. These reactions presumably proceed via DBU-catalyzed O-sulfonylation/intramolecular Baylis-Hillman/1,3-H shift or dehydration tandem sequences, respectively.

Process for producing furan from furfural aldehyde

DOEpatents

Diebold, James P.; Evans, Robert J.

1988-01-01

A process of producing furan and derivatives thereof is disclosed. The process includes generating furfural aldehyde vapors and then passing those vapors over a zeolite catalyst at a temperature and for a residence time effective to decarbonylate the furfural aldehydes to form furans and derivatives thereof. The resultant furan vapors and derivatives are then separated. In a preferred form, the furfural aldehyde vapors are generated during the process of converting biomass materials to liquid and gaseous fuels.

Process for producing furan from furfural aldehyde

DOEpatents

Diebold, J.P.; Evans, R.J.

1987-04-06

A process of producing furan and derivatives thereof as disclosed. The process includes generating furfural aldehyde vapors and then passing those vapors over a zeolite catalyst at a temperature and for a residence time effective to decarbonylate the furfural aldehydes to form furans and derivatives thereof. The resultant furan vapors and derivatives are then separated. In a preferred form, the furfural aldehyde vapors are generated during the process of converting biomass materials to liquid and gaseous fuels.

Biomarkers of furan exposure by metabolic profiling of rat urine with liquid chromatography-tandem mass spectrometry and principal component analysis.

PubMed

Kellert, Marco; Wagner, Silvia; Lutz, Ursula; Lutz, Werner K

2008-03-01

Furan has been found in a number of heated food items and is carcinogenic in the liver of rats and mice. Estimates of human exposure on the basis of concentrations measured in food are not reliable because of the volatility of furan. A biomarker approach is therefore indicated. We searched for metabolites excreted in the urine of male Fischer 344 rats treated by oral gavage with 40 mg of furan per kg of body weight. A control group received the vehicle oil only. Urine collected over two 24-h periods both before and after treatment was analyzed by a column-switching LC-MS/MS method. Data were acquired by a full scan survey scan in combination with information dependent acquisition of fragmentation spectra by the use of a linear ion trap. Areas of 449 peaks were extracted from the chromatograms and used for principal component analysis (PCA). The first principal component fully separated the samples of treated rats from the controls in the first post-treatment sampling period. Thirteen potential biomarkers selected from the corresponding loadings plot were reanalyzed using specific transitions in the MRM mode. Seven peaks that increased significantly upon treatment were further investigated as biomarkers of exposure. MS/MS information indicated conjugation with glutathione on the basis of the characteristic neutral loss of 129 for mercapturates. Adducts with the side chain amino group of lysine were characterized by a neutral loss of 171 for N-acetyl- l-lysine. Analysis of products of in vitro incubations of the reactive furan metabolite cis-2-butene-1,4-dial with the respective amino acid derivatives supported five structures, including a new 3-methylthio-pyrrole metabolite probably formed by beta-lyase reaction on a glutathione conjugate, followed by methylation of the thiol group. Our results demonstrate the potential of comprehensive mass spectrometric analysis of urine combined with multivariate analyses for metabolic profiling in search of biomarkers of

Pyrolysis of furan in a microreactor

NASA Astrophysics Data System (ADS)

Urness, Kimberly N.; Guan, Qi; Golan, Amir; Daily, John W.; Nimlos, Mark R.; Stanton, John F.; Ahmed, Musahid; Ellison, G. Barney

2013-09-01

A silicon carbide microtubular reactor has been used to measure branching ratios in the thermal decomposition of furan, C4H4O. The pyrolysis experiments are carried out by passing a dilute mixture of furan (approximately 0.01%) entrained in a stream of helium through the heated reactor. The SiC reactor (0.66 mm i.d., 2 mm o.d., 2.5 cm long) operates with continuous flow. Experiments were performed with a reactor inlet pressure of 100-300 Torr and a wall temperature between 1200 and 1600 K; characteristic residence times in the reactor are 60-150 μs. The unimolecular decomposition pathway of furan is confirmed to be: furan (+ M) rightleftharpoons α-carbene or β-carbene. The α-carbene fragments to CH2=C=O + HC≡CH while the β-carbene isomerizes to CH2=C=CHCHO. The formyl allene can isomerize to CO + CH3C≡CH or it can fragment to H + CO + HCCCH2. Tunable synchrotron radiation photoionization mass spectrometry is used to monitor the products and to measure the branching ratio of the two carbenes as well as the ratio of [HCCCH2]/[CH3C≡CH]. The results of these pyrolysis experiments demonstrate a preference for 80%-90% of furan decomposition to occur via the β-carbene. For reactor temperatures of 1200-1400 K, no propargyl radicals are formed. As the temperature rises to 1500-1600 K, at most 10% of the decomposition of CH2=C=CHCHO produces H + CO + HCCCH2 radicals. Thermodynamic conditions in the reactor have been modeled by computational fluid dynamics and the experimental results are compared to the predictions of three furan pyrolysis mechanisms. Uncertainty in the pressure-dependency of the initiation reaction rates is a possible a source of discrepancy between experimental results and theoretical predictions.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part I: Furan.

PubMed

Liu, Dong; Togbé, Casimir; Tran, Luc-Sy; Felsmann, Daniel; Oßwald, Patrick; Nau, Patrick; Koppmann, Julia; Lackner, Alexander; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2014-03-01

Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has - to the best of our knowledge - not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (φ=1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combustion and Flame 158 (2011) 756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the

Effects of certain polyphenols and extracts on furans and acrylamide formation in model system, and total furans during storage.

PubMed

Oral, Rasim Alper; Dogan, Mahmut; Sarioglu, Kemal

2014-01-01

Using a glucose-glycine and asparagine-fructose system as a Maillard reaction model, the effects of seven polyphenols and solid phase extracts of three plants on the formation of furans and acrylamide were investigated. The polyphenols and extracts were used in biscuit formulation and acrylamide formation was observed. They were used for the storage of the glycine-glucose model system at three different temperatures. The addition of some of the extracts and polyphenols significantly decreased furan formation to different extents. All phenolic compounds and plant extracts decreased in the range of 30.8-85% in the model system except for oleuropein, and all of them decreased in the range of 10.3-19.2% in biscuit. Total furan formation was inhibited by caffeic acid, punicalagin, epicatechin, ECE and PPE during storage. This study evaluated and found the inhibitory effect on the formation of furans and acrylamide in Maillard reactions by the use of some plant extracts and polyphenols. Copyright © 2013 Elsevier Ltd. All rights reserved.

Thermodynamic properties of 5(nitrophenyl) furan-2-carbaldehyde isomers.

PubMed

Dibrivnyi, Volodymyr; Sobechko, Iryna; Puniak, Marian; Horak, Yuriy; Obushak, Mykola; Van-Chin-Syan, Yuriy; Andriy, Marshalek; Velychkivska, Nadiia

2015-01-01

The aim of the current work was to determine thermo dynamical properties of 5(2-nitro phenyl)-furan-2-carbaldehyde, 5(3-nitro phenyl)-furan-2-carbaldehyde and 5(4-nitro phenyl)-furan-2-carbaldehyde. The temperature dependence of saturated vapor pressure of 5(2-nitro phenyl)-furan-2-carbaldehyde, 5(3-nitro phenyl)-furan-2-carbaldehyde and 5(4-nitro phenyl)-furan-2-carbaldehyde was determined by Knudsen's effusion method. The results are presented by the Clapeyron-Clausius equation in linear form, and via this form, the standard enthalpies, entropies and Gibbs energies of sublimation and evaporation of compounds were calculated at 298.15 K. The standard molar formation enthalpies of compounds in crystalline state at 298.15 K were determined indirectly by the corresponding standard molar combustion enthalpy, obtained using bomb calorimetry combustion. Determination of the thermodynamic properties for these compounds may contribute to solving practical problems pertaining optimization processes of their synthesis, purification and application and it will also provide a more thorough insight regarding the theoretical knowledge of their nature.Graphical abstract:Generalized structural formula of investigated compounds and their formation enthalpy determination scheme in the gaseous state.

Trajectory Calculations for Bergman Cyclization Predict H/D Kinetic Isotope Effects Due to Nonstatistical Dynamics in the Product.

PubMed

Doubleday, Charles; Boguslav, Mayla; Howell, Caronae; Korotkin, Scott D; Shaked, David

2016-06-22

An unusual H/D kinetic isotope effect (KIE) is described, in which isotopic selectivity arises primarily from nonstatistical dynamics in the product. In DFT-based quasiclassical trajectories of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy, and 28% of nascent p-benzyne recrosses back to the enediyne on a vibrational time scale. The competing process of intramolecular vibrational redistribution (IVR) in p-benzyne is too slow to prevent this. Deuteration increases the rate of IVR, which decreases the fraction of recrossing and increases the yield of statistical (trapable) p-benzyne, 2. Trapable yields for three isotopomers of 2 range from 72% to 86%. The resulting KIEs for Bergman cyclization differ substantially from KIEs predicted by transition state theory, which suggests that IVR in this reaction can be studied by conventional KIEs. Leakage of vibrational zero point energy (ZPE) into the reaction coordinate was probed by trajectories in which initial ZPE in the CH/CD stretching modes was reduced by 25%. This did not change the predicted KIEs.

Formation and reduction of furan in a soy sauce model system.

PubMed

Kim, Min Yeop; Her, Jae-Young; Kim, Mina K; Lee, Kwang-Geun

2015-12-15

The formation and reduction of furan using a soy sauce model system were investigated in the present study. The concentration of furan fermented up to 30 days increased by 211% after sterilization compared to without sterilization. Regarding fermentation temperature, furan level after 30 days' fermentation was the highest at 30°C (86.21 ng/mL). The furan levels in the soy sauce fermentation at 20°C and 40°C were reduced by 45% and 88%, respectively compared to 30°C fermentation. Five metal ions (iron sulfate, zinc sulfate, manganese sulfate, magnesium sulfate, and calcium sulfate), sodium sulfite, ascorbic acid, dibutyl hydroxyl toluene (BHT), and butylated hydroxyanisole (BHA) were added in a soy sauce model system. The addition of metal ions such as magnesium sulfate and calcium sulfate reduced the furan concentration significantly by 36-90% and 27-91%, respectively in comparison to furan level in the control sample (p<0.05). Iron sulfate and ascorbic acid increased the furan level at 30 days' fermentation in the soy sauce model system by 278% and 87%, respectively. In the case of the BHT and BHA, furan formation generally was reduced in the soy sauce model system by 84%, 56%, respectively. Copyright © 2015 Elsevier Ltd. All rights reserved.

Furan formation during storage and reheating of sterilised vegetable purées.

PubMed

Palmers, Stijn; Grauwet, Tara; Buvé, Carolien; Van de Vondel, Lore; Kebede, Biniam T; Hendrickx, Marc E; Van Loey, Ann

2015-01-01

To this day, research for furan mitigation has mostly targeted the levels of food production and handling of prepared foods by the consumer. However, part of the furan concentrations found in commercially available food products might originate from chemical deterioration reactions during storage. A range of individual vegetable purées was stored at two different temperatures to investigate the effects of storage on the furan concentrations of shelf-stable, vegetable-based foods. After 5 months of storage at 35°C (temperature-abuse conditions), a general increase in furan concentrations was observed. The furan formation during storage could be reduced by storing the vegetable purées at a refrigerated temperature of 4°C, at which the furan concentrations remained approximately constant for at least 5 months. Following storage, the vegetable purées were briefly reheated to 90°C to simulate the effect of the final preparation step before consumption. Contrary to storage, furan concentrations decreased as a result of evaporative losses. Both refrigerated storage and the reheating step prior to consumption showed the potential of mitigation measures for furan formation in vegetable-based foods (e.g. canned vegetables, ready-to-eat soups, sauces or baby foods). Next to furan, the vegetable purées were analysed for 2- and 3-methylfuran. Tomato was very susceptible to the formation of both alkylated derivatives of furan, as opposed to the other vegetables in this study. Methylfuran concentrations rapidly decreased during storage, which was contrary to the results observed for furan.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part I: Furan

PubMed Central

Liu, Dong; Togbé, Casimir; Tran, Luc-Sy; Felsmann, Daniel; Oßwald, Patrick; Nau, Patrick; Koppmann, Julia; Lackner, Alexander; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2013-01-01

Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has – to the best of our knowledge – not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (φ=1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combustion and Flame 158 (2011) 756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the

Furan levels in fruit and vegetables juices, nutrition drinks and bakery products.

PubMed

Wegener, Jan-Willem; López-Sánchez, Patricia

2010-07-05

Furan, an oxygen containing monocyclic aromatic hydrocarbon, is considered possibly carcinogenic to humans. In the framework of the EU-project "Role of Genetic and Non-Genetic Mechanisms in Furan Risk", furan levels in food have been collected from the literature. Three food type categories have been selected on the basis of the collected data for sampling and analysis on furan with headspace GC-MS. This paper describes the results for the selected food categories, fruit and vegetables juices, nutrition drinks and bakery products. An attempt has been made to correlate the furan levels with the ingredients of the products. Copyright 2010 Elsevier B.V. All rights reserved.

Electron-impact vibrational excitation of furan

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

Hargreaves, L. R.; Albaridy, R.; Serna, G.

2011-12-15

We report measurements of differential cross sections for the vibrational excitation of furan (C{sub 4}H{sub 4}O), obtaining results for nine features spanning the electron energy loss range from 0 to 0.8 eV, at electron-impact energies of 5, 6, 7.5, 10, and 15 eV and for scattering angles ranging from 10{sup o} to 130{sup o}. The normalization of the differential cross sections was done using elastic differential cross sections for furan determined earlier by our group [Khakoo et al., Phys. Rev A 81, 062716 (2010)].

Furan in heat-treated foods: formation, exposure, toxicity, and aspects of risk assessment.

PubMed

Moro, Sabrina; Chipman, James Kevin; Wegener, Jan-Willem; Hamberger, Carolin; Dekant, Wolfgang; Mally, Angela

2012-08-01

Furan is formed in a variety of heat-treated foods through thermal degradation of natural food constituents. Relatively high levels of furan contamination are found in ground roasted coffee, instant coffee, and processed baby foods. European exposure estimates suggest that mean dietary exposure to furan may be as high as 1.23 and 1.01 μg/kg bw/day for adults and 3- to 12-month-old infants, respectively. Furan is a potent hepatotoxin and hepatocarcinogen in rodents, causing hepatocellular adenomas and carcinomas in rats and mice, and high incidences of cholangiocarcinomas in rats at doses ≥ 2 mg/kg bw. There is therefore a relatively low margin of exposure between estimated human exposure and doses that cause a high tumor incidence in rodents. Since a genotoxic mode of action cannot be excluded for furan-induced tumor formation, the present exposures may indicate a risk to human health and need for mitigation. This review summarizes the current knowledge on mechanisms of furan formation in food, human dietary exposure to furan, and furan toxicity, and highlights the need to establish the risk resulting from the genotoxic and carcinogenic properties of furan at doses lower than 2 mg/kg bw. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Furan production from glycoaldehyde over HZSM-5

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

Kim, Seonah; Evans, Tabitha J.; Mukarakate, Calvin

Catalytic fast pyrolysis of biomass over zeolite catalysts results primarily in aromatic (e.g. benzene, toluene, xylene) and olefin products. However, furans are a higher value intermediate for their ability to be readily transformed into gasoline, diesel, and chemicals. Here we investigate possible mechanisms for the coupling of glycoaldehyde, a common product of cellulose pyrolysis, over HZSM-5 for the formation of furans. Experimental measurements of neat glycoaldehyde over a fixed bed of HZSM-5 confirm furans (e.g. furanone) are products of this reaction at temperatures below 300 degrees C with several aldol condensation products as co-products (e.g. benzoquinone). However, under typical catalyticmore » fast pyrolysis conditions (>400 degrees C), further reactions occur that lead to the usual aromatic product slate. ONIOM calculations were utilized to identify the pathway for glycoaldehyde coupling toward furanone and hydroxyfuranone products with dehydration reactions serving as the rate determining steps with typical intrinsic reaction barriers of 40 kcal mol-1. The reaction mechanisms for glycoaldehyde will likely be similar to that of other small oxygenates such as acetaldehyde, lactaldehyde, and hydroxyacetone and this study provides a generalizable mechanism of oxygenate coupling and furan formation over zeolite catalysts.« less

Furan production from glycoaldehyde over HZSM-5

DOE PAGES

Kim, Seonah; Evans, Tabitha J.; Mukarakate, Calvin; ...

2016-04-03

Catalytic fast pyrolysis of biomass over zeolite catalysts results primarily in aromatic (e.g. benzene, toluene, xylene) and olefin products. However, furans are a higher value intermediate for their ability to be readily transformed into gasoline, diesel, and chemicals. Here we investigate possible mechanisms for the coupling of glycoaldehyde, a common product of cellulose pyrolysis, over HZSM-5 for the formation of furans. Experimental measurements of neat glycoaldehyde over a fixed bed of HZSM-5 confirm furans (e.g. furanone) are products of this reaction at temperatures below 300 degrees C with several aldol condensation products as co-products (e.g. benzoquinone). However, under typical catalyticmore » fast pyrolysis conditions (>400 degrees C), further reactions occur that lead to the usual aromatic product slate. ONIOM calculations were utilized to identify the pathway for glycoaldehyde coupling toward furanone and hydroxyfuranone products with dehydration reactions serving as the rate determining steps with typical intrinsic reaction barriers of 40 kcal mol-1. The reaction mechanisms for glycoaldehyde will likely be similar to that of other small oxygenates such as acetaldehyde, lactaldehyde, and hydroxyacetone and this study provides a generalizable mechanism of oxygenate coupling and furan formation over zeolite catalysts.« less

A validated method for rapid determination of dibenzo-p-dioxins/furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in human milk: focus on utility of tandem solid phase extraction (SPE) cleanup.

PubMed

Lin, Yuanjie; Feng, Chao; Xu, Qian; Lu, Dasheng; Qiu, Xinlei; Jin, Yu'e; Wang, Guoquan; Wang, Dongli; She, Jianwen; Zhou, Zhijun

2016-07-01

An improved method based on tandem solid phase extraction (SPE) cleanup and gas chromatography-high resolution mass spectrometry (GC-HRMS) has been validated for a rapid determination of dibenzo-p-dioxins/furans (PCDD/Fs), dioxin-like polychlorinated biphenyls (PCBs), marker polychlorinated biphenyls (M-PCBs), and polybrominated diphenyl ethers (PBDEs) using a large volume (50 mL) of human milk. This method was well validated for the measurement of these analytes in human milk from the general population with low limits of detection (LODs, 0.004-0.12 ng/g lipid), satisfactory accuracy (75-120 % of recoveries), and precision [less than 10 % of relative standard deviations (RSDs)]. To comprehensively evaluate the performance of this method, a good, presently validated and routinely used method based on an automated sample clean-up system (ASCS, based on the commercial acid multilayer silica, basic alumina, and carbon columns) was used in parallel for comparison. Compared with the ASCS method, this method presented comparable specificity. Additionally, this method, in contrast to ASCS method, highly reduced consumption of solvents (40 mL versus 500 mL), which results in much lower background in the procedural blank, reduced time, and enhanced sample pretreatment throughput. This method was also applied in a pilot study to measure a batch of human milk samples with satisfactory results. Graphical Abstract Characteristics of the application of tandem SPE cleanup for determination of PCDD/Fs, DL-PCBs,M-PCBs and PBDEs in human milk.

Impact of cooking and handling conditions on furanic compounds in breaded fish products.

PubMed

Pérez-Palacios, T; Petisca, C; Henriques, R; Ferreira, I M P L V O

2013-05-01

This study evaluates the influence of cooking and handling conditions on the quantity of furanic compounds (furan, 2-furfural, furfuryl alcohol, 2-pentylfuran, 5-hydroxymethylfurfural) in breaded fish products. Oven-baking and reheating in the microwave lead to low furanic compounds formation in comparison with deep-frying. The use of olive oil for deep-frying promoted higher levels of furanic compounds than sunflower oil. The amounts of these compounds diminished as the temperature and time of deep-frying decreased as well as after a delay after deep-frying. Thus, the generation of furanic compounds can be minimized by adjusting the cooking method and conditions, such as using an electric oven, deep-frying in sunflower oil at 160°C during 4min, or waiting 10min after cooking. However, these conditions that reduce furanic compounds levels also reduce the content of volatile compounds related to the aroma and flavour of fried foods. In this sense, new efforts should be done to reduce the formation of furanic compounds without being detrimental to the volatile profile. Copyright © 2013 Elsevier Ltd. All rights reserved.

In vivo genotoxicity of furan in F344 rats at cancer bioassay doses

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

Ding, Wei, E-mail: Wei.Ding@fda.hhs.gov; Petibone, Dayton M.; Latendresse, John R.

2012-06-01

Furan, a potent rodent liver carcinogen, is found in many cooked food items and thus represents a human cancer risk. Mechanisms for furan carcinogenicity were investigated in male F344 rats using the in vivo Comet and micronucleus assays, combined with analysis of histopathological and gene expression changes. In addition, formamidopyrimidine DNA glycosylase (Fpg) and endonuclease III (EndoIII)-sensitive DNA damage was monitored as a measure of oxidative DNA damage. Rats were treated by gavage on four consecutive days with 2, 4, and 8 mg/kg bw furan, doses that were tumorigenic in 2-year cancer bioassays, and with two higher doses, 12 andmore » 16 mg/kg. Rats were killed 3 h after the last dose, a time established as producing maximum levels of DNA damage in livers of furan-treated rats. Liver Comet assays indicated that both DNA strand breaks and oxidized purines and pyrimidines increased in a near-linear dose-responsive fashion, with statistically significant increases detected at cancer bioassay doses. No DNA damage was detected in bone marrow, a non-target tissue for cancer, and peripheral blood micronucleus assays were negative. Histopathological evaluation of liver from furan-exposed animals produced evidence of inflammation, single-cell necrosis, apoptosis, and cell proliferation. In addition, genes related to apoptosis, cell-cycle checkpoints, and DNA-repair were expressed at a slightly lower level in the furan-treated livers. Although a mixed mode of action involving direct DNA binding cannot be ruled out, the data suggest that furan induces cancer in rat livers mainly through a secondary genotoxic mechanism involving oxidative stress, accompanied by inflammation, cell proliferation, and toxicity. -- Highlights: ► Furan is a potent rodent liver carcinogen and represents a human cancer risk. ► Furan induces DNA damage in rat liver at cancer bioassay doses. ► Furan induces oxidative stress, inflammation and cell proliferation in rat liver. �

Furan-induced hepatotoxic and hematologic changes in diabetic rats: the protective role of lycopene.

PubMed

Baş, Hatice; Pandır, Dilek; Kalender, Suna

2016-09-01

Furan forms as a result of thermal treatment of food and induces harmful effects on organisms. In our work, lycopene, furan, and a combination of the two were given to diabetic male rats for 28 days. Hematological changes, total protein and cholesterol, triglyceride, and albumin levels, alanine aminotransferase, aspartate aminotransferase, lactate dehydrogenase, and alkaline phosphatase activities of the serum, malondialdehyde levels, glutathione peroxidase, catalase, glutathione-S-transferase, superoxide dismutase activities, DNA damage in liver tissues and hepatic histopathological alterations were compared to a control group. There were significant changes in the liver function tests, DNA damage, activities of antioxidant enzymes, and malondialdehyde levels between diabetic control and non-diabetic control groups, between diabetic control and diabetic lycopene groups, and also between diabetic furan and diabetic control groups. In diabetic lycopene and diabetic furan + lycopene treated groups we designated the preventive effects of lycopene against diabetes and furan, however, on the analysed parameters only. In spite of some pathological alterations designated in diabetic furan treated group's liver, fewer pathological alterations were observed in furan+lycopene treated groups at the end of week 4. Consequently, lycopene significantly reduced furan- and diabetes-induced toxicity in rat liver.

Furan levels in coffee as influenced by species, roast degree, and brewing procedures.

PubMed

Arisseto, Adriana Pavesi; Vicente, Eduardo; Ueno, Mariana Soares; Tfouni, Silvia Amélia Verdiani; Toledo, Maria Cecília De Figueiredo

2011-04-13

Brazilian green coffee beans of Coffea arabica and Coffea canephora species were roasted to light, medium, and dark roast degrees and analyzed in relation to furan content by using an in-house validated method based on gas chromatography coupled to mass spectrometry preceded by headspace solid-phase microextraction. Furan was not detected in green coffees, whereas levels between 911 and 5852 μg/kg were found in the roasted samples. Higher concentrations were found in Coffea canephora species and darker ground coffees. Some of the potential furan precursors were observed in significant amounts in green coffee, especially sucrose and linoleic acid, but their concentrations could not be correlated to furan formation. Additionally, coffee brews were prepared from roasted ground coffees by using two different procedures, and furan levels in the beverages varied from <10 to 288 μg/kg. The factor that most influenced the furan content in coffee brew was the brewing procedure.

Formation and reduction of carcinogenic furan in various model systems containing food additives.

PubMed

Kim, Jin-Sil; Her, Jae-Young; Lee, Kwang-Geun

2015-12-15

The aim of this study was to analyse and reduce furan in various model systems. Furan model systems consisting of monosaccharides (0.5M glucose and ribose), amino acids (0.5M alanine and serine) and/or 1.0M ascorbic acid were heated at 121°C for 25 min. The effects of food additives (each 0.1M) such as metal ions (iron sulphate, magnesium sulphate, zinc sulphate and calcium sulphate), antioxidants (BHT and BHA), and sodium sulphite on the formation of furan were measured. The level of furan formed in the model systems was 6.8-527.3 ng/ml. The level of furan in the model systems of glucose/serine and glucose/alanine increased 7-674% when food additives were added. In contrast, the level of furan decreased by 18-51% in the Maillard reaction model systems that included ribose and alanine/serine with food additives except zinc sulphate. Copyright © 2014 Elsevier Ltd. All rights reserved.

Reactive Metabolites in the Biotransformation of Molecules Containing a Furan Ring

PubMed Central

Peterson, Lisa A.

2012-01-01

Many xenobiotics containing a furan ring are toxic and/or carcinogenic. The harmful effects of these compounds require furan ring oxidation. This reaction generates an electrophilic intermediate. Depending on the furan ring substituents, the intermediate is either an epoxide or a cis-enedione with more ring substitution favoring epoxide formation. Either intermediate reacts with cellular nucleophiles such as protein or DNA to trigger toxicities. The reactivity of the metabolite determines which cellular nucleophiles are targeted. The toxicity of a particular furan is also influenced by the presence of competing metabolic pathways or efficient detoxification routes. GSH plays an important role in modulating the harmful effects of this class of compound by reacting with the reactive metabolite. However, this may not represent a detoxification step in all cases. PMID:23061605

Crystal structures of fac-tri-carbonyl-chlorido-(6,6'-dihy-droxy-2,2'-bi-pyridine)-rhenium(I) tetra-hydro-furan monosolvate and fac-bromido-tricarbon-yl(6,6'-dihy-droxy-2,2'-bi-pyridine)-manganese(I) tetra-hydro-furan monosolvate.

PubMed

Lense, Sheri; Piro, Nicholas A; Kassel, Scott W; Wildish, Andrew; Jeffery, Brent

2016-08-01

The structures of two facially coordinated Group VII metal complexes, fac-[ReCl(C10H8N2O2)(CO)3]·C4H8O (I·THF) and fac-[MnBr(C10H8N2O2)(CO)3]·C4H8O (II·THF), are reported. In both complexes, the metal ion is coordinated by three carbonyl ligands, a halide ligand, and a 6,6'-dihy-droxy-2,2'-bi-pyridine ligand in a distorted octa-hedral geometry. Both complexes co-crystallize with a non-coordinating tetra-hydro-furan (THF) solvent mol-ecule and exhibit inter-molecular but not intra-molecular hydrogen bonding. In both crystal structures, chains of complexes are formed due to inter-molecular hydrogen bonding between a hy-droxy group from the 6,6'-dihy-droxy-2,2'-bi-pyridine ligand and the halide ligand from a neighboring complex. The THF mol-ecule is hydrogen bonded to the remaining hy-droxy group.

Furan Levels and Sensory Profiles of Commercial Coffee Products Under Various Handling Conditions.

PubMed

Han, Jeesoo; Kim, Mina K; Lee, Kwang-Geun

2017-11-01

In this study, the levels of furan in coffee with consideration towards common coffee consumption was investigated. The concentration of furan in brewed coffee was the highest among the coffee types studied, with an average of 110.73 ng/mL, followed by canned coffee (28.08 ng/mL) and instant coffee (8.55 ng/mL). In instant and brewed coffee, the furan levels decreased by up to an average of 20% and 22%, after 5 min of pouring in a cup without a lid. The degree of reduction was greater when coffee was served without a lid, regardless of coffee type (P < 0.05). In canned coffee, the level of furan decreased by an average of 14% after storage at 60 °C without a lid, and the degree of furan reduction in coffee was greater in coffee served warm (60 °C) than in coffee served cold (4 °C). A time-dependent intensities of sensory attributes in commercial coffees with various handling condition were different (P < 0.05), suggesting that coffee kept in a cup with lid closed, holds the aroma of coffee longer than coffee in a cup without a lid. Consumption of coffee has increased rapidly in Korea over the past few years. Consequently, the probability of exposure to chemical hazards presence in coffee products increases. Furan is a heterocyclic compound, formed mainly from Maillard reaction, therefore present in coffee products. This work demonstrated the strategy to reduce the levels of furan in coffee products at individual consumer level, by investigating the levels of furan served in common handling scenarios of coffee in Korea: canned coffee, instant coffee, and brewed coffee. Findings of this study can practically guide industry, government, and consumer agencies to reduce the risk exposure to furan during coffee consumptions. © 2017 Institute of Food Technologists®.

Direct decarbonylation of furfural to furan: A density functional theory study on Pt-graphene

NASA Astrophysics Data System (ADS)

Fellah, Mehmet Ferdi

2017-05-01

The catalytic mechanism of direct decarbonylation of furfural to furan on Pt graphene surface has been investigated by means of density functional theory (DFT) calculations. The main catalytic mechanism proposed in this study has six steps such as furfural adsorption, dissociation of H from adsorbed furfural, dissociation of carbon monoxide (molecularly) from adsorbed complex, furan formation and desorption of products. It has been concluded that the rate determining step for direct decarbonylation of furfural to furan is furan formation step and global activation barrier for this catalytic system is 82 kJ/mol consisting of zero point energy and thermal energy corrections. Pt-graphene structure has an important role on the catalytic decarbonylation of furfural to furan without any other reactants. This accordingly points out that Pt doped graphene structure might be an encouraging catalyst for direct decarbonylation of furfural to furan molecule as a valuable chemical material.

Stereodivergent Synthesis of N-Heterocycles by Catalyst-Controlled, Activity-Directed Tandem Annulation of Diazo Compounds with Amino Alkynes.

PubMed

Liu, Kai; Zhu, Chenghao; Min, Junxiang; Peng, Shiyong; Xu, Guangyang; Sun, Jiangtao

2015-10-26

A stereodivergent synthesis of five-membered N-heterocycles, such as 2,3-dihydropyrroles, and 2-methylene and 3-methylene pyrrolidines, has been developed through a tandem annulation of amino alkynes with diazo compounds and involves the trapping of in situ formed intermediates. Mechanistic investigations indicate that the copper-catalyzed tandem annulations proceed by allenoate formation and subsequent intramolecular hydroamination. In contrast, the rhodium-catalyzed protocol features a carbenoid insertion into the NH bond and subsequent Conia-ene cyclization. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Furan fatty acids - Beneficial or harmful to health?

PubMed

Xu, Long; Sinclair, Andrew J; Faiza, Muniba; Li, Daoming; Han, Xianlin; Yin, Huiyong; Wang, Yonghua

2017-10-01

Furan fatty acids are found in plants, algae, and fish, and reported to have some positive health benefits, including anti-oxidant and anti-inflammatory activities, and inhibition of non-enzymatic lipid peroxidation. A major metabolite of furan fatty acids, 3-carboxy-4-methyl-5-propyl-2-furanpropanoic acid (CMPF), has been reported to be increased in patients who progress from prediabetes to type 2 diabetes, although CMPF is not necessarily associated with impaired glucose metabolism. Other studies report that CMPF levels are lower in subjects with diabetes than control subjects. Plasma CMPF levels increase in subjects who consume fish or fish oil, and in patients with renal failure. It is not known where furan fatty acids are converted to CMPF and it is speculated that this might be a result of microbiome activity. The plasma levels reported for CMPF in healthy, diabetic and patients with renal disease vary by factors of more than 100-fold within each of these three groups, so measurement error appears to be limiting the ability to interpret studies. This review explores these controversies and raises questions about whether CMPF is a marker for healthy diets or indeed associated with diabetes and renal health. The review concludes that, on balance, furan fatty acids are beneficial for health. Copyright © 2017 Elsevier Ltd. All rights reserved.

Formation of furan and methylfuran by maillard-type reactions in model systems and food.

PubMed

Limacher, Anita; Kerler, Josef; Davidek, Tomas; Schmalzried, Frank; Blank, Imre

2008-05-28

The formation of furan and 2-methylfuran was studied in model systems based on sugars and selected amino acids. Both compounds were preferably formed under roasting conditions in closed systems yielding up to 330 micromol of furan and 260 micromol of 2-methylfuran per mol of precursor. The amounts obtained under pressure cooking conditions were much lower, usually below 20 micromol/mol, except for 2-furaldehyde, which yielded 70-100 micromol/mol of furan. Labeling studies indicated two major formation pathways for both furans: (i) from the intact sugar skeleton and (ii) by recombination of reactive C(2) and/or C(3) fragments. Under roasting conditions in the absence of amino acids, furan was mainly formed from the intact sugar skeleton. Formic and acetic acid were identified as byproducts of sugar degradation, indicating the split off of C(1) and/or C(2) units from hexoses. The presence of alanine, threonine, or serine promoted furan formation by the recombination of C(2) fragments, such as acetaldehyde and glycolaldehyde, which may originate from both sugars and amino acids. In aqueous solution, about half of furan was generated by the recombination of sugar fragments. 2-Methylfuran was preferably formed in the presence of amino acids by aldol-type reactions of C(2) and C(3) fragments with lactaldehyde as a key intermediate, the Strecker aldehyde of threonine. The total furan levels in cooked vegetables were increased by spiking with hexoses. However, in pumpkin puree, only about 20% of furan was formed from sugars, preferably from the intact carbon skeleton.

On-fiber furan formation from volatile precursors: a critical example of artefact formation during Solid-Phase Microextraction.

PubMed

Adams, An; Van Lancker, Fien; De Meulenaer, Bruno; Owczarek-Fendor, Agnieszka; De Kimpe, Norbert

2012-05-15

For the analysis of furan, a possible carcinogen formed during thermal treatment of food, Solid-Phase Microextraction (SPME) is a preferred and validated sampling method. However, when volatile furan precursors are adsorbed on the carboxen/PDMS fiber, additional amounts of furan can be formed on the fiber during thermal desorption, as shown here for 2-butenal and furfural. No significant increase in furan amounts was found upon heating the furan precursor 2-butenal, indicating that the furan amounts formed during precursor heating experiments are negligible as compared to the additional amounts of furan formed during fiber desorption. This artefactual furan formation increased with increasing desorption time, but especially with increasing desorption temperature. Although this effect was most pronounced on the Carboxen/PDMS SPME-fiber, it was also noted on two other SPME-fibers tested (PDMS and DVB/Carboxen/PDMS). The general impact on furan data from food and model systems in literature will depend on the amounts of volatile precursors present, but will probably remain limited. However, considering the importance of this worldwide food contaminant, special care has to be taken during SPME-analysis of furan. Especially when performing precursor studies, static headspace sampling should preferably be applied for furan analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

Furan Decorated Nucleoside Analogues as Fluorescent Probes: synthesis, photophysical evaluation and site-specific incorporation

PubMed Central

Greco, Nicholas J.; Tor, Yitzhak

2007-01-01

The synthesis and photophysical evaluation of modified nucleoside analogues in which a five-membered heterocycle (furan, thiophene, oxazole and thiazole) is attached to the 5 position of 2′-deoxyuridine are reported. The furan containing derivative is identified as the most promising responsive nucleoside of this family due to its emission quantum efficiency and degree of sensitivity to its microenvironment. The furan moiety was then attached to the 5 position of 2′-deoxycytidine as well as the 8 position of adenosine and guanosine. Photophysical evaluation of these four furan containing nucleoside analogues reveal distinct differences in the absorption, emission and quantum efficiency depending upon the class of nucleoside (pyrimidine or purine). Comparing the photophysical properties of all furan containing nucleosides, identifies the furan thymidine analogue, 5-(fur-2-yl)-2′-deoxyuridine, as the best candidate for use as a responsive fluorescent probe in nucleic acids. 5-(fur-2-yl)-2′-deoxyuridine was then converted to the corresponding phosphoramidite and site specifically incorporated into DNA oligonucleotides with greater than 88% coupling efficiency. Such furan-modified oligonucleotides form stable duplexes upon hybridization to their complementary DNA strands and display favorable fluorescent features. PMID:18431439

Occurrence of furan in coffee from Spanish market: Contribution of brewing and roasting.

PubMed

Altaki, M S; Santos, F J; Galceran, M T

2011-06-15

In this work, we evaluated the occurrence of furan in brews obtained from regular, decaffeinated, and instant coffee and commercial packed capsules. For this purpose, a previously developed automated headspace solid-phase microextraction method coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS) was used. Initially, the influence of HS-SPME conditions on furan formation was evaluated. In addition, the effect of roasting conditions (temperature and time) used for coffee beans on furan formation was also studied. We found that low temperature and long roasting time (140°C and 20min) decreases the final furan content. Furan concentrations in regular ground coffee brews from an espresso coffee machine were higher (43-146ng/ml) than those obtained from a home drip coffee maker (20 and 78ng/ml), while decaffeinated coffee brews from a home drip coffee maker (14-65ng/ml) showed a furan concentration similar to that obtained from regular coffee. Relatively low concentrations of this compound (12-35ng/ml) were found in instant coffee brews, while commercial packed coffee capsules showed the highest concentrations (117-244ng/ml). Finally, the daily intake of furan through coffee consumption in Barcelona (Spain) (0.03-0.38μg/kg of body weight) was estimated. Copyright © 2010 Elsevier Ltd. All rights reserved.

Formation and emission of large furans and oxygenated hydrocarbons from flames.

PubMed

Johansson, K Olof; Dillstrom, Tyler; Monti, Matteo; El Gabaly, Farid; Campbell, Matthew F; Schrader, Paul E; Popolan-Vaida, Denisia M; Richards-Henderson, Nicole K; Wilson, Kevin R; Violi, Angela; Michelsen, Hope A

2016-07-26

Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. We used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that furans are produced in the high-temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ∼100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbon- and oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming.

Formation and emission of large furans and oxygenated hydrocarbons from flames

PubMed Central

Johansson, K. Olof; Dillstrom, Tyler; Monti, Matteo; El Gabaly, Farid; Campbell, Matthew F.; Schrader, Paul E.; Popolan-Vaida, Denisia M.; Richards-Henderson, Nicole K.; Wilson, Kevin R.; Violi, Angela; Michelsen, Hope A.

2016-01-01

Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. We used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that furans are produced in the high-temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ∼100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbon- and oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming. PMID:27410045

Mutagenicity of furan in female Big Blue B6C3F1 mice

PubMed Central

Terrell, Ashley N.; Huynh, Mailee; Grill, Alex E.; Kovi, Ramesh C.; O’Sullivan, M. Gerard; Guttenplan, Joseph B.; Ho, Yen-Yi; Peterson, Lisa A.

2014-01-01

Furan is an abundant food and environmental contaminant that is a potent liver carcinogen in rodent models. To determine if furan is genotoxic in vivo, female B6C3F1 Big Blue transgenic mice were treated with 15 mg/kg bw furan by gavage 5 days a week for 6 weeks, or once weekly for 3 weeks. Liver cII trans-gene mutation-frequency and mutation spectra were determined. Furan did not increase the mutation frequency under either treatment condition. In the 6-week treatment regimen, there was a change in the cII transgene mutation-spectrum, with the fraction of GC to AT transitions significantly reduced. The only other significant change was an increase in GC to CG transversions; these represented a minor contribution to the overall mutation spectrum. A much larger furan-dependent shift was observed in the 3-week study. There was a significant increase in transversion mutations, predominantly GC to TA transversions as well as smaller non-significant changes in GC to CG and AT to TA transversions. To determine if these mutations were caused by cis-2-butene-1,4-dial (BDA), a reactive metabolite of furan, the mutagenic activity and the mutation spectrum of BDA was determined in vitro, in Big Blue mouse embryonic fibroblasts. This compound did not increase the cII gene mutation-frequency but caused a substantial increase in AT to CG transversions. This increase, however, lost statistical significance when adjusted for multiple comparisons. Together, these findings suggest that BDA may not be directly responsible for the in-vivo effects of furan on mutational spectra. Histopathological analysis of livers from furan-treated mice revealed that furan induced multifocal, hepatocellular necrosis admixed with reactive leukocytes and pigment-laden Kupffer cells, enhanced oval-cell hyperplasia, and increased hepatocyte mitoses, some of which were atypical. An indirect mechanism of genotoxicity is proposed in which chronic toxicity followed by inflammation and secondary cell

How ingredients influence furan and aroma generation in sponge cake.

PubMed

Cepeda-Vázquez, Mayela; Rega, Barbara; Descharles, Nicolas; Camel, Valérie

2018-04-15

A wide range of compounds can be formed during thermal processing of food, some of which are relevant for aroma (e.g., furfural), while others are of great health concern (e.g., furan). This paper presents the study of formulation as affecting the simultaneous generation of furan and furfural, along with other aroma quality markers, in sponge cake by means of headspace trap/GC-MS. Ingredients were screened according to their category (fat, salt, sugar, egg-based). Glucose-containing formulation resulted in the highest content of furan and furfural (12.5 ± 0.5 ng g -1 and 9.2 ± 0.2 μg g -1 , dry basis, respectively), while their lowest amount was found in the egg-white recipe (3.1 ± 0.1 ng g -1 for furan and 0.287 ± 0.078 µg g -1 for furfural, dry basis). The latter also related negatively to all studied compounds. This work will be useful for developing novel strategies to deliver safe foods with appealing organoleptic attributes. Copyright © 2017 Elsevier Ltd. All rights reserved.

PHD domain-mediated E3 ligase activity directs intramolecular sumoylation of an adjacent bromodomain required for gene silencing.

PubMed

Ivanov, Alexey V; Peng, Hongzhuang; Yurchenko, Vyacheslav; Yap, Kyoko L; Negorev, Dmitri G; Schultz, David C; Psulkowski, Elyse; Fredericks, William J; White, David E; Maul, Gerd G; Sadofsky, Moshe J; Zhou, Ming-Ming; Rauscher, Frank J

2007-12-14

Tandem PHD and bromodomains are often found in chromatin-associated proteins and have been shown to cooperate in gene silencing. Each domain can bind specifically modified histones: the mechanisms of cooperation between these domains are unknown. We show that the PHD domain of the KAP1 corepressor functions as an intramolecular E3 ligase for sumoylation of the adjacent bromodomain. The RING finger-like structure of the PHD domain is required for both Ubc9 binding and sumoylation and directs modification to specific lysine residues in the bromodomain. Sumoylation is required for KAP1-mediated gene silencing and functions by directly recruiting the SETDB1 histone methyltransferase and the CHD3/Mi2 component of the NuRD complex via SUMO-interacting motifs. Sumoylated KAP1 stimulates the histone methyltransferase activity of SETDB1. These data provide a mechanistic explanation for the cooperation of PHD and bromodomains in gene regulation and describe a function of the PHD domain as an intramolecular E3 SUMO ligase.

Furan formation from fatty acids as a result of storage, gamma irradiation, UV-C and heat treatments.

PubMed

Fan, Xuetong

2015-05-15

The effects of gamma and UV-C irradiation in comparison with thermal processing and storage at 25°C on formation of furan from different fatty acids were investigated. Results showed that furan was generated from polyunsaturated fatty acids such as linoleic and linolenic acid during thermal (120°C, 25 min) and UV-C (11.5 J/cm(2)) treatments. Gamma irradiation (up to 20 kGy) did not induce formation of significant amounts of furan from any of the fatty acids studied. Storage of unsaturated fatty acid emulsions at 25°C for 3 days led to the formation of furan (7-11 ng/mL) even without prior thermal or non-thermal treatments. pH significantly impacted furan formation with >3.5 times more furan formed at pH 9 than at pHs 3 or 6 during 3 days at 25°C. The addition of Trolox, BHA, and propyl gallate had no significant effect on furan formation from linolenic acid while α-tocopherol and FeSO4 promoted furan formation. Published by Elsevier Ltd.

Furan induced ovarian damage in non-diabetic and diabetic rats and cellular protective role of lycopene.

PubMed

Uçar, Semra; Pandir, Dilek

2017-11-01

In our work, furan, lycopene, and furan + lycopene treatments were applied to non-diabetic and diabetic female rats via gavage. Ovarian tissue alterations with histopathology, immunohistochemistry, malondialdehyde levels, oxidative stress parameters such as superoxide dismutase, catalase, glutathione peroxidase, glutathione-S-transferase and harmful effect on ovarian tissue DNA were evaluated in all groups for 28 days. Furan caused the changes histological, ovarian cell's DNA structure, malondialdehyde levels, antioxidant enzymes activities as in a statistically significant manner in each group. Useful effect of lycopene was determined both in non-diabetic and diabetic treatment groups against furan according to the used experimental parameters. Although some histopathological alterations were seen in diabetic and non-diabetic/diabetic plus furan-treated group's ovarians, lycopene restored these variations near to normal levels in furan + lycopene treated groups for in 28 days. Additionally, the results of our immunohistochemical analysis and alterations of the oxidative stress parameters results also supported these findings. Our result confirms that lycopene has protective effect and significantly altered diabetes and furan-induced toxicity in the rat ovarian tissue.

Furan in coffee: pilot studies on formation during roasting and losses during production steps and consumer handling.

PubMed

Guenther, H; Hoenicke, K; Biesterveld, S; Gerhard-Rieben, E; Lantz, I

2010-03-01

The occurrence of furan in some food products has already been known for a few decades, and it has been reconfirmed in more recent investigations that furan is present in a variety of foodstuffs. This list of products includes roasted coffee, which has been shown to generate furan as a result of the heat treatment at roasting which is applied to achieve the desired aroma and flavour profile of a roasted coffee. The objective of this study is to provide data to allow a better understanding of the available data of furan in coffee, the kinetics of furan generated during roasting, and to estimate the reduction of furan levels afterwards due to subsequent processing steps and consumer handling. Finally, the study is meant as a contribution to establish exposure data on the basis of scientific data at the stage of coffee consumption. This paper shows that the formation of furan during roasting is dependent on roasting conditions and is, therefore, directly linked to achieving targeted flavour profiles. Furthermore, it is demonstrated that modifications in process conditions potentially to reduce furan levels may have the opposite effect on other undesired reaction products of the roasting chemistry such as, for example, acrylamide. Due to the high volatility of furan, any subsequent processing step or consumer handling has an impact on the level of furan. As a guidance from this study and in consideration of the identified losses of each process and handling step on the basis of the trial conditions, it is estimated that only approximately 10% of the initially generated furan during roasting gets into the cup of coffee for consumption.

Occurrence of furan in commercial processed foods in Brazil.

PubMed

Arisseto, A P; Vicente, E; Furlani, R P Z; Ueno, M S; Pereira, A L D; Toledo, M C F

2012-01-01

Selected commercial processed foods available in the Brazilian market (306 samples) were analysed for furan content using a validated gas chromatography-mass spectrometry method preceded by headspace solid phase micro-extraction (HS-SPME-GC/MS). Canned and jarred foods, including vegetable, meat, fruit and sweet products, showed levels up to 32.8 µg kg⁻¹, with the highest concentrations observed in vegetables and meats. For coffee, furan content ranged from 253.0 to 5021.4 µg kg⁻¹ in the roasted ground coffee and from not detected to 156.6 µg kg⁻¹ in the beverage. For sauces, levels up to 138.1 µg kg⁻¹ were found. In cereal-based products, the highest concentrations (up to 191.3 µg kg⁻¹) were observed in breakfast cereal (corn flakes), cracker (cream crackers) and biscuit (wafer). In general, these results are comparable with those reported in other countries and will be useful for a preliminary estimate of the furan dietary intake in Brazil.

Abundant Rodent Furan-Derived Urinary Metabolites Are Associated with Tobacco Smoke Exposure in Humans.

PubMed

Grill, Alex E; Schmitt, Thaddeus; Gates, Leah A; Lu, Ding; Bandyopadhyay, Dipankar; Yuan, Jian-Min; Murphy, Sharon E; Peterson, Lisa A

2015-07-20

Furan, a possible human carcinogen, is found in heat treated foods and tobacco smoke. Previous studies have shown that humans are capable of converting furan to its reactive metabolite, cis-2-butene-1,4-dial (BDA), and therefore may be susceptible to furan toxicity. Human risk assessment of furan exposure has been stymied because of the lack of mechanism-based exposure biomarkers. Therefore, a sensitive LC-MS/MS assay for six furan metabolites was applied to measure their levels in urine from furan-exposed rodents as well as in human urine from smokers and nonsmokers. The metabolites that result from direct reaction of BDA with lysine (BDA-N(α)-acetyllysine) and from cysteine-BDA-lysine cross-links (N-acetylcysteine-BDA-lysine, N-acetylcysteine-BDA-N(α)-acetyllysine, and their sulfoxides) were targeted in this study. Five of the six metabolites were identified in urine from rodents treated with furan by gavage. BDA-N(α)-acetyllysine, N-acetylcysteine-BDA-lysine, and its sulfoxide were detected in most human urine samples from three different groups. The levels of N-acetylcysteine-BDA-lysine sulfoxide were more than 10 times higher than that of the corresponding sulfide in many samples. The amount of this metabolite was higher in smokers relative to that in nonsmokers and was significantly reduced following smoking cessation. Our results indicate a strong relationship between BDA-derived metabolites and smoking. Future studies will determine if levels of these biomarkers are associated with adverse health effects in humans.

Effects of heat-induced food contaminant furan on reproductive system of male rats from weaning through postpuberty.

PubMed

Karacaoğlu, Elif; Selmanoğlu, Güldeniz

2010-05-01

Furan (C(4)H(4)O) is a volatile, colorless liquid and is used in some segments of the chemical manufacturing industry. It is found in variety of foods such as coffee, jarred and canned foods that undergo heat treatment. This study was designed to investigate the effect of furan exposure on reproductive system of male rats. Three to four weeks old rats were exposed to furan at 2, 4 and 8 mg/kg/day doses by orally for 90 days. Hematology, weights, histology and morphometry of reproductive organs, serum LH and testosterone levels, sperm count and morphology and apoptosis in testis were evaluated. Slight changes were observed in hematological parameters of furan-treated rats. The weights of seminal vesicle reduced significantly whereas the weights of prostate increased significantly in the highest furan dose group. LH and testosterone levels decreased in furan-treated rats. Histological examinations have revealed that furan caused impairments in testis, epididymis and prostate gland. Furan showed no effects on sperm counts and morphology. On the other hand apoptotic cells in testis increased significantly. According to morphometrical examination, the epithelial heights and lumen diameters of the reproductive organs have changed in treatment groups. These results indicate that subchronic furan treatment induces toxicity of the male reproductive system. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Multivariate optimization of headspace trap for furan and furfural simultaneous determination in sponge cake.

PubMed

Cepeda-Vázquez, Mayela; Blumenthal, David; Camel, Valérie; Rega, Barbara

2017-03-01

Furan, a possibly carcinogenic compound to humans, and furfural, a naturally occurring volatile contributing to aroma, can be both found in thermally treated foods. These process-induced compounds, formed by close reaction pathways, play an important role as markers of food safety and quality. A method capable of simultaneously quantifying both molecules is thus highly relevant for developing mitigation strategies and preserving the sensory properties of food at the same time. We have developed a unique reliable and sensitive headspace trap (HS trap) extraction method coupled to GC-MS for the simultaneous quantification of furan and furfural in a solid processed food (sponge cake). HS Trap extraction has been optimized using an optimal design of experiments (O-DOE) approach, considering four instrumental and two sample preparation variables, as well as a blocking factor identified during preliminary assays. Multicriteria and multiple response optimization was performed based on a desirability function, yielding the following conditions: thermostatting temperature, 65°C; thermostatting time, 15min; number of pressurization cycles, 4; dry purge time, 0.9min; water / sample amount ratio (dry basis), 16; and total amount (water + sample amount, dry basis), 10g. The performances of the optimized method were also assessed: repeatability (RSD: ≤3.3% for furan and ≤2.6% for furfural), intermediate precision (RSD: 4.0% for furan and 4.3% for furfural), linearity (R 2 : 0.9957 for furan and 0.9996 for furfural), LOD (0.50ng furan g sample dry basis -1 and 10.2ng furfural g sample dry basis -1 ), LOQ (0.99ng furan g sample dry basis -1 and 41.1ng furfural g sample dry basis -1 ). Matrix effect was observed mainly for furan. Finally, the optimized method was applied to other sponge cakes with different matrix characteristics and levels of analytes. Copyright © 2016. Published by Elsevier B.V.

A new approach to the synthesis of monomers and polymers incorporating furan/maleimide Diels-Alder adducts

NASA Astrophysics Data System (ADS)

Banella, Maria Barbara; Gioia, Claudio; Vannini, Micaela; Colonna, Martino; Celli, Annamaria; Gandini, Alessandro

2016-05-01

The Diels-Alder reaction between furan and maleimide moieties is a well-known and widely used strategy to build bio-based macromolecular structures with peculiar properties. The furan-maleimide adducts are thermally reversible because they can be broken above about 120°C and recombined at lower temperatures. At the moment only the monomers exhibiting the furan or the maleimide moieties on their extremity are used in order to get linear or cross-linked polymeric structures. The innovative idea described here consists in using a monomer bearing two carboxylic acidic groups on its extremities and a furan-maleimide Diels-Alder adduct within its structure. This monomer can give rise to classical polycondensation reactions leading to polymers. These polymers (which are polyesters in the present case) can be broken at high temperatures in correspondence of the furane-maleimide Diels-Alder adduct leading to segments exhibiting furan or maleimide moieties at their extremities, which at lower temperature recombine leading to random or block copolymers.

Total synthesis of (+/-)-taiwaniaquinol B via a domino intramolecular friedel-crafts acylation/carbonyl alpha-tert-alkylation reaction.

PubMed

Fillion, Eric; Fishlock, Dan

2005-09-28

The first synthesis of taiwaniaquinol B, a 6-nor-5(6-->7)abeoabietane-type diterpenoid exhibiting the uncommon fused 6-5-6 tricyclic carbon skeleton, was accomplished in 15 steps. A Lewis acid-promoted tandem intramolecular Friedel-Crafts/carbonyl alpha-tert-alkylation reaction was exploited as the core strategy for the synthesis of the sterically congested 1-indanone-containing tricyclic structure. This multiple carbon-carbon bond forming reaction exploits the unique reactivity of Meldrum's acid. The facile precursor synthesis makes this a useful methodology for the expedient modification and assembly of sterically congested 1-indanone-containing ring systems.

The Nature of the Intramolecular Charge Transfer State in Peridinin

PubMed Central

Wagner, Nicole L.; Greco, Jordan A.; Enriquez, Miriam M.; Frank, Harry A.; Birge, Robert R.

2013-01-01

Experimental and theoretical evidence is presented that supports the theory that the intramolecular charge transfer (ICT) state of peridinin is an evolved state formed via excited-state bond-order reversal and solvent reorganization in polar media. The ICT state evolves in <100 fs and is characterized by a large dipole moment (∼35 D). The charge transfer character involves a shift of electron density within the polyene chain, and it does not involve participation of molecular orbitals localized in either of the β-rings. Charge is moved from the allenic side of the polyene into the furanic ring region and is accompanied by bond-order reversal in the central portion of the polyene chain. The electronic properties of the ICT state are generated via mixing of the “11Bu+” ionic state and the lowest-lying “21Ag–” covalent state. The resulting ICT state is primarily 1Bu+-like in character and exhibits not only a large oscillator strength but an unusually large doubly excited character. In most solvents, two populations exist in equilibrium, one with a lowest-lying ICT ionic state and a second with a lowest-lying “21Ag–” covalent state. The two populations are separated by a small barrier associated with solvent relaxation and cavity formation. PMID:23528091

2-Arylbenzo[b]furan derivatives as potent human lipoxygenase inhibitors.

PubMed

Lang, Li; Dong, Ningning; Wu, Deyan; Yao, Xue; Lu, Weiqiang; Zhang, Chen; Ouyang, Ping; Zhu, Jin; Tang, Yun; Wang, Wei; Li, Jian; Huang, Jin

2016-01-01

Human lipoxygenases (LOXs) have been emerging as effective therapeutic targets for inflammatory diseases. In this study, we found that four natural 2-arylbenzo[b]furan derivatives isolated from Artocarpus heterophyllus exhibited potent inhibitory activities against human LOXs, including moracin C (1), artoindonesianin B-1 (2), moracin D (3), moracin M (4). In our in vitro experiments, compound 1 was identified as the most potent LOX inhibitor and the moderate subtype selective inhibitor of 12-LOX. Compounds 1 and 2 act as competitive inhibitors of LOXs. Moreover, 1 significantly inhibits LTB4 production and chemotactic capacity of neutrophils, and is capable of protecting vascular barrier from plasma leakage in vivo. In addition, the preliminary structure-activity relationship analysis was performed based on the above four naturally occurring (1-4) and six additional synthetic 2-arylbenzo[b]furan derivatives. Taken together, these 2-arylbenzo[b]furan derivatives, as LOXs inhibitors, could represent valuable leads for the future development of therapeutic agents for inflammatory diseases.

[Studies on the occurrence of furan in food for infants by gas chromatography with mass spectrometry method].

PubMed

Minorczyk, Maria; Starski, Andrzej; Jedra, Małgorzata; Gawarska, Halina; Sawilska-Rautenstrauch, Dorota

2011-01-01

Furan is an organic compound formed during heat treatment. It has been shown to be carcinogenic in animal laboratory studies. The aim of this study was to determine the content of furan in vegetables and vegetable-meat products intended for infants. The testing system used during this study was gas chromatography coupled with mass spectrometry (GC/MS). The content of furan in 48 samples of processed food ready to eat has been determined. In all samples furan was detected within the range from 13.2 to 91.1 microg/kg, and its average value was 43.3 microg/kg. The paper estimate the exposure assessment of infants to furan found in food. The calculated exposure ranged from 0.23 to 1.77 microg/kg bw/day with the average content of furan in ready to eat products ranged from 35.3 to 52.2 microg/kg. Exposure did not exceed the ADI value 2 microg/kg bw/day.

Formation and emission of large furans and oxygenated hydrocarbons from flames

DOE PAGES

Johansson, K. Olof; Dillstrom, Tyler; Monti, Matteo; ...

2016-07-07

Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. Wemore » used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that fura ns are produced in the high- Temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ~100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbonand oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming.« less

Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components

DOE PAGES

Christensen, Earl; Fioroni, Gina M.; Kim, Seonah; ...

2017-11-06

Alkylated furans such as 2,5-dimethylfuran and 2-methylfuran can be produced from biomass and have very attractive properties for use as spark-ignition fuel blendstocks. Their high octane numbers, relatively high energy density, low water solubility, and minimal effect on gasoline blend volatility are potentially significant advantages over alcohol-based fuels. However, prior studies have reported poor oxidative stability for furanic compound-gasoline blends, as well as the potential for the formation of dangerous organic peroxides. We show that alkylated furans have very low oxidative stability compared to conventional gasoline. Upon oxidation they form highly polar ring-opening products that can react with the startingmore » furanic compound to form dimers, trimers, and higher polymers with intact furan rings. Dimers of the starting furan compounds were also observed. These gasoline-insoluble gums can be problematic for fuel storage or in vehicle fuel systems. Evaporation to dryness under ambient conditions also produced gum with similar composition. Gums produced via evaporation were found to contain peroxides; however, whether these pose a threat of shock initiated explosion has not been determined. We also propose a density functional theory-based analysis of possible reaction pathways, showing that OH radicals can form by reaction of the alkyl group and that addition of OH radicals to the furan ring is energetically favored and leads to ring opening products. As a result, antioxidant additives can be effective at limiting the oxidation reaction in gasoline, but require much higher concentrations than are commonly used in commercial gasolines.« less

Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components

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

Christensen, Earl; Fioroni, Gina M.; Kim, Seonah

Alkylated furans such as 2,5-dimethylfuran and 2-methylfuran can be produced from biomass and have very attractive properties for use as spark-ignition fuel blendstocks. Their high octane numbers, relatively high energy density, low water solubility, and minimal effect on gasoline blend volatility are potentially significant advantages over alcohol-based fuels. However, prior studies have reported poor oxidative stability for furanic compound-gasoline blends, as well as the potential for the formation of dangerous organic peroxides. We show that alkylated furans have very low oxidative stability compared to conventional gasoline. Upon oxidation they form highly polar ring-opening products that can react with the startingmore » furanic compound to form dimers, trimers, and higher polymers with intact furan rings. Dimers of the starting furan compounds were also observed. These gasoline-insoluble gums can be problematic for fuel storage or in vehicle fuel systems. Evaporation to dryness under ambient conditions also produced gum with similar composition. Gums produced via evaporation were found to contain peroxides; however, whether these pose a threat of shock initiated explosion has not been determined. We also propose a density functional theory-based analysis of possible reaction pathways, showing that OH radicals can form by reaction of the alkyl group and that addition of OH radicals to the furan ring is energetically favored and leads to ring opening products. As a result, antioxidant additives can be effective at limiting the oxidation reaction in gasoline, but require much higher concentrations than are commonly used in commercial gasolines.« less

Structure-Odor Correlations in Homologous Series of Mercapto Furans and Mercapto Thiophenes Synthesized by Changing the Structural Motifs of the Key Coffee Odorant Furan-2-ylmethanethiol.

PubMed

Schoenauer, Sebastian; Schieberle, Peter

2018-04-25

Furan-2-ylmethanethiol (2-furfurylthiol; 2-FFT, 1) is long-known as a key odorant in roast and ground coffee and was also previously identified in a wide range of thermally treated foods such as meat, bread, and roasted sesame seeds. Its unique coffee-like odor quality elicited at very low concentrations, and the fact that only a very few compounds showing a similar structure have previously been described in foods make 1 a suitable candidate for structure-odor activity studies. To gain insight into the structural features needed to evoke a coffee-like odor at low concentrations, 46 heterocyclic mercaptans and thio ethers were synthesized, 32 of them for the first time, and their odor qualities and odor thresholds were determined. A movement of the mercapto group to the 3-position kept the coffee-like aroma but led to an increase in odor threshold. A separation of the thiol group from the furan ring by an elongation of the carbon side chain caused a loss of the coffee-like odor and also led to an increase in odor thresholds, especially for ω-(furan-2-yl)alkane-1-thiols with six or seven carbon atoms in the side chain. A displacement of the furan ring by a thiophene ring had no significant influence on the odor properties of most of the compounds studied, but the newly synthesized longer-chain 1-(furan-2-yl)- and 1-(thiophene-2-yl)alkane-1-thiols elicited interesting passion fruit-like scents. In total, only 4 out of the 46 compounds also showed a coffee-like odor quality like 1, but none showed a lower odor threshold. Besides the odor attributes, also retention indices, mass spectra, and NMR data of the synthesized compounds were elaborated, which are helpful in possible future identification of these compounds in trace levels in foods or other materials.

Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers.

PubMed

Song, Hai-Jie; Deng, Jin; Cui, Min-Shu; Li, Xing-Long; Liu, Xin-Xin; Zhu, Rui; Wu, Wei-Peng; Fu, Yao

2015-12-21

Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification of Furan Metabolites Derived from Cysteine-cis-2-Butene-1,4-Dial-Lysine Crosslinks

PubMed Central

Lu, Ding; Peterson, Lisa A.

2010-01-01

Furan is a rodent hepatotoxicant and carcinogen. Since this compound is an important industrial intermediate and has been detected in heat-processed foods and smoke, humans are likely exposed to this toxic compound. Characterization of urinary metabolites of furan will lead to the development of biomarkers to assess human health risks associated with furan exposure. Previous studies indicate that furan is oxidized to a reactive α, β-unsaturated dialdehyde, cis-2-butene-1,4-dial (BDA), in a reaction catalyzed by cytochrome P450. Five previously characterized metabolites are derived from the reaction of BDA with cellular nucleophiles such as glutathione and protein. They include the mono-glutathione reaction product, N-[4-carboxy-4-(3-mercapto-1H-pyrrol-1-yl)-1-oxobutyl]-L-cysteinylglycine cyclic sulfide and its downstream metabolite, S-[1-(1,3-dicarboxypropyl)-1H-pyrrol-3-yl]methylthiol as well as R-2-acetylamino-6-(2,5-dihydro-2-oxo-1H-pyrrol-1-yl)-1-hexanoic acid and N-acetyl-S-[1-(5-acetylamino-5-carboxypentyl)-1H-pyrrol-3-yl]-L-cysteine and its sulfoxide. The last two compounds are downstream metabolites of a BDA-derived cysteine-lysine crosslink, S-[1-(5-amino-5-carboxypentyl)-1H-pyrrol-3-yl]-L-cysteine. In this report, we present the characterization of seven additional urinary furan metabolites, all of which are derived from this crosslink. The cysteinyl residue is subject to several biotransformation reactions, including N-acetylation and S-oxidation. Alternatively, it can undergo β-elimination followed by S-methylation to a methylthiol intermediate that is further oxidized to a sulfoxide. The lysine portion of the crosslink is either N-acetylated or undergoes an oxidative transamination reaction to generate an α-ketoacid metabolite that undergoes oxidative decarboxylation. Some of these metabolites are among the most abundant furan metabolites present in urine as judged by LC-MS/MS analysis, indicating that the oxidation of furan to BDA and BDA�

Estimation of furan contamination across the Belgian food chain.

PubMed

Scholl, G; Scippo, M-L; De Pauw, E; Eppe, G; Saegerman, C

2012-01-01

This paper provides an estimate of the furan content of Belgian foods. The objective of the study was to achieve the best food chain coverage with a restricted number of samples (n = 496). The geographic distribution, different market chains and labels, and consumption frequencies were taken into account in the construction of the sampling plan. Weighting factors such as contamination levels, consumption frequency and the diversity of food items were applied to set up the model. The very low detection capabilities (CC(β)) of the analytical methods used (sub-ppb) allowed reporting of 78.2% of the overall dataset above CC(β) and, in particular, 96.7% for the baby food category. The highest furan levels were found in powdered roasted bean coffee (1912 µg kg(-1)) with a mean of 756 µg kg(-1) for this category. Prepared meat, pasta and rice, breakfast cereals, soups, and baby food also showed high mean furan contents ranging from 16 to 43 µg kg(-1). Comparisons with contamination surveys carried out in other countries pointed out differences for the same food group and therefore contamination levels are related to the geographical origin of food items.

Designed synthesis and supramolecular architectures of furan-substituted perylene diimide.

PubMed

Yu, Yanwen; Li, Yongjun; Qin, Zhihong; Jiang, Runsheng; Liu, Huibiao; Li, Yuliang

2013-06-01

Novel furan-substituted perylene diimides are successfully synthesized and an efficient supramolecular architecture approach to construct zero/one-dimensional nano- and micro-structures by controlling solvents has been demonstrated. The aggregate structure conversion in different molecular structures can be controlled in the form of sphere-like, rod-like, and vesicle-like structures. As expected, these solid supramolecular rod-like architectures displayed interesting optical waveguide behavior, which indicates the aggregate structure materials of furan-substituted perylene diimides have the potential application as micro-scale photonic elements. Copyright © 2013 Elsevier Inc. All rights reserved.

Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT) of calix[4]arene: A TDDFT study

NASA Astrophysics Data System (ADS)

Wang, Se; Wang, Zhuang; Hao, Ce

2016-01-01

The time-dependent density functional theory (TDDFT) method was performed to investigate the excited-state intramolecular double proton transfer (ESIDPT) reaction of calix[4] arene (C4A) and the role of the intramolecular hydrogen bonds in the ESIDPT process. The geometries of C4A in the ground state and excited states (S1, S2 and T1) were optimized. Four intramolecular hydrogen bonds formed in the C4A are strengthened or weakened in the S2 and T1 states compared to those in the ground state. Interestingly, upon excitation to the S1 state of C4A, two protons H1 and H2 transfer along the two intramolecular hydrogen bonds O1-H1···O2 and O2-H2···O3, while the other two protons do not transfer. The ESIDPT reaction breaks the primary symmetry of C4A in the ground state. The potential energy curves of proton transfer demonstrate that the ESIDPT process follows the stepwise mechanism but not the concerted mechanism. Findings indicate that intramolecular hydrogen bonding is critical to the ESIDPT reactions in intramolecular hydrogen-bonded systems.

On the Brønsted acid-catalyzed homogeneous hydrolysis of furans.

PubMed

Nikbin, Nima; Caratzoulas, Stavros; Vlachos, Dionisios G

2013-11-01

Furan affairs: Electronic structure calculations of the homogeneous Brønsted acid-catalyzed hydrolysis of 2,5-dimethylfuran show that proton transfer to the β-position is rate-limiting and provides support that the hydrolysis follows general acid catalysis. By means of projected Fukui indices, we show this to be the case for unsubstituted, 2-, and 2,5-substituted furans with electron-donating groups. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable Oleo-Furan Surfactants by Acylation of Renewable Furans

DOE PAGES

Park, Dae Sung; Joseph, Kristeen E.; Koehle, Maura; ...

2016-10-19

One important advance in fluid surface control was the amphiphilic surfactant composed of coupled molecular structures (i.e., hydrophilic and hydrophobic) to reduce surface tension between two distinct fluid phases. However, implementation of simple surfactants has been hindered by the broad range of applications in water containing alkaline earth metals (i.e., hard water). This disrupts surfactant function and requires extensive use of undesirable and expensive chelating additives. We show that sugar-derived furans can be linked with triglyceride-derived fatty acid chains via Friedel–Crafts acylation within single layer (SPP) zeolite catalysts. Finally, these alkylfuran surfactants independently suppress the effects of hard water whilemore » simultaneously permitting broad tunability of size, structure, and function, which can be optimized for superior capability for forming micelles and solubilizing in water.« less

Tunable Oleo-Furan Surfactants by Acylation of Renewable Furans

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

Park, Dae Sung; Joseph, Kristeen E.; Koehle, Maura

2016-11-23

An important advance in fluid surface control was the amphiphilic surfactant comprised of coupled molecular structures (i.e. hydrophilic and hydrophobic) to reduce surface tension between two distinct fluid phases. However, implementation of simple surfactants has been hindered by the broad range of applications in water containing alkaline earth metals (i.e. hard water), which disrupt surfactant function and require extensive use of undesirable and expensive chelating additives. Here we show that sugar-derived furans can be linked with triglyceride-derived fatty acid chains via Friedel-Crafts acylation within single layer (SPP) zeolite catalysts. These alkylfuran surfactants independently suppress the effects of hard water whilemore » simultaneously permitting broad tunability of size, structure, and function, which can be optimized for superior capability for forming micelles and solubilizing in water.« less

Polyamide copolymers having 2,5-furan dicarboxamide units

DOEpatents

Chisholm, Bret Ja; Samanta, Satyabrata

2017-09-19

Polyamide copolymers, and methods of making and using polyamide copolymers, having 2,5-furan dicarboxamide units are disclosed herein. Such polymers can be useful for engineering thermoplastics having advantageous physical and/or chemical properties.

PHD Domain-Mediated E3 Ligase Activity Directs Intramolecular Sumoylation of an Adjacent Bromodomain which is Required for Gene Silencing

PubMed Central

Ivanov, Alexey V.; Peng, Hongzhuang; Yurchenko, Vyacheslav; Yap, Kyoko L.; Negorev, Dmitri G.; Schultz, David C.; Psulkowski, Elyse; Fredericks, William J.; White, David E.; Maul, Gerd G.; Sadofsky, Moshe J.; Zhou, Ming-Ming; Rauscher, Frank J.

2015-01-01

SUMMARY Tandem PHD and bromodomains are often found in chromatin-associated proteins and have been shown to cooperate in gene silencing. Each domain can bind specifically modified histones: the mechanisms of cooperation between these domains are unknown. We show that the PHD domain of the KAP1 corepressor functions as an intramolecular E3 ligase for sumoylation of the adjacent bromodomain. The RING finger-like structure of the PHD domain is required for both Ubc9 binding and sumoylation and directs modification to specific lysine residues in the bromodomain. Sumoylation is required for KAP1-mediated gene silencing and functions by directly recruiting the SETDB1 histone methyltransferase and the CHD3/Mi2 component of the NuRD complex via SUMO interacting motifs. Sumoylated KAP1 stimulates the histone methyltransferase activity of SETDB1. These data provide a mechanistic explanation for the cooperation of PHD and bromodomains in gene regulation and describe a new function of the PHD domain as an intramolecular E3 SUMO ligase. PMID:18082607

Synthesis of 2-aryl and 3-aryl benzo[b]furan thioethers using aryl sulfonyl hydrazides as sulfenylation reagents.

PubMed

Zhao, Xia; Zhang, Lipeng; Lu, Xiaoyu; Li, Tianjiao; Lu, Kui

2015-03-06

An efficient, metal-free protocol used to synthesize aryl benzo[b]furan thioethers based on the I2-catalyzed cross-coupling of benzo[b]furans as well as the electrophilic cyclization of 2-alkynylphenol derivatives with aryl sulfonyl hydrazides was developed. Various 2-aryl and 3-aryl benzo[b]furan thioethers were obtained in moderate to good yields.

Tree-ring cellulose exhibits several distinct intramolecular 13C signals

NASA Astrophysics Data System (ADS)

Wieloch, Thomas; Ehlers, Ina; Frank, David; Gessler, Arthur; Grabner, Michael; Yu, Jun; Schleucher, Jürgen

2017-04-01

Stable carbon isotopes are a key tool in biogeosciences. Present applications including compound-specific isotope analysis measure 13C/12C ratios (δ13C) of bulk material or of whole molecules. However, it is well known that primary metabolites also show large intramolecular 13C variation - also called isotopomer variation. This variation reflects 13C fractionation by enzyme reactions and therefore encodes metabolic information. Furthermore, δ13C must be considered an average of the intramolecular 13C distribution. Here we will present (1) methodology to analyse intramolecular 13C distributions of tree-ring cellulose by quantitative 13C NMR (Chaintreau et al., 2013, Anal Chim Acta, 788, 108-113); (2) intramolecular 13C distributions of an annually-resolved tree ring chronology (Pinus nigra, 1961-1995); (3) isotope parameters and terminology for analysis of intramolecular isotope time series; (4) a method for correcting for heterotrophic C redistribution. We will show that the intramolecular 13C distribution of tree-ring cellulose shows large variation, with differences between isotopomers exceeding 10‰Ṫhus, individual 13C isotopomers of cellulose constitute distinct 13C inputs into major global C pools such as wood and soil organic matter. When glucose units with the observed intramolecular 13C pattern are broken down along alternative catabolic pathways, it must be expected that respired CO2 with strongly differing δ13C will be released; indicating that intramolecular 13C variation affects isotope signals of atmosphere-biosphere C exchange fluxes. taking this variation into account will improve modelling of the global C cycle. Furthermore, cluster analysis shows that tree-ring glucose exhibits several independent intramolecular 13C signals, which constitute distinct ecophysiological information channels. Thus, whole-molecule 13C analysis likely misses a large part of the isotope information stored in tree rings. As we have shown for deuterium (Ehlers et al

Evaluation of serum and liver toxicokinetics for furan and liver DNA adduct formation in male Fischer 344 rats.

PubMed

Churchwell, M I; Scheri, R C; Von Tungeln, L S; Gamboa da Costa, G; Beland, F A; Doerge, D R

2015-12-01

Furan is a food processing contaminant found in many common cooked foods that induces liver toxicity and liver cancer in animal models treated with sufficient doses. The metabolism of furan occurs primarily in the liver where CYP 2E1 produces a highly reactive bis-electrophile, cis-2-butene-1,4-dial (BDA). BDA reacts with nucleophilic groups in amino acids and DNA in vitro to form covalent adducts. Evidence for BDA-nucleoside adduct formation in vivo is limited but important for assessing the carcinogenic hazard of dietary furan. This study used controlled dosing with furan in Fischer 344 rats to measure serum and liver toxicokinetics and the possible formation of BDA-nucleoside adducts in vivo. After gavage exposure, furan concentrations in the liver were consistently higher than those in whole blood (∼6-fold), which is consistent with portal vein delivery of a lipophilic compound into the liver. Formation of BDA-2'-deoxycytidine in furan-treated rat liver DNA was not observed using LC/MS/MS after single doses as high as 9.2 mg/kg bw or repeated dosing for up to 360 days above a consistent background level (1-2 adducts per 10(8) nucleotides). This absence of BDA-nucleoside adduct formation is consistent with the general lack of evidence for genotoxicity of furan in vivo. Published by Elsevier Ltd.

Increased Furan Tolerance in Escherichia coli Due to a Cryptic ucpA Gene

PubMed Central

Wang, Xuan; Miller, Elliot N.; Yomano, Lorraine P.; Shanmugam, K. T.

2012-01-01

Expression arrays were used to identify 4 putative oxidoreductases that were upregulated (>3-fold) by furfural (15 mM, 15 min). Plasmid expression of one (ucpA) increased furan tolerance in ethanologenic strain LY180 and wild-type strain W. Deleting ucpA decreased furfural tolerance. Although the mechanism remains unknown, the cryptic ucpA gene is now associated with a phenotype: furan resistance. PMID:22267665

Same-sample determination of ultratrace levels of polybromodiphenylethers, polybromodibenzo-p-dioxins/furans, and polychlorodibenzo-p-dioxins/furans from combustion flue gas

EPA Science Inventory

The analytical method used for determination of polychlorinated dibenzo-p-dioxins and -furans (PCDDs/Fs) emissions from municipal waste combustors and other stationary sources was modified and validated to enable simultaneous analysis of ultra trace levels of polybrominated diphe...

An experimental study of furan adsorption and decomposition on vicinal palladium surfaces using scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Loui, A.; Chiang, S.

2018-04-01

The intact adsorption and decomposition of furan (C4H4O) on vicinal palladium surfaces with (111)-oriented terraces has been studied by scanning tunneling microscopy (STM) over a range of temperatures. STM images at 225 K show that furan molecules lie flat and prefer to adsorb at upper step edges. At 225 K, furan molecules adsorbed on "narrow" terraces of 20 to 45 Å in width appear to diffuse more readily than those adsorbed on "wide" terraces of 160 to 220 Å. A distinct population of smaller features appears in STM images on "narrow" terraces at 288 K and on "wide" terraces at 415 K and is identified with the C3H3 decomposition product, agreeing with prior studies which demonstrated that furan dissociates on Pd(111) to yield carbon monoxide (CO) and a C3H3 moiety in the 280 to 320 K range. Based on our direct visualization of this reaction using STM, we propose a spatial mechanism in which adsorption of furan at upper step edges allows catalysis of the dissociation, followed by diffusion of the product to lower step edges.

Risk assessment for infants exposed to furan from ready-to-eat thermally processed food products in Poland.

PubMed

Minorczyk, Maria; Góralczyk, Katarzyna; Struciński, Paweł; Hernik, Agnieszka; Czaja, Katarzyna; Łyczewska, Monika; Korcz, Wojciech; Starski, Andrzej; Ludwicki, Jan K

2012-01-01

Thermal processes and long storage of food lead to reactions between reducing sugars and amino acids, or with ascorbic acid, carbohydrates or polyunsaturated fatty acids. As a result of these reactions, new compounds are created. One of these compounds having an adverse effect on human health is furan. The aim of this paper was to estimate the infants exposure to furan found in thermally processed jarred food products, as well as characterizing the risk by comparing the exposure to the reference dose (RfD) and calculating margins of exposure. The material consisted of 301 samples of thermally processed food for infants taken from the Polish market in years 2008 - 2010. The samples included vegetable-meat, vegetables and fruit jarred meals for infants and young children in which the furan levels were analyzed by GC/MS technique. The exposure to furan has been assessed for the 3, 4, 6, 9,12 months old infants using different consumption scenarios. The levels of furan ranged from <1 microg/kg (LOQ) to 166.9 microg/kg. The average furan concentration in all samples was 40.2 microg/kg. The estimated exposures, calculated with different nutrition scenarios, were in the range from 0.03 to 3.56 microg/kg bw/day and exceeded in some cases RfD set at level of 1 microg/kg bw/day. Margins of exposure (MOE) achieved values even below 300 for scenarios assuming higher consumption of vegetable and vegetable-meat products. The magnitude of exposure to furan present in ready-to-eat meals among Polish infants is similar to data reported previously in other European countries but slightly higher than indicated in the recent EFSA report. As for some cases the estimated intake exceeds the RfD, and MOE) values are much lower than 10000 indicating a potential health concern, it is necessary to continue monitoring of furan in jarred food and estimate of its intake by infants.

Covalent modification of cytochrome c by reactive metabolites of furan.

PubMed

Phillips, Martin B; Sullivan, Mathilde M; Villalta, Peter W; Peterson, Lisa A

2014-01-21

Metabolism of the hepatotoxicant furan leads to protein adduct formation in the target organ. The initial bioactivation step involves cytochrome P450-catalyzed oxidation of furan, generating cis-2-butene-1,4-dial (BDA). BDA reacts with lysine to form pyrrolin-2-one adducts. Metabolic studies indicate that BDA also reacts with glutathione (GSH) to generate 2-(S-glutathionyl)butanedial (GSH-BDA), which then reacts with lysine to form GSH-BDA-lysine cross-links. To explore the relative reactivity of these two reactive intermediates, cytochrome c was reacted with BDA in the presence and absence of GSH. As judged by MALDI-TOF mass spectrometry, BDA reacts extensively with cytochrome c to form adducts that add 66 Da to the protein, consistent with the formation of pyrrolinone adducts. Addition of GSH to the reaction mixture reduced the overall extent of adduct formation. The mass of the adducted protein was shifted by 355 Da as expected for GSH-BDA-protein cross-link formation. LC-MS/MS analysis of the tryptic digests of the alkylated protein indicated that the majority of adducts occurred on lysine residues, with BDA reacting less selectively than GSH-BDA. Both types of adducts may contribute to the toxic effects of furan.

Covalent Modification of Cytochrome C by Reactive Metabolites of Furan

PubMed Central

Phillips, Martin B.; Sullivan, Mathilde M.; Villalta, Peter W.; Peterson, Lisa A.

2014-01-01

Metabolism of the hepatotoxicant furan leads to protein adduct formation in the target organ. The initial bioactivation step involves cytochrome P450-catalyzed oxidation of furan, generating cis-2-butene-1,4-dial (BDA). BDA reacts with lysine to form pyrrolin-2-one adducts. Metabolic studies indicate that BDA also reacts with glutathione (GSH) to generate 2-(S-glutathionyl)butanedial (GSH-BDA), which then reacts with lysine to form GSH-BDA-lysine cross-links. To explore the relative reactivity of these two reactive intermediates, cytochrome c was reacted with BDA in the presence and absence of GSH. As judged by MALDI-TOF mass spectrometry, BDA reacts extensively with cytochrome c to form adducts that add 66 Da to the protein, consistent with the formation of pyrrolinone adducts. Addition of GSH to the reaction mixture reduced the overall extent of adduct formation. The mass of the adducted protein was shifted by 355 Da as expected for GSH-BDA-protein cross-link formation. LC-MS/MS analysis of the tryptic digests of the alkylated protein indicated that the majority of adducts occurred on lysine residues, with BDA reacting less selectively than GSH-BDA. Both types of adducts may contribute to the toxic effects of furan. PMID:24364757

Degraded protein adducts of cis-2-butene-1,4-dial are urinary and hepatocyte metabolites of furan.

PubMed

Lu, Ding; Sullivan, Mathilde M; Phillips, Martin B; Peterson, Lisa A

2009-06-01

Furan is a liver toxicant and carcinogen in rodents. On the basis of these observations and the large potential for human exposure, furan has been classified as a possible human carcinogen. The mechanism of tumor induction by furan is unknown. However, the toxicity requires cytochrome P450-catalyzed oxidation of furan. The product of this oxidation, cis-2-butene-1,4-dial (BDA), reacts readily with glutathione, amino acids, and DNA and is a bacterial mutagen in Ames assay strain TA104. Characterization of the urinary metabolites of furan is expected to provide information regarding the structure(s) of the reactive metabolite(s). Recently, several urinary metabolites have been identified. We reported the presence of a monoglutathione-BDA reaction product, N-[4-carboxy-4-(3-mercapto-1H-pyrrol-1-yl)-1-oxobutyl]-l-cysteinylglycine cyclic sulfide. Three additional urinary metabolites of furan were also characterized as follows: R-2-acetylamino-6-(2,5-dihydro-2-oxo-1H-pyrrol-1-yl)-1-hexanoic acid, N-acetyl-S-[1-(5-acetylamino-5-carboxypentyl)-1H-pyrrol-3-yl]-l-cysteine, and its sulfoxide. It was postulated that these three metabolites are derived from degraded protein adducts. However, the possibility that these metabolites result from the reaction of BDA with free lysine and/or cysteine was not ruled out. In this latter case, one might predict that the reaction of thiol-BDA with free lysine would not occur exclusively on the epsilon-amino group. Reaction of BDA with N-acetylcysteine or GSH in the presence of lysine indicated that both the alpha- and the epsilon-amino groups of lysine can be modified by thiol-BDA. The N-acetylcysteine-BDA-N-acetyllysine urinary metabolites were solely linked through the epsilon-amino group of lysine. A GSH-BDA-lysine cross-link was a significant hepatocyte metabolite of furan. In this case, the major product resulted from reaction with the epsilon-amino group of lysine; however, small amounts of the alpha-amino reaction product were also

Degraded protein adducts of cis-2-butene-1,4-dial are urinary and hepatocyte metabolites of furan

PubMed Central

Lu, Ding; Sullivan, Mathilde M.; Phillips, Martin B.; Peterson, Lisa A.

2009-01-01

Furan is a liver toxicant and carcinogen in rodents. Based on these observations and the large potential for human exposure, furan has been classified as a possible human carcinogen. The mechanism of tumor induction by furan is unknown. However, the toxicity requires cytochrome P450 catalyzed oxidation of furan. The product of this oxidation, cis-2-butene-1,4-dial (BDA), reacts readily with glutathione, amino acids and DNA and is a bacterial mutagen in Ames assay strain TA104. Characterization of the urinary metabolites of furan is expected to provide information regarding the structure(s) of the reactive metabolite(s). Recently, several urinary metabolites have been identified. We reported the presence of a mono-glutathione-BDA reaction product, N-[4-carboxy-4-(3-mercapto-1H-pyrrol-1-yl)-1-oxobutyl]-L-cysteinylglycine cyclic sulfide. Three additional urinary metabolites of furan were also characterized: R-2-acetylamino-6-(2,5-dihydro-2-oxo-1H-pyrrol-1-yl)-1-hexanoic acid, N-acetyl-S-[1-(5-acetylamino-5-carboxypentyl)-1H-pyrrol-3-yl]-L-cysteine and its sulfoxide. It was postulated that these three metabolites are derived from degraded protein adducts. However, the possibility that these metabolites result from reaction of BDA with free lysine and/or cysteine was not ruled out. In this latter case, one might predict that the reaction of thiol-BDA with free lysine would not occur exclusively on the ε-amino group. Reaction of BDA with N-acetylcysteine or GSH in the presence of lysine indicated that both the α- and ε-amino groups of lysine can be modified by thiol-BDA. The N-acetylcysteine-BDA-N-acetyllysine urinary metabolites were solely linked through the ε-amino group of lysine. A GSH-BDA-lysine crosslink was a significant hepatocyte metabolite of furan. In this case, the major product resulted from reaction with the ε-amino group of lysine, however, small amounts of the α-amino reaction product were also observed. Western analysis of liver and hepatocyte

Determination of furan levels in commercial samples of baby food from Brazil and preliminary risk assessment.

PubMed

Pavesi Arisseto, A; Vicente, E; De Figueiredo Toledo, M C

2010-08-01

Commercial baby food samples available on the Brazilian market (n = 31) were analysed for furan content using a gas chromatography-mass spectrometry method preceded by solid-phase microextraction. A limit of detection of 0.7 microg kg(-1), a limit of quantitation of 2.4 microg kg(-1), mean recoveries varying from 80% to 107%, and coefficients of variation ranging from 5.6% to 9.4% for repeatability and from 7.4% to 12.4% for within-laboratory reproducibility were obtained during an in-house validation. The levels of furan found in the samples were from not detected to 95.5 microg kg(-1). Samples containing vegetables and meat showed higher furan levels as compared with those containing only fruits. An exposure assessment showed furan intakes up to 2.4 microg kg(-1) body weight day(-1) (99th percentile) for babies fed exclusively with commercial baby foods. Margins of exposure obtained from intakes estimated in this work indicated a potential public health concern.

Intramolecular Hydrogen Bonding Restricts Gd-Aqua-Ligand Dynamics [The Day the Water Stood Still: Intramolecular Hydrogen Bonding to Restrict Gd-Aqua Ligand Dynamics

DOE PAGES

Boros, Eszter; Srinivas, Raja; Kim, Hee -Kyung; ...

2017-04-11

Aqua ligands can undergo rapid internal rotation about the M-O bond. For magnetic resonance contrast agents, this rotation results in diminished relaxivity. Herein, we show that an intramolecular hydrogen bond to the aqua ligand can reduce this internal rotation and increase relaxivity. Molecular modeling was used to design a series of four Gd complexes capable of forming an intramolecular H-bond to the coordinated water ligand, and these complexes had anomalously high relaxivities compared to similar complexes lacking a H-bond acceptor. Molecular dynamics simulations supported the formation of a stable intramolecular H-bond, while alternative hypotheses that could explain the higher relaxivitymore » were systematically ruled out. Finally, intramolecular H-bonding represents a useful strategy to limit internal water rotational motion and increase relaxivity of Gd complexes.« less

Furanic compounds and furfural in different coffee products by headspace liquid-phase micro-extraction followed by gas chromatography-mass spectrometry: survey and effect of brewing procedures.

PubMed

Chaichi, Maryam; Ghasemzadeh-Mohammadi, Vahid; Hashemi, Maryam; Mohammadi, Abdorreza

2015-01-01

In this study, the levels of furan, 2-methylfuran, 2,5-dimethylfuran, vinyl furan, 2-methoxymethyl-furan and furfural in different coffee products were evaluated. Simultaneous determination of these six furanic compounds was performed by a head space liquid-phase micro-extraction (HS-LPME) method. A total of 67 coffee powder samples were analysed. The effects of boiling and espresso-making procedures on the levels of furanic compounds were investigated. The results showed that different types of coffee samples contained different concentrations of furanic compounds, due to the various processing conditions such as temperature, degree of roasting and fineness of grind. Among the different coffee samples, the highest level of furan (6320 µg kg⁻¹) was detected in ground coffee, while coffee-mix samples showed the lowest furan concentration (10 µg kg⁻¹). Levels in brewed coffees indicated that, except for furfural, brewing by an espresso machine caused significant loss of furanic compounds.

Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

PubMed

Lin, Chen; Kumar, Manoj; Finney, Brian A; Francisco, Joseph S

2017-09-28

High level Brueckner doubles with triples correction method-based ab initio calculations have been used to investigate the nature of intramolecular hydrogen bonding and intramolecular hydrogen atom transfer in cis-malonaldehyde (MA) and its radical analogues. The radicals considered here are the ones that correspond to the homolytic cleavage of C-H bonds in cis-MA. The results suggest that cis-MA and its radical analogues, cis-MA RS , and cis-MA RA , both exist in planar geometry. The calculated intramolecular O-H⋯O=C bond in cis-MA is shorter than that in the radical analogues. The intramolecular hydrogen bond in cis-MA is stronger than in its radicals by at least 3.0 kcal/mol. The stability of a cis-malonaldehyde radical correlates with the extent of electron spin delocalization; cis-MA RA , in which the radical spin is more delocalized, is the most stable MA radical, whereas cis-MA RS , in which the radical spin is strongly localized, is the least stable radical. The natural bond orbital analysis indicates that the intramolecular hydrogen bonding (O⋯H⋯O) in cis-malonaldehyde radicals is stabilized by the interaction between the lone pair orbitals of donor oxygen and the σ * orbital of acceptor O-H bond (n → σ * OH ). The calculated barriers indicate that the intramolecular proton transfer in cis-MA involves 2.2 kcal/mol lower barrier than that in cis-MA RS .

Gas-phase Reactivity of meta-Benzyne Analogs Toward Small Oligonucleotides of Differing Lengths

NASA Astrophysics Data System (ADS)

Widjaja, Fanny; Max, Joann P.; Jin, Zhicheng; Nash, John J.; Kenttämaa, Hilkka I.

2017-07-01

The gas-phase reactivity of two aromatic carbon-centered σ,σ-biradicals ( meta-benzyne analogs) and a related monoradical towards small oligonucleotides of differing lengths was investigated in a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer coupled with laser-induced acoustic desorption (LIAD). The mono- and biradicals were positively charged to allow for manipulation in the mass spectrometer. The oligonucleotides were evaporated into the gas phase as intact neutral molecules by using LIAD. One of the biradicals was found to be unreactive. The reactive biradical reacts with dinucleoside phosphates and trinucleoside diphosphates mainly by addition to a nucleobase moiety followed by cleavage of the glycosidic bond, leading to a nucleobase radical (e.g., base-H) abstraction. In some instances, after the initial cleavage, the unquenched radical site of the biradical abstracts a hydrogen atom from the neutral fragment, which results in a net nucleobase abstraction. In sharp contrast, the related monoradical mainly undergoes facile hydrogen atom abstraction from the sugar moiety. As the size of the oligonucleotides increases, the rate of hydrogen atom abstraction from the sugar moiety by the monoradical was found to increase due to the presence of more hydrogen atom donor sites, and it is the only reaction observed for tetranucleoside triphosphates. Hence, the monoradical only attacks sugar moieties in these substrates. The biradical also shows significant attack at the sugar moiety for tetranucleoside triphosphates. This drastic change in reactivity indicates that the size of the oligonucleotides plays a key role in the outcome of these reactions. This finding is attributed to more compact conformations in the gas phase for the tetranucleoside triphosphates than for the smaller oligonucleotides, which result from stronger stabilizing interactions between the nucleobases.

Potential protective effect of L-cysteine against the toxicity of acrylamide and furan in exposed Xenopus laevis embryos: an interaction study.

PubMed

Williams, John Russell; Rayburn, James R; Cline, George R; Sauterer, Roger; Friedman, Mendel

2014-08-06

The embryo toxicities of two food-processing-induced toxic compounds, acrylamide and furan, with and without added L-cysteine were examined individually and in mixtures using the frog embryo teratogenesis assay-Xenopus (FETAX). The following measures of developmental toxicity were used: (a) 96 h LC50, the median concentration causing 50% embryo lethality; (b) 96 h EC50, the median concentration causing 50% malformations of the surviving embryos; and (c) teratogenic index (96 h LC50/96 h EC50), an estimate of teratogenic risk. Calculations of toxic units (TU) were used to assess possible antagonism, synergism, or response addition of several mixtures. The evaluated compounds demonstrated counterintuitive effects. Furan had lower than expected toxicity in Xenopus embryos and, unlike acrylamide, does not seem to be teratogenic. However, the short duration of the tests may not show the full effects of furan if it is truly primarily genotoxic and carcinogenic. L-Cysteine showed unexpected properties in the delay of hatching of the embryos. The results from the interaction studies between combination of two or three components (acrylamide plus L-cysteine; furan plus L-cysteine; acrylamide plus furan; acrylamide plus furan and L-cysteine) show that furan and acrylamide seem to have less than response addition at 1:1 toxic unit ratio in lethality. Acrylamide and L-cysteine show severe antagonism even at low 19 acrylamide/1 L-cysteine TU ratios. Data from the mixture of acrylamide, furan, and L-cysteine show a slight antagonism, less than would have been expected from binary mixture exposures. Bioalkylation mechanisms and their prevention are discussed. There is a need to study the toxicological properties of mixtures of acrylamide and furan concurrently formed in heat-processed food.

Thermochemistry of Hydroxyl and Hydroperoxide Substituted Furan, Methylfuran, and Methoxyfuran.

PubMed

Hudzik, Jason M; Bozzelli, Joseph W

2017-06-15

Reaction pathways are influenced by thermochemical properties, species stability, and chemical kinetics. Understanding these factors allows for an understanding of the reaction paths and formation of intermediate species. Enthalpies of formation (ΔH f,298 ° ), entropies (S 298 ° ), heat capacities (C p (T)), oxygen-hydrogen (O-H), oxygen-oxygen (O-O), and (R-O) bond dissociation energies (BDEs) are reported for hydroxyl and hydroperoxide substituted furan, methylfuran, and methoxyfuran species. Standard enthalpies of formation for parent and radical species have been determined using density functional theory B3LYP/6-31G(d,p), B3LYP/6-311G(2d,2p), and M06-2X/6-31G(d,p) along with higher-level CBS-QB3 and CBS-APNO composite methods. Isodesmic work reactions were employed to improve accuracy by canceling error and show consistency between the levels of theory. Corresponding O-H and O-O BDEs are determined and compared to other similar structures. The stability of the furan moiety coupled with the double-bond-forming capability of the oxygen moiety results in a number of bond energies significantly lower than one might have expected. Substituted hydroperoxides are calculated to have ROO-H BDEs between 86.9 and 94.2 kcal mol -1 , and their RO-OH BDEs show a large 49 kcal mol -1 range of -2.3-46.8 kcal mol -1 . Substituted alcohols also show a wide 48 kcal mol -1 range with RO-H BDEs, ranging from 59.3 to 106.9 kcal mol -1 . Bond lengths of parent and radical species are presented to highlight potential bonds of interest leading to furan ring opening. Group additivity is discussed, and groups for substituted furan, methylfuran, and methoxyfuran species are derived. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) density functional level and are used to determine the S 298 ° and C p (T) values.

Mass Spectrometry Profiles Superoxide-Induced Intra-molecular Disulfide in the FMN-binding Subunit of Mitochondrial Complex I

PubMed Central

Zhang, Liwen; Xu, Hua; Chen, Chwen-Lih; Green-Church, Kari B.; Freitas, Michael A.; Chen, Yeong-Renn

2008-01-01

Protein thiols with regulatory functions play a critical role in maintaining the homeostasis of the redox state in mitochondria. One major host of regulatory cysteines in mitochondria is complex I, with the thiols primarily located on its 51 kDa FMN-binding subunit. In response to oxidative stress, these thiols are expected to form intra-molecular disulfide bridges as one of their oxidative post-translational modifications. Here, to test this hypothesis and gain insights into the molecular pattern of disulfide in complex I, the isolated bovine complex I was prepared. Superoxide (O2•−) is generated by complex I under the conditions of enzyme turnover. O2•−-induced intra-molecular disulfide formation at the 51 kDa subunit was determined by tandem mass spectrometry and database searching, with the latter accomplished by adaptation of the in-house developed database search engine, MassMatrix [Xu H., et. al J. Proteome Res. (2008) 7, 138–44]. LC/MS/MS analysis of tryptic/chymotryptic digests of the 51 kDa subunit from alkylated complex I revealed that four specific cysteines (C125, C142, C187, and C206) of the 51 kDa subunit were involved in the formation of mixed intra-molecular disulfide linkages. In all, three cysteine pairs were observed: C125/C142, C187/C206, and C142/C206. The formation of disulfide bond was subsequently inhibited by superoxide dismutase, indicating the involvement of O2•−. These results elucidated by mass spectrometry indicates that the residues of C125, C142, C187, and C206 are the specific regulatory cysteines of complex I, and they participate in the oxidative modification with disulfide formation under the physiological or pathophysiological conditions of oxidative stress. PMID:18789718

Sustainable pathway to furanics from biomass via ...

EPA Pesticide Factsheets

An organic sulfonated graphitic carbon nitride is synthesized and its application has been demonstrated inthe conversion of carbohydrates into furanics and related value-added products. The most importantfeature of the material is the stability and acidity, which could be utilized at elevated temperatures forcleaving carbohydrates and converting them into biologically important scaffolds and platform chemicals. Prepared for submission to the Royal Society of Chemistry (RSC) Journal, Green Chemistry.

Tandem Cu-catalyzed ketenimine formation and intramolecular nucleophile capture: Synthesis of 1,2-dihydro-2-iminoquinolines from 1-(o-acetamidophenyl)propargyl alcohols

PubMed Central

Kant, Ruchir

2014-01-01

Summary The copper-catalyzed ketenimine formation reaction of 1-(o-acetamidophenyl)propargyl alcohols with various sulfonyl azides is found to undergo a concomitant intramolecular nucleophile attack to generate 1,2-dihydro-2-iminoquinolines after aromatization (via elimination of acetyl and hydroxy groups) and tautomerization. The reaction produces 4-substituted and 3,4-unsubstituted title compounds in moderate to good yields under mild reaction conditions. PMID:24991276

Intramolecular interactions in the polar headgroup of sphingosine: serinol.

PubMed

Loru, Donatella; Peña, Isabel; Alonso, José L; Sanz, M Eugenia

2016-03-04

The intramolecular interactions in the lipid sphingosine have been elucidated through the investigation of the amino alcohol serinol which mimics its polar headgroup. Intricate networks of intramolecular hydrogen bonds involving the hydroxyl groups and the amino group contribute to the stabilisation of five different conformations observed in the broadband rotational spectrum.

Substituent effects on furan-phenylene copolymer for photovoltaic improvement: A density functional study

NASA Astrophysics Data System (ADS)

Janprapa, Nuttaporn; Vchirawongkwin, Viwat; Kritayakornupong, Chinapong

2018-06-01

The structural, electronic and photovoltaic properties of furan-phenylene copolymer ((Fu-co-Ph)4) and its derivatives were evaluated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The calculated band gaps of pristine furan and phenylene are in good agreement with the available experimental data. The lower band gap value of 2.72 eV was obtained from -NO2 and -NHCH3 substituents, leading to broader solar absorption range. With respected to the reorganization energy, -OCH3, -NHCH3, -OH, -SCH3, -CH3, -CF3, -NO2, and -F substituted (Fu-co-Ph)4 structures were classified as better electron donor materials. For combination with PC61BM, -NO2, -CN, -CF3 and -F functionalized copolymers demonstrated significantly higher open circuit voltage (Voc) values ranging from 1.07 to 2.10 eV. Our results revealed that electron withdrawing group substitution on furan-phenylene copolymers was an effective way for improving electronic and optical properties of donor materials used in photovoltaic applications.

Demethylation of 5,n-di-tert-butyl-8,n-dimethoxy[2.n]metacyclophane-1-ynes with BBr3 to afford novel [n]benzofuranophanes

NASA Astrophysics Data System (ADS)

Akther, Thamina; Islam, Md Monarul; Matsumoto, Taisuke; Tanaka, Junji; Feng, Xing; Redshaw, Carl; Yamato, Takehiko

2016-10-01

Novel [n]benzofuranophanes (n = 8 & 10) 2a-b have been prepared by successive intramolecular cyclization from 5,19-di-tert-butyl-8,22-dimethoxy[n]metacyclophane-1-yne (syn-1a-b) by treatment with BBr3 in CH2Cl2 at room temperature for 8h. [2.n]Benzofuranophanes 2a-b were also obtained by treatment of 1,2-di-endo-bromo-5,19-di-tert-butyl-8,22-dimethoxy[n]metacyclophane (meso-3a-b) with BBr3 in CH2Cl2 by using the same reaction conditions. 1H NMR spectra of 2a-b reveals the formation of intramolecular hydrogen bonding between hydroxyl proton with the oxygen of the furan moiety and X-ray analysis shows that the lengths between H (OH) and O (furan) are 1.981 and 1.823 Å̊, respectively. The conformation of [8]benzofuranophane 2a in solution is rigid with restricted rotation around the diaryl linkage rather than [10]benzofuranophane 2b because of weak intramolecular hydrogen bonding and the short length of the cross-linking chain.

Body burden levels of dioxin, furans, and PCBs among frequent consumers of Great Lakes sport fish

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

Falk, C.; Hanrahan, L.; Anderson, H.A.

1999-02-01

Dioxins, furans, and polychlorinated biphenyls (PCBs) are toxic, persist in the environment, and bioaccumulate to concentrations that can be harmful to humans. The Health Departments of five GL states, Wisconsin, Michigan, Ohio, Illinois, and Indiana, formed a consortium to study body burden levels of chemical residues in fish consumers of Lakes Michigan, Huron, and Erie. In Fall 1993, a telephone survey was administered to sport angler households to obtain fish consumption habits and demographics. A blood sample was obtained from a portion of the study subjects. One hundred serum samples were analyzed for 8 dioxin, 10 furan, and 4 coplanarmore » PCB congeners. Multiple linear regression was conducted to assess the predictability of the following covariates: GL sport fish species, age, BMI, gender, years sport fish consumed, and lake. Median total dioxin toxic equivalents (TEq), total furan TEq, and total coplanar PCB TEq were higher among all men than all women (P = 0.0001). Lake trout, salmon, age, BMI, and gender were significant regression predictors of log (total coplanar PCBs). Lake trout, age, gender, and lake were significant regression predictors of log (total furans). Age was the only significant predictor of total dioxin levels.« less

Sustainable pathway to furanics from biomass via heterogeneous organo-catalysis

EPA Science Inventory

An organic sulfonated graphitic carbon nitride is synthesized and its application has been demonstrated inthe conversion of carbohydrates into furanics and related value-added products. The most importantfeature of the material is the stability and acidity, which could be utilize...

New stereoselective intramolecular

PubMed

Alajarin; Vidal; Tovar; Ramirez De Arellano MC; Cossio; Arrieta; Lecea

2000-11-03

Efficient 1,4-asymmetric induction has been achieved in the highly stereocontrolled intramolecular [2 + 2] cycloadditions between ketenimines and imines, leading to 1,2-dihydroazeto[2, 1-b]quinazolines. The chiral methine carbon adjacent to the iminic nitrogen controls the exclusive formation of the cycloadducts with relative trans configuration at C2 and C8. The stepwise mechanistic model, based on theoretical calculations, fully supports the stereochemical outcome of these cycloadditions.

Versatile Tandem Ring-Opening/Ring-Closing Metathesis Polymerization: Strategies for Successful Polymerization of Challenging Monomers and Their Mechanistic Studies.

PubMed

Park, Hyeon; Kang, Eun-Hye; Müller, Laura; Choi, Tae-Lim

2016-02-24

Tandem ring-opening/ring-closing metathesis (RO/RCM) results in extremely fast living polymerization; however, according to previous reports, only monomers containing certain combinations of cycloalkenes, terminal alkynes, and nitrogen linkers successfully underwent tandem polymerization. After examining the polymerization pathways, we proposed that the relatively slow intramolecular cyclization might lead to competing side reactions such as intermolecular cross metathesis reactions to form inactive propagating species. Thus, we developed two strategies to enhance tandem polymerization efficiency. First, we modified monomer structures to accelerate tandem RO/RCM cyclization by enhancing the Thorpe-Ingold effect. This strategy increased the polymerization rate and suppressed the chain transfer reaction to achieve controlled polymerization, even for challenging syntheses of dendronized polymers. Alternatively, reducing the reaction concentration facilitated tandem polymerization, suggesting that the slow tandem RO/RCM cyclization step was the main reason for the previous failure. To broaden the monomer scope, we used monomers containing internal alkynes and observed that two different polymer units with different ring sizes were produced as a result of nonselective α-addition and β-addition on the internal alkynes. Thorough experiments with various monomers with internal alkynes suggested that steric and electronic effects of the alkyne substituents influenced alkyne addition selectivity and the polymerization reactivity. Further polymerization kinetics studies revealed that the rate-determining step of monomers containing certain internal alkynes was the six-membered cyclization step via β-addition, whereas that for other monomers was the conventional intermolecular propagation step, as observed in other chain-growth polymerizations. This conclusion agrees well with all those polymerization results and thus validates our strategies.

Sustainable pathway to furanics from biomass via heterogeneous organo-catalysis

EPA Science Inventory

An organic sulfonated graphitic carbon nitride is synthesized and its application has been demonstrated in the conversion of carbohydrates into furanics and related value-added products. The most important feature of the material is the stability and acidity, which could be utili...

Hydrogen bond docking preference in furans: Osbnd H ⋯ π vs. Osbnd H ⋯ O

NASA Astrophysics Data System (ADS)

Jiang, Xiaotong; Tsona, Narcisse T.; Tang, Shanshan; Du, Lin

2018-02-01

The docking sites of hydrogen bonds in complexes formed between 2,2,2-trifluoroethanol (TFE), furan (Fu), and 2-methyl furan (MF) have been investigated. Using density functional theory (DFT) calculations, gas phase and matrix isolation FTIR spectroscopies, the strengths of Osbnd H ⋯ O and Osbnd H ⋯ π hydrogen bonds in the complexes were compared to find the docking preference. Calculations suggest that the hydrogen bond donor, TFE, is more likely to dock onto the oxygen atom of the aromatic furans ring, and consequently, the Osbnd H ⋯ O type hydrogen bond is relatively stronger than the Osbnd H ⋯ π type. The FTIR spectrum in the OH-stretching fundamental range obtained at room temperatures has been compared with that obtained at extremely low temperatures in the matrix. The fundamental and the red shifts of OH-stretching vibrations were observed in both FTIR spectra, confirming the formation of hydrogen bonded complexes. By assessing the ability of furan and MF to participate in the formation of Osbnd H ⋯ O hydrogen bond, the effect of ring methylation has been highlighted. From the calculated geometric and thermodynamic parameters as well as the frequency shift of the OH-stretching vibrations in complexes, TFE-MF is found to be more stable than TFE-Fu, which suggests that the strength of the Osbnd H ⋯ O hydrogen bond in TFE-MF originates from the high activity of the furan molecule caused by the methylation of the aromatic ring. The present study furthers the knowledge of docking preference in heteroaromatic molecules and is helpful to understand the nature of intermolecular interactions between hydrogen bond donors and acceptors, including both electron-deficient atoms and π cloud.

Synthesis and structure-activity relationship studies of furan-ring fused chalcones as antiproliferative agents.

PubMed

Saito, Yusuke; Kishimoto, Maho; Yoshizawa, Yuko; Kawaii, Satoru

2015-02-01

As part of our continuing investigation of flavonoid derivatives as potential anticancer substances, the synthesis of 25 cinnamoyl derivatives of benzofuran as furan-fused chalcones was carried-out and these compounds were further evaluated for their antiproliferative activity towards HL60 promyelocytic leukemia cells. In comparison with 2',4'-dihydroxychalcone, attachment of a furan moiety on the A-ring enhanced activity by more than twofold. Benzofurans may be useful in the design of biologically active flavonoids. Copyright© 2015 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

Predictors of Serum Dioxin, Furan and PCB Concentrations among Women from Chapaevsk, Russia

PubMed Central

Humblet, Olivier; Williams, Paige L.; Korrick, Susan A.; Sergeyev, Oleg; Emond, Claude; Birnbaum, Linda S.; Burns, Jane S.; Altshul, Larisa; Patterson, Donald G.; Turner, Wayman E.; Lee, Mary M.; Revich, Boris; Hauser, Russ

2011-01-01

INTRODUCTION Dioxins, furans and polychlorinated biphenyls (PCBs) are persistent and bioaccumulative toxic chemicals that are ubiquitous in the environment. We assessed predictors of their serum concentrations among women living in a Russian town contaminated by past industrial activity. METHODS Blood samples from 446 mothers aged 23–52 years were collected between 2003–2005 as part of the Russian Children’s Study. Serum dioxin, furan and PCB concentrations were quantified using high-resolution gas chromatography-mass spectrometry. Potential determinants of exposure were collected through interviews. Multivariate linear regression models were used to identify predictors of serum concentrations and toxic equivalencies (TEQs). RESULTS AND DISCUSSION The median total PCB concentrations and total TEQs were 260 ng/g lipid and 25 pg TEQ/g lipid, respectively. In multivariate analyses, both total PCB concentrations and total TEQs increased significantly with age, residential proximity to a local chemical plant, duration of local farming, and consumption of local beef. Both decreased with longer breastfeeding, recent increases in body mass index, and later blood draw date. These demographic and lifestyle predictors showed generally similar associations with the various measures of serum dioxins, furans, and PCBs. PMID:20578718

Tandem intramolecular silylformylation and silicon-assisted cross-coupling reactions. synthesis of geometrically defined alpha,beta-unsaturated aldehydes.

PubMed

Denmark, Scott E; Kobayashi, Tetsuya

2003-06-27

The palladium- and copper-catalyzed cross-coupling reactions of cyclic silyl ethers with aryl iodides are reported. Silyl ethers 3 were readily prepared by intramolecular silylformylation of homopropargyl silyl ethers 2 under a carbon monoxide atmosphere. The reaction of cyclic silyl ethers 3with various aryl iodides 7 in the presence of [(allyl)PdCl](2), CuI, a hydrosilane, and KF.2H(2)O in DMF at room temperature provided the alpha,beta-unsaturated aldehyde coupling products 8 in high yields. The need for copper in this process suggested that transmetalation from silicon to copper is an important step in the mechanism. Although siloxane 3 and the product 8 are not stable under basic conditions, KF.2H(2)O provided the appropriate balance of reactivity toward silicon and reduced basicity. The addition of a hydrosilane to [(allyl)PdCl](2) was needed to reduce the palladium(II) to the active palladium(0) form.

Theoretical verification of nonthermal microwave effects on intramolecular reactions.

PubMed

Kanno, Manabu; Nakamura, Kosuke; Kanai, Eri; Hoki, Kunihito; Kono, Hirohiko; Tanaka, Motohiko

2012-03-08

There have been a growing number of articles that report dramatic improvements in the experimental performance of chemical reactions by microwave irradiation compared to that under conventional heating conditions. We theoretically examined whether nonthermal microwave effects on intramolecular reactions exist or not, in particular, on Newman-Kwart rearrangements and intramolecular Diels-Alder reactions. The reaction rates of the former calculated by the transition state theory, which consider only the thermal effects of microwaves, agree quantitatively with experimental data, and thus, the increases in reaction rates can be ascribed to dielectric heating of the solvent by microwaves. In contrast, for the latter, the temperature dependence of reaction rates can be explained qualitatively by thermal effects but the possibility of nonthermal effects still remains regardless of whether competitive processes are present or not. The effective intramolecular potential energy surface in the presence of a microwave field suggests that nonthermal effects arising from potential distortion are vanishingly small in intramolecular reactions. It is useful in the elucidation of the reaction mechanisms of microwave synthesis to apply the present theoretical approach with reference to the experiments where thermal and nonthermal effects are separated by screening microwave fields.

The actin-microtubule cross-linking activity of Drosophila Short stop is regulated by intramolecular inhibition

PubMed Central

Applewhite, Derek A.; Grode, Kyle D.; Duncan, Mara C.; Rogers, Stephen L.

2013-01-01

Actin and microtubule dynamics must be precisely coordinated during cell migration, mitosis, and morphogenesis—much of this coordination is mediated by proteins that physically bridge the two cytoskeletal networks. We have investigated the regulation of the Drosophila actin-microtubule cross-linker Short stop (Shot), a member of the spectraplakin family. Our data suggest that Shot's cytoskeletal cross-linking activity is regulated by an intramolecular inhibitory mechanism. In its inactive conformation, Shot adopts a “closed” conformation through interactions between its NH2-terminal actin-binding domain and COOH-terminal EF-hand-GAS2 domain. This inactive conformation is targeted to the growing microtubule plus end by EB1. On activation, Shot binds along the microtubule through its COOH-terminal GAS2 domain and binds to actin with its NH2-terminal tandem CH domains. We propose that this mechanism allows Shot to rapidly cross-link dynamic microtubules in response to localized activating signals at the cell cortex. PMID:23885120

Intramolecular addition of benzylic radicals onto ketenimines. Synthesis of 2-alkylindoles.

PubMed

Alajarín, Mateo; Vidal, Angel; Ortín, María-Mar

2003-12-07

The inter- and intramolecular addition of free radicals onto ketenimines is studied. All the attempts to add intermolecularly several silicon, oxygen or carbon centered radicals to N-(4-methylphenyl)-C,C-diphenyl ketenimine were unsuccessful. In contrast, the intramolecular addition of benzylic radicals, generated from xanthates, onto the central carbon of a ketenimine function with its N atom linked to the ortho position of the aromatic ring occurred under a variety of reaction conditions. These intramolecular cyclizations provide a novel radical-mediated synthesis of 2-alkylindoles.

Case study on the utility of hepatic global gene expression profiling in the risk assessment of the carcinogen furan

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

Jackson, Anna Francina, E-mail: Francina.Jackson@hc-sc.gc.ca; Department of Biology, Carleton University, 1125 Colonel By Drive, Ottawa K1S 5B6; Williams, Andrew, E-mail: Andrew.Williams@hc-sc.gc.ca

2014-01-01

Furan is a chemical hepatocarcinogen in mice and rats. Its previously postulated cancer mode of action (MOA) is chronic cytotoxicity followed by sustained regenerative proliferation; however, its molecular basis is unknown. To this end, we conducted toxicogenomic analysis of B3C6F1 mouse livers following three week exposures to non-carcinogenic (0, 1, 2 mg/kg bw) or carcinogenic (4 and 8 mg/kg bw) doses of furan. We saw enrichment for pathways responsible for cytotoxicity: stress-activated protein kinase (SAPK) and death receptor (DR5 and TNF-alpha) signaling, and proliferation: extracellular signal-regulated kinases (ERKs) and TNF-alpha. We also noted the involvement of NF-kappaB and c-Jun inmore » response to furan, which are genes that are known to be required for liver regeneration. Furan metabolism by CYP2E1 produces cis-2-butene-1,4-dial (BDA), which is required for ensuing cytotoxicity and oxidative stress. NRF2 is a master regulator of gene expression during oxidative stress and we suggest that chronic NFR2 activity and chronic inflammation may represent critical transition events between the adaptive (regeneration) and adverse (cancer) outcomes. Another objective of this study was to demonstrate the applicability of toxicogenomics data in quantitative risk assessment. We modeled benchmark doses for our transcriptional data and previously published cancer data, and observed consistency between the two. Margin of exposure values for both transcriptional and cancer endpoints were also similar. In conclusion, using furan as a case study we have demonstrated the value of toxicogenomics data in elucidating dose-dependent MOA transitions and in quantitative risk assessment. - Highlights: • Global gene expression changes in furan-exposed mouse livers were analyzed. • A molecular mode of action for furan-induced hepatocarcinogenesis is proposed. • Key pathways include NRF2, SAPK, ERK and death receptor signaling. • Important roles for TNF-alpha, c

From Biomass-Derived Furans to Aromatics with Ethanol over Zeolite.

PubMed

Teixeira, Ivo F; Lo, Benedict T W; Kostetskyy, Pavlo; Stamatakis, Michail; Ye, Lin; Tang, Chiu C; Mpourmpakis, Giannis; Tsang, Shik Chi Edman

2016-10-10

We report a novel catalytic conversion of biomass-derived furans and alcohols to aromatics over zeolite catalysts. Aromatics are formed via Diels-Alder cycloaddition with ethylene, which is produced in situ from ethanol dehydration. The use of liquid ethanol instead of gaseous ethylene, as the source of dienophile in this one-pot synthesis, makes the aromatics production much simpler and renewable, circumventing the use of ethylene at high pressure. More importantly, both our experiments and theoretical studies demonstrate that the use of ethanol instead of ethylene, results in significantly higher rates and higher selectivity to aromatics, due to lower activation barriers over the solid acid sites. Synchrotron-diffraction experiments and proton-affinity calculations clearly suggest that a preferred protonation of ethanol over the furan is a key step facilitating the Diels-Alder and dehydration reactions in the acid sites of the zeolite. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

47 CFR 69.111 - Tandem-switched transport and tandem charge.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 47 Telecommunication 3 2011-10-01 2011-10-01 false Tandem-switched transport and tandem charge. 69... SERVICES (CONTINUED) ACCESS CHARGES Computation of Charges § 69.111 Tandem-switched transport and tandem...-switched transport shall consist of two rate elements, a transmission charge and a tandem switching charge...

Effects of furan derivatives on biohydrogen fermentation from wet steam-exploded cornstalk and its microbial community.

PubMed

Liu, Zhidan; Zhang, Chong; Wang, Linjun; He, Jianwei; Li, Baoming; Zhang, Yuanhui; Xing, Xin-Hui

2015-01-01

Understanding the role of furan derivatives, furfural (FUR) and 5-hydroxymethyl furfural (HMF), is important for biofuel production from lignocellulosic biomass. In this study, the effects of furan derivatives on hydrogen fermentation from wet steam-exploded cornstalk were investigated. The control experiments with only seed sludge indicated that HMF addition of up to 1g/L stimulated hydrogen production. Similar results were obtained using steam-exploded cornstalk as the feedstock. Hydrogen productivity was increased by up to 40% with the addition of HMF. In addition, over 90% of furan derivatives with an initial concentration below 1g/L were degraded. Pyosequencing showed that the addition of HMF and FUR resulted in different microbial communities. HMF led to a higher proportion of the genera Clostridium and Ruminococcaceae, supporting the increased hydrogen production. This study suggested that hydrogen fermentation could be a detoxifying step for steam-exploded cornstalk, and HMF and FUR exhibited different functions for hydrogen fermentation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Investigation of Thermochemistry Associated with the Carbon–Carbon Coupling Reactions of Furan and Furfural Using ab Initio Methods

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

Liu, Cong; Assary, Rajeev S.; Curtiss, Larry A.

2014-06-26

Upgrading of furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan, can be coupled with various C1 to C4 lower molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase tomore » produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (~25 kcal/mol) are lower than the cellulose activation or decomposition reactions (~50 kcal/mol). Cycloaddition of C5-C8 cyclo-ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ~20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.« less

Copper-Catalyzed Coupling of 2-Siloxy-1-alkenes and Diazocarbonyl Compounds: Approach to Multisubstituted Furans, Pyrroles, and Thiophenes.

PubMed

Tan, Wei Wen; Yoshikai, Naohiko

2016-07-01

We report herein copper(II)-catalyzed cyclization reactions of silyl enol ethers derived from methyl ketones with α-diazo-β-ketoesters or α-diazoketones to afford 2-siloxy-2,3-dihydrofuran derivatives or 2,3,5-trisubstituted furans, respectively, under mild conditions. The former cyclization products serve as versatile 1,4-diketone surrogates, allowing facile preparation of 2,3,5-trisubstituted furans, pyrroles, and thiophenes.

Highly efficient induction of chirality in intramolecular

PubMed

Cossio; Arrieta; Lecea; Alajarin; Vidal; Tovar

2000-06-16

Highly stereocontrolled, intramolecular [2 + 2] cycloadditions between ketenimines and imines leading to 1,2-dihydroazeto[2, 1-b]quinazolines have been achieved. The source of stereocontrol is a chiral carbon atom adjacent either to the iminic carbon or nitrogen atom. In the first case, the stereocontrol stems from the preference for the axial conformer in the first transition structure. In the second case, the origin of the stereocontrol lies on the two-electron stabilizing interaction between the C-C bond being formed and the sigma orbital corresponding to the polar C-X bond, X being an electronegative atom. These models can be extended to other related systems for predicting the stereochemical outcome in this intramolecular reaction.

Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

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

Liu, Cong; Evans, Tabitha J.; Cheng, Lei

2015-10-02

These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Majormore » products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.« less

Triple quadrupole tandem mass spectrometry: A real alternative to high resolution magnetic sector instrument for the analysis of polychlorinated dibenzo-p-dioxins, furans and dioxin-like polychlorinated biphenyls.

PubMed

García-Bermejo, Ángel; Ábalos, Manuela; Sauló, Jordi; Abad, Esteban; González, María José; Gómara, Belén

2015-08-19

This paper reports on the optimisation, characterisation, validation and applicability of gas chromatography coupled to triple quadrupole mass spectrometry in its tandem operation mode (GC-QqQ(MS/MS) for the quantification of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs, dioxins) and dioxin-like polychlorinated biphenyls (DL-PCBs) in environmental and food matrices. MS/MS parameters were selected to achieve the high sensitivity and selectivity required for the analysis of this type of compounds and samples. Good repeatability for areas (RSD = 1-10%, for PCDD/Fs and DL-PCBs) and for ion transition ratios (RSD = 0.3-10%, for PCDD/Fs, and 0.2-15%, for DL-PCBs) and low instrumental limits of detection, 0.07-0.75 pg μL(-1) (for dioxins) and 0.05-0.63 pg μL(-1) (for DL-PCBs), were obtained. A comparative study of the congener specific determination using both GC-QqQ(MS/MS) and gas chromatography-high resolution mass spectrometry (GC-HRMS) was also performed by analysing several fortified samples and certified reference materials (CRMs) with low (feed and foodstuffs), median (sewage sludge) and high (fly ash) toxic equivalency (TEQ) concentration levels, i.e. 0.60, 1.83, 72.9 and 3609 pg WHO-TEQ(PCDD/Fs) g(-1). The agreement between the results obtained for the total TEQs (dioxins) on GC-QqQ(MS/MS) and GC-HRMS in all the investigated samples were within the range of ±4%, and that of DL-PCBs at concentration levels of 0.84 pg WHO-TEQs (DL-PCBs) g(-1), in the case of feedstuffs, was 0.11%. Both instrumental methods have similar and comparable linearity, precision and accuracy. The GC-QqQ(MS/MS) sensitivity, lower than that of GC-HRMS, is good enough (iLODs in the down to low pg levels) to detect the normal concentrations of these compounds in food and environmental samples. These results make GC-QqQ(MS/MS) suitable for the quantitative analysis of dioxins and DL-PCBs and a real alternative tool to the reference sector HRMS instruments. Copyright © 2015 Elsevier

Dioxins, Furans, PCBs, and Congeners Analytical Service within the Superfund Contract Laboratory Program

EPA Pesticide Factsheets

This page contains information about the DLM02.2 analytical service for the analysis of dioxins and furans at hazardous waste sites. The SOW contains the analytical method and contractual requirements for laboratories.

One-Pot Conversion of Carbohydrates into Furan Derivatives via Furfural and 5-Hydroxylmethylfurfural as Intermediates.

PubMed

Liu, Bing; Zhang, Zehui

2016-08-23

Recently, there has been growing interest in the transformation of renewable biomass into value-added fuels and chemicals. The catalytic conversion of naturally abundant carbohydrates can generate two-important furan chemicals: 5-hydroxymethylfurfural (HMF) from C6 carbohydrates and furfural from C5 carbohydrates. Both HMF and furfural have received great interest as precursors in the synthesis of commodity chemicals and liquid fuels. In recent years, a trend has emerged to integrate sequential catalytic processes involving multistep reactions for the direct one-pot transformation of carbohydrates into the aimed fuels and chemicals. One-pot reactions have remarkably unique and environmentally friendly benefits, including the fact that isolation and purification of intermediate compounds can be avoided. Herein, the present article aims to review recent advances in the one-pot conversion of carbohydrates into furan derivatives via furfural and HMF as intermediates. Special attention will be paid to the catalytic systems, mechanistic insight, reaction pathways, and catalyst stability. It is expected that this review will guide researchers to develop effective catalytic systems for the one-pot transformation of carbohydrates into furan derivatives. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synchrotron Photoionization Study of Furan and 2-Methylfuran Reactions with Methylidyne Radical (CH) at 298 K.

PubMed

Carrasco, Erica; Smith, Kenneth J; Meloni, Giovanni

2018-01-11

The reactions of furan and 2-methylfuran with methylidyne CH (X 2 Π) radical were investigated at 298 K using synchrotron radiation produced at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Reaction products were observed by multiplexed photoionization mass spectrometry and characterized based on their photoionization spectra and kinetic time traces. Primary products observed in furan + CH are 2,4-cyclopentadien-1-one (m/z = 80), 2-penten-4-ynal (m/z = 80), and vinylacetylene (m/z = 52). From 2-methylfuran + CH, 2-4-cyclopentadien-1-carbaldehyde (m/z = 94), 2,3,4-hexatrienal (m/z = 94), 1,3 cyclopentadiene (m/z = 66), 3-penten-1-yne (Z) (m/z = 66), and vinylacetylene (m/z = 52) are the primary products observed. Using potential energy surface scans, thermodynamically favorable reaction pathways are proposed. CH addition to the π-bonds in furan and 2-methylfuran rings was found to be the entrance channel that led to formation of all identified primary products. Both reactions follow patterns of H loss and CHO loss, as well as formation of cyclic and acyclic isomers.

Stereocontrolled intramolecular iron-mediated diene/olefin cyclocoupling

NASA Astrophysics Data System (ADS)

Dorange, Ismet B.

A methodology for stereocontrol during the intramolecular coupling between cyclohexadiene-Fe(CO)3 complexes and pendant alkenes is presented. Introduction of a methoxy group at the C(3) position of the diene moiety controls pre- and post-cyclization rearrangements of the diene Fe(CO)3 unit, allowing the preparation of spirolactams with defined relative stereochemistry and with a cyclohexenone framework, thus making this reaction a potentially valuable tool for the construction of quaternary carbon centers.* A new methodology for the formation of tricarbonyl(cyclohexadienyl)ketone iron complexes was also developed. This method involves the coupling of a Grignard reagent with an acyl mesylate iron complex, giving rise to ketone derivatives in excellent yields. The possibility of intramolecular coupling between diene-Fe(CO)3 complexes and homoallylic olefin was demonstrated. The stereospecific formation of spiroketones occurred in excellent yields under thermal conditions, but appeared to be limited to the simpler, less substituted pendant alkenes. The control of the stereochemical outcome of these spirocyclization was achieved using the "C(3) substitution method" previously described. The same trends were observed in these series. Also illustrated in these studies is the extension of this spirocoupling to the formation of a spiro[5.5]undecane framework. It is the first time that this framework has been accessed using this intramolecular coupling.* *Please refer to dissertation for diagram.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part II: 2-Methylfuran.

PubMed

Tran, Luc-Sy; Togbé, Casimir; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Fournet, René; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2014-03-01

This is Part II of a series of three papers which jointly address the combustion chemistry of furan and its alkylated derivatives 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) under premixed low-pressure flame conditions. Some of them are considered to be promising biofuels. With furan as a common basis studied in Part I of this series, the present paper addresses two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of MF which were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) for equivalence ratios φ=1.0 and 1.7, identical conditions to those for the previously reported furan flames. Mole fractions of reactants, products as well as stable and reactive intermediates were measured as a function of the distance above the burner. Kinetic modeling was performed using a comprehensive reaction mechanism for all three fuels given in Part I and described in the three parts of this series. A comparison of the experimental results and the simulation shows reasonable agreement, as also seen for the furan flames in Part I before. This set of experiments is thus considered to be a valuable additional basis for the validation of the model. The main reaction pathways of MF consumption have been derived from reaction flow analyses, and differences to furan combustion chemistry under the same conditions are discussed.

Formation of furan fatty alkyl esters from their bis-epoxide fatty esters

USDA-ARS?s Scientific Manuscript database

Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2-ethylhexanol, and benzyl alcohol were investigated in the presence of Bronsted acid catalyst. Products not reported in prior studies of similar reactions were found. These were furan fatty acid alkyl est...

Formation of furan fatty alkyl esters from their bis-epoxide fatty esters

USDA-ARS?s Scientific Manuscript database

Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2-ethylhexanol, benzyl alcohol, in the presence of Bronsted acid catalyst, were investigated. Products that were not reported in prior studies of similar reactions were found. These were furan fatty acid a...

Preliminary assessment of the risk linked to furan ingestion by babies consuming only ready-to-eat food.

PubMed

Scholl, Georges; Humblet, Marie-France; Scippo, Marie-Louise; De Pauw, Edwin; Eppe, Gauthier; Saegerman, Claude

2013-01-01

The risk linked to furan ingestion has been assessed in previous papers for Belgian adults and children. The present paper focuses on infants consuming only ready-to-eat baby food. As there is no Belgian baby dietary database, the furan exposure assessment was carried out by using an Italian infant consumption database and Belgian contamination data. The estimated daily intake (EDI) was calculated according to a deterministic methodology. It involved 42 commercially available ready-to-eat baby food and 36 baby consumption records. The mean EDI was 1460 ng*(kg(bw)*day)⁻¹ which is 3.8 times higher than the 381 ng*(kg(bw)*day)⁻¹ reported for Belgian adults, and 3.5 times higher than the 419 ng*(kg(bw)*day)⁻¹ measured for Belgian children. To assess and characterise the risk for babies' exposure, the margin of exposure (MoE) was calculated. It highlighted that 74% of infants have a MoE < 1000, with a minimum of 140. However, these are only preliminary results as they were calculated from a very small dataset and the infant cytochrome P450 activity is significantly different compared with the adult's. Therefore, the risk linked to furan ingestion by babies should be assessed in a different manner. To this end, additional data regarding a baby diet as well as a better understanding of furan toxicity for babies are needed to characterise more accurately the risk for infants.

Femtochemistry of Intramolecular Charge and Proton Transfer Reactions in Solution

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

Douhal, Abderrazzak; Sanz, Mikel; Carranza, Maria Angeles

2005-03-17

We report on the first observation of ultrafast intramolecular charge- and proton-transfer reactions in 4'-dimethylaminoflavonol (DAMF) in solution. Upon femtosecond excitation of a non-planar structure of DMAF in apolar medium, the intramolecular charge transfer (ICT) does not occur, and a slow (2 ps) proton motion takes place. However, in polar solvents, the ICT is very fast (100-200 fs) and the produced structure is stabilized that proton motion takes place in few or tens of ps.

Effect of high hydrostatic pressure on background microflora and furan formation in fruit purée based baby foods.

PubMed

Kultur, Gulcin; Misra, N N; Barba, Francisco J; Koubaa, Mohamed; Gökmen, Vural; Alpas, Hami

2018-03-01

The baby foods industry is currently seeking technologies to pasteurize products without formation of processing contaminants such as furan. This work demonstrates the applicability of high hydrostatic pressure (HHP) as a non-thermal decontamination intervention for fruit purée based baby foods. HHP processing was evaluated at 200, 300, and 400 MPa pressures, for 5, 10 and 15 min of treatment times at 25, 35 and 45 °C. HHP application at 400 MPa, 45 °C for 15 min ensured complete inactivation (about 6 log 10 ) of total mesophilic aerophiles, as well as yeasts and molds. No furan was detected in HHP processed products. Thus, the key advantage of HHP over thermal processing is the ability to achieve commercially acceptable microbiological inactivation while avoiding the formation of processing contaminants such as furan.

MR-Tandem: parallel X!Tandem using Hadoop MapReduce on Amazon Web Services.

PubMed

Pratt, Brian; Howbert, J Jeffry; Tasman, Natalie I; Nilsson, Erik J

2012-01-01

MR-Tandem adapts the popular X!Tandem peptide search engine to work with Hadoop MapReduce for reliable parallel execution of large searches. MR-Tandem runs on any Hadoop cluster but offers special support for Amazon Web Services for creating inexpensive on-demand Hadoop clusters, enabling search volumes that might not otherwise be feasible with the compute resources a researcher has at hand. MR-Tandem is designed to drop in wherever X!Tandem is already in use and requires no modification to existing X!Tandem parameter files, and only minimal modification to X!Tandem-based workflows. MR-Tandem is implemented as a lightly modified X!Tandem C++ executable and a Python script that drives Hadoop clusters including Amazon Web Services (AWS) Elastic Map Reduce (EMR), using the modified X!Tandem program as a Hadoop Streaming mapper and reducer. The modified X!Tandem C++ source code is Artistic licensed, supports pluggable scoring, and is available as part of the Sashimi project at http://sashimi.svn.sourceforge.net/viewvc/sashimi/trunk/trans_proteomic_pipeline/extern/xtandem/. The MR-Tandem Python script is Apache licensed and available as part of the Insilicos Cloud Army project at http://ica.svn.sourceforge.net/viewvc/ica/trunk/mr-tandem/. Full documentation and a windows installer that configures MR-Tandem, Python and all necessary packages are available at this same URL. brian.pratt@insilicos.com

Opening Furan for Tailoring Properties of Bio-based Poly(Furfuryl Alcohol) Thermoset.

PubMed

Falco, Guillaume; Guigo, Nathanael; Vincent, Luc; Sbirrazzuoli, Nicolas

2018-06-11

This work shows how furan ring-opening reactions were controlled by polymerization conditions to tune the cross-link density in bio-based poly(furfuryl alcohol) (PFA). The influence of water and isopropyl alcohol (IPA) on the polymerization of furfuryl alcohol, and particularly on furan ring-opening, was investigated by means of 13 C NMR and FT-IR spectroscopy. Results indicated that formation of open structures were favored in the presence of solvents, thus leading to modification of the thermo-mechanical properties compared to PFA cross-linked without solvent. Dynamic mechanical analyses showed that when slightly more open structures were present in PFA it resulted in an important decrease of the cross-link density. Despite lower glass-transition temperature and lower elastic modulus for PFA polymerized with solvent, the thermal stability remains very high (>350 °C) even with more open structures in PFA. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DISTRIBUTION OF DIOXINS, FURANS, AND COPLANAR PCBS IN DIFFERENT FAT MATRICES IN CATTLE

EPA Science Inventory

The United States Environmental Protection Agency (EPA) and the United States Department of Agriculture (USDA) recently collaborated on a statistically-based, national survey of dioxin-like compounds, including dioxins, furans, and coplanar PCBs, in the back fat from slaughtered ...

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

PubMed Central

Nagy, Peter I.

2014-01-01

A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic) in acid-base complexes have been surveyed. PMID:25353178

MR-Tandem: parallel X!Tandem using Hadoop MapReduce on Amazon Web Services

PubMed Central

Pratt, Brian; Howbert, J. Jeffry; Tasman, Natalie I.; Nilsson, Erik J.

2012-01-01

Summary: MR-Tandem adapts the popular X!Tandem peptide search engine to work with Hadoop MapReduce for reliable parallel execution of large searches. MR-Tandem runs on any Hadoop cluster but offers special support for Amazon Web Services for creating inexpensive on-demand Hadoop clusters, enabling search volumes that might not otherwise be feasible with the compute resources a researcher has at hand. MR-Tandem is designed to drop in wherever X!Tandem is already in use and requires no modification to existing X!Tandem parameter files, and only minimal modification to X!Tandem-based workflows. Availability and implementation: MR-Tandem is implemented as a lightly modified X!Tandem C++ executable and a Python script that drives Hadoop clusters including Amazon Web Services (AWS) Elastic Map Reduce (EMR), using the modified X!Tandem program as a Hadoop Streaming mapper and reducer. The modified X!Tandem C++ source code is Artistic licensed, supports pluggable scoring, and is available as part of the Sashimi project at http://sashimi.svn.sourceforge.net/viewvc/sashimi/trunk/trans_proteomic_pipeline/extern/xtandem/. The MR-Tandem Python script is Apache licensed and available as part of the Insilicos Cloud Army project at http://ica.svn.sourceforge.net/viewvc/ica/trunk/mr-tandem/. Full documentation and a windows installer that configures MR-Tandem, Python and all necessary packages are available at this same URL. Contact: brian.pratt@insilicos.com PMID:22072385

Tuning Solvatochromism of Azo Dyes with Intramolecular Hydrogen Bonding in Solution and on Titanium Dioxide Nanoparticles

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

Zhang, Lei; Cole, Jacqueline M.; Liu, Xiaogang

2013-11-25

“Smart tuning” of optical properties in three azo dyes containing intramolecular hydrogen bonding is realized by the judicious control of solvents, when the dyes are in solution or adsorbed onto titanium dioxide nanoparticles. In solution, certain solvents destabilizing intramolecular hydrogen bonding induce a distinctive ≈70 nm “blue-shifted” absorption peak, compared with other solvents. In parallel, the optical properties of azo dye/TiO2 nanocomposites can be tuned using solvents with different hydrogen-bond accepting/donating abilities, giving insights into smart materials and dye-sensitized solar cell device design. It is proposed that intramolecular hydrogen bonding alone plays the leading role in such phenomena, which ismore » fundamentally different to other mechanisms, such as tautomerism and cis–trans isomerization, that explain the optical control of azo dyes. Hybrid density functional theory (DFT) is employed in order to trace the origin of this optical control, and these calculations support the mechanism involving intramolecular hydrogen bonding. Two complementary studies are also reported: 1H NMR spectroscopy is conducted in order to further understand the solvent effects on intramolecular hydrogen bonding; crystal structure analysis from associated research indicates the importance of intramolecular hydrogen bonding on intramolecular charge transfer.« less

Synthesis of fused tricyclic systems by thermal Cope rearrangement of furan-substituted vinyl cyclopropanes.

PubMed

Klaus, Verena; Wittmann, Stéphane; Senn, Hans M; Clark, J Stephen

2018-05-15

A novel method for the stereoselective construction of hexahydroazuleno[4,5-b]furans from simple precursors has been developed. The route involves the use of our recently developed Brønsted acid catalysed cyclisation reaction of acyclic ynenones to prepare fused 1-furanyl-2-alkenylcyclopropanes that undergo highly stereoselective thermal Cope rearrangement to produce fused tricyclic products. Substrates possessing an E-alkene undergo smooth Cope rearrangement at 40 °C, whereas the corresponding Z-isomers do not react at this temperature. Computational studies have been performed to explain the difference in behaviour of the E- and Z-isomers in the Cope rearrangement reaction. The hexahydroazuleno[4,5-b]furans produced by Cope rearrangement have potential as advanced intermediates for the synthesis of members of the guaianolide family of natural products.

Palladium-Catalyzed Indole, Pyrrole, and Furan Arylation by Aryl Chlorides

PubMed Central

Nadres, Enrico T.; Lazareva, Anna; Daugulis, Olafs

2011-01-01

The palladium-catalyzed direct arylation of indoles, pyrroles, and furans by aryl chlorides has been demonstrated. The method employs a palladium acetate catalyst, 2-(dicyclohexylphosphino)-biphenyl ligand, and an inorganic base. Electron-rich and electron-poor aryl chlorides as well as chloropyridine coupling partners can be used and arylated heterocycles are obtained in moderate to good yields. Optimization of base, ligand, and solvent is required for achieving best results. PMID:21192652

A review of dioxins/furans and methyl mercury in fish from the Penobscot river, located near Lincoln, Maine.

PubMed

Williams, Robert L; Cseh, Larry

2007-04-01

The Agency for Toxic Substances and Disease Registry (ATSDR) was requested to review the analytical results of tissue samples from fish caught in the Penobscot river in Maine, calculate fish consumption limits and provide a public health opinion regarding the health implications associated with eating the contaminated fish. Fish consumption limits were calculated to provide guidance on the amount of fish that a person may eat monthly that would probably not pose a public health threat. Earlier, in 1987, the Maine Bureau of Health (BOH) issued a fish consumption advisory for portions of the Penobscot river to protect the public from exposures to dioxins/furans and methyl mercury-contaminated fish. From 1988 to 2003 the state of Maine conducted fish surveys at four locations along the Penobscot river to monitor the levels of dioxins/furans and methyl mercury contamination. In 2005, ATSDR reviewed the sampling results for two fish species (i.e., bottom feeders and predators) collected from the Penobscot river that revealed various levels of dioxins/furans and methyl mercury. The United States Environmental Protection Agency's (US EPA) guidance for evaluating potential health threats associated with contaminated fish recommends that a minimum of two target species be sampled including one predatory and one bottom feeding species. Target species are chosen to meet the following criteria: (1) known to accumulate high concentrations of target contaminants in their tissues; (2) normally populate the freshwater system being studied; (3) are routinely caught and consumed by anglers; (4) nonmigratory; (5) pollutant-tolerant; (6) easily identified; (7) abundant and easy to collect and (8) of sufficient size to provide adequate tissue samples for analyses of contaminants (US EPA, 2000). The analytical results of these fish tissue samples appear to indicate that toxic equivalency quotients concentrations of dioxins/furans have slightly decreased since 1988. In contrast, fish

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part II: 2-Methylfuran

PubMed Central

Tran, Luc-Sy; Togbé, Casimir; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Fournet, René; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2013-01-01

This is Part II of a series of three papers which jointly address the combustion chemistry of furan and its alkylated derivatives 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) under premixed low-pressure flame conditions. Some of them are considered to be promising biofuels. With furan as a common basis studied in Part I of this series, the present paper addresses two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of MF which were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) for equivalence ratios φ=1.0 and 1.7, identical conditions to those for the previously reported furan flames. Mole fractions of reactants, products as well as stable and reactive intermediates were measured as a function of the distance above the burner. Kinetic modeling was performed using a comprehensive reaction mechanism for all three fuels given in Part I and described in the three parts of this series. A comparison of the experimental results and the simulation shows reasonable agreement, as also seen for the furan flames in Part I before. This set of experiments is thus considered to be a valuable additional basis for the validation of the model. The main reaction pathways of MF consumption have been derived from reaction flow analyses, and differences to furan combustion chemistry under the same conditions are discussed. PMID:24518895

Accounting for intra-molecular vibrational modes in open quantum system description of molecular systems.

PubMed

Roden, Jan; Strunz, Walter T; Whaley, K Birgitta; Eisfeld, Alexander

2012-11-28

Electronic-vibrational dynamics in molecular systems that interact with an environment involve a large number of degrees of freedom and are therefore often described by means of open quantum system approaches. A popular approach is to include only the electronic degrees of freedom into the system part and to couple these to a non-Markovian bath of harmonic vibrational modes that is characterized by a spectral density. Since this bath represents both intra-molecular and external vibrations, it is important to understand how to construct a spectral density that accounts for intra-molecular vibrational modes that couple further to other modes. Here, we address this problem by explicitly incorporating an intra-molecular vibrational mode together with the electronic degrees of freedom into the system part and using the Fano theory for a resonance coupled to a continuum to derive an "effective" bath spectral density, which describes the contribution of intra-molecular modes. We compare this effective model for the intra-molecular mode with the method of pseudomodes, a widely used approach in simulation of non-Markovian dynamics. We clarify the difference between these two approaches and demonstrate that the respective resulting dynamics and optical spectra can be very different.

Effects of furan derivatives and phenolic compounds on electricity generation in microbial fuel cells

NASA Astrophysics Data System (ADS)

Catal, Tunc; Fan, Yanzhen; Li, Kaichang; Bermek, Hakan; Liu, Hong

Lignocellulosic biomass is an attractive fuel source for MFCs due to its renewable nature and ready availability. Furan derivatives and phenolic compounds could be potentially formed during the pre-treatment process of lignocellulosic biomass. In this study, voltage generation from these compounds and the effects of these compounds on voltage generation from glucose in air-cathode microbial fuel cells (MFCs) were examined. Except for 5-hydroxymethyl furfural (5-HMF), all the other compounds tested were unable to be utilized directly for electricity production in MFCs in the absence of other electron donors. One furan derivate, 5-HMF and two phenolic compounds, trans-cinnamic acid and 3,5-dimethoxy-4-hydroxy-cinnamic acid did not affect electricity generation from glucose at a concentration up to 10 mM. Four phenolic compounds, including syringaldeyhde, vanillin, trans-4-hydroxy-3-methoxy, and 4-hydroxy cinnamic acids inhibited electricity generation at concentrations above 5 mM. Other compounds, including 2-furaldehyde, benzyl alcohol and acetophenone, inhibited the electricity generation even at concentrations less than 0.2 mM. This study suggests that effective electricity generation from the hydrolysates of lignocellulosic biomass in MFCs may require the employment of the hydrolysis methods with low furan derivatives and phenolic compounds production, or the removal of some strong inhibitors prior to the MFC operation, or the improvement of bacterial tolerance against these compounds through the enrichment of new bacterial cultures or genetic modification of the bacterial strains.

An experimental and kinetic investigation of premixed furan/oxygen/argon flames

PubMed Central

Tian, Zhenyu; Yuan, Tao; Fournet, Rene; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Zhang, Kuiwen; Qi, Fei

2013-01-01

The detailed chemical structures of three low-pressure (35 Torr) premixed laminar furan/oxygen/argon flames with equivalence ratios of 1.4, 1.8 and 2.2 have been investigated by using tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry. About 40 combustion species including hydrocarbons and oxygenated intermediates have been identified by measurements of photoionization efficiency spectra. Mole fraction profiles of the flame species including reactants, intermediates and products have been determined by scanning burner position with some selected photon energies near ionization thresholds. Flame temperatures have been measured by a Pt-6%Rh/Pt-30%Rh thermocouple. A new mechanism involving 206 species and 1368 reactions has been proposed whose predictions are in reasonable agreement with measured species profiles for the three investigated flames. Rate-of-production and sensitivity analyses have been performed to track the key reaction paths governing furan consumption for different equivalence ratios. Both experimental and modeling results indicate that few aromatics could be formed in these flames. Furthermore, the current model has been validated against previous pyrolysis results of the literature obtained behind shock waves and the agreement is reasonable as well. PMID:23814311

An experimental and kinetic investigation of premixed furan/oxygen/argon flames.

PubMed

Tian, Zhenyu; Yuan, Tao; Fournet, Rene; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Zhang, Kuiwen; Qi, Fei

2011-04-01

The detailed chemical structures of three low-pressure (35 Torr) premixed laminar furan/oxygen/argon flames with equivalence ratios of 1.4, 1.8 and 2.2 have been investigated by using tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry. About 40 combustion species including hydrocarbons and oxygenated intermediates have been identified by measurements of photoionization efficiency spectra. Mole fraction profiles of the flame species including reactants, intermediates and products have been determined by scanning burner position with some selected photon energies near ionization thresholds. Flame temperatures have been measured by a Pt-6%Rh/Pt-30%Rh thermocouple. A new mechanism involving 206 species and 1368 reactions has been proposed whose predictions are in reasonable agreement with measured species profiles for the three investigated flames. Rate-of-production and sensitivity analyses have been performed to track the key reaction paths governing furan consumption for different equivalence ratios. Both experimental and modeling results indicate that few aromatics could be formed in these flames. Furthermore, the current model has been validated against previous pyrolysis results of the literature obtained behind shock waves and the agreement is reasonable as well.

Proximity vs. strain in intramolecular ring-closing reactions

NASA Astrophysics Data System (ADS)

Karaman, Rafik

2010-07-01

The DFT and ab initio calculation results for ring-closing reactions of eight different ω-bromoalkanecarboxylate anions (1-8) reveal that the activation energy (ΔG ‡) for the intramolecular cyclization process is strongly correlated with both (i) the experimental intramolecular cyclization rate (log k intra) and (ii) the distance between the two reactive centres, whereas the slope values of the change in enthalpy (ΔH) vs. the attack angle (α) and the distance between the two reacting centres (r) were found to correlate strongly with the experimental strain energy of the cycle being formed (E s Exp). These results assist in designing pro-prodrug systems that can be utilized to improve the overall biopharmaceutical profile of current medications in order to enhance their effectiveness and ease their utility.

Direct carbon-carbon coupling of furanics with acetic acid over Bronsted zeolites

DOE PAGES

Gumidyala, Abhishek; Wang, Bin; Crossley, Steven

2016-09-16

Effective carbon-carbon coupling of acetic acid to form larger products while minimizing CO 2 emissions is critical to achieving a step change in efficiency for the production of transportation fuels from sustainable biomass. Here, we report the direct acylation of methylfuran with acetic acid in the presence ofwater, all ofwhich can be readily produced from biomass. This direct coupling limits unwanted polymerization of furanics while producing acetyl methylfuran. Reaction kinetics and density functional theory calculations illustrate that the calculated apparent barrier for the dehydration of the acid to form surface acyl species is similar to the experimentally measured barrier, implyingmore » that this step plays a significant role in determining the net reaction rate. Water inhibits the overall rate, but selectivity to acylated products is not affected.We show that furanic species effectively stabilize the charge of the transition state, therefore lowering the overall activation barrier. These results demonstrate a promising new route to C–C bond–forming reactions for the production of higher-value products from biomass.« less

Isolation of a furan fatty acid from Hevea brasiliensis latex employing the combined use of pH-zone-refining and conventional countercurrent chromatography.

PubMed

Englert, Michael; Ulms, Kerstin; Wendlinger, Christine; Vetter, Walter

2016-02-01

Furan fatty acids are valuable and bioactive minor fatty acids that usually contribute <0.1% to the fatty acid content of food samples. Their biological role still remains unclear as authentic furan fatty acid standards are not readily available and thorough experimental studies verifying the relevance of furan fatty acids are thus virtually impossible. An efficient protocol for the isolation of the furan fatty acid 9-(3-methyl-5-pentylfuran-2-yl)-nonanoic acid from hydrolyzed and centrifuged latex of Hevea brasiliensis was developed using countercurrent chromatography. A first run using pH-zone-refining countercurrent chromatography provided 48.4 mg of 9-(3-methyl-5-pentylfuran-2-yl)-nonanoic acid from 210 mg latex extract in a purity of 95%. The purity was increased to 99% by means of one second run in conventional countercurrent chromatography mode. The Structure and purity of 9-(3-methyl-5-pentylfuran-2-yl)-nonanoic acid were determined by gas chromatography coupled to mass spectrometry and (1)H and (13)C NMR spectroscopy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intramolecular bonds resolved on a semiconductor surface

NASA Astrophysics Data System (ADS)

Sweetman, Adam; Jarvis, Samuel P.; Rahe, Philipp; Champness, Neil R.; Kantorovich, Lev; Moriarty, Philip

2014-10-01

Noncontact atomic force microscopy (NC-AFM) is now routinely capable of obtaining submolecular resolution, readily resolving the carbon backbone structure of planar organic molecules adsorbed on metal substrates. Here we show that the same resolution may also be obtained for molecules adsorbed on a reactive semiconducting substrate. Surprisingly, this resolution is routinely obtained without the need for deliberate tip functionalization. Intriguingly, we observe two chemically distinct apex types capable of submolecular imaging. We characterize our tip apices by "inverse imaging" of the silicon adatoms of the Si (111)-7×7 surface and support our findings with detailed density functional theory (DFT) calculations. We also show that intramolecular resolution on individual molecules may be readily obtained at 78 K, rather than solely at 5 K as previously demonstrated. Our results suggest a wide range of tips may be capable of producing intramolecular contrast for molecules adsorbed on semiconductor surfaces, leading to a much broader applicability for submolecular imaging protocols.

A high temperature and atmospheric pressure experimental and detailed chemical kinetic modelling study of 2-methyl furan oxidation

PubMed Central

Somers, Kieran P.; Simmie, John M.; Gillespie, Fiona; Burke, Ultan; Connolly, Jessica; Metcalfe, Wayne K.; Battin-Leclerc, Frédérique; Dirrenberger, Patricia; Herbinet, Olivier; Glaude, Pierre-Alexandre; Curran, Henry J.

2013-01-01

An experimental ignition delay time study for the promising biofuel 2-methyl furan (2MF) was performed at equivalence ratios of 0.5, 1.0 and 2.0 for mixtures of 1% fuel in argon in the temperature range 1200–1800 K at atmospheric pressure. Laminar burning velocities were determined using the heat-flux method for mixtures of 2MF in air at equivalence ratios of 0.55–1.65, initial temperatures of 298–398 K and atmospheric pressure. A detailed chemical kinetic mechanism consisting of 2059 reactions and 391 species has been constructed to describe the oxidation of 2MF and is used to simulate experiment. Accurate reproduction of the experimental data has been obtained over all conditions with the developed mechanism. Rate of production and sensitivity analyses have been carried out to identify important consumption pathways of the fuel and key kinetic parameters under these conditions. The reactions of hydrogen atom with the fuel are highlighted as important under all experimental conditions studied, with abstraction by the hydrogen atom promoting reactivity and hydrogen atom addition to the furan ring inhibiting reactivity. This work, to the authors knowledge, is the first to combine theoretical and experimental work to describe the oxidation of any of the alkylated furans. The mechanism developed herein to describe 2MF combustion should also function as a sub-mechanism to describe the oxidation of 2,5-dimethyl furan whilst also providing key insights into the oxidation of this similar biofuel candidate. PMID:23814505

Inter- and intramolecular epitope spreading in equine recurrent uveitis.

PubMed

Deeg, Cornelia A; Amann, Barbara; Raith, Albert J; Kaspers, Bernd

2006-02-01

To test the hypothesis that inter- and intramolecular spreading to S-antigen (S-Ag) and interphotoreceptor retinoid binding protein (IRBP)-derived epitopes occurs in a spontaneous model of recurrent uveitis in the horse. The immune response of eight horses with equine recurrent uveitis (ERU) was compared with that of five control horses with healthy eyes. Lymphocytes derived from peripheral blood (PBLs) were tested every 8 weeks for their reactivity against S-Ag and various S-Ag and IRBP-derived peptides for 12 to 39 months (median, 22 months). During uveitic episodes, additional blood samples were analyzed. Intermolecular epitope spreading was detectable in all ERU cases during the study. Intramolecular spreading occurred in seven (of eight) horses with ERU. Fourteen relapses were analyzed during the observation period. Ten uveitic episodes were accompanied by neoreactivity to S-Ag or IRBP-derived peptides during the relapse. Shifts in the immune response profile were also detectable without any clinical signs of inflammation. Eye-healthy control horses were negative at all time points in the in vitro proliferation assays. Inter- and intramolecular spreading was detectable in a spontaneous model of recurrent uveitis. The shifts in immunoreactivity could account for the remitting-relapsing character of the disease.

Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules - Synthesis and Characterization

DTIC Science & Technology

2016-04-12

AFRL-AFOSR-CL-TR-2016-0012 Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules Ronald Ziolo CIQA Final Report 07/07...3. DATES COVERED (From - To)  15 Aug 2014 to 14 Jan 2016 4. TITLE AND SUBTITLE Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene...characterization of a new series of conjugated macromolecules bearing ferrocene as a highly efficient electron donor material coupled to 2,5-di(alcoxy) benzene

Application to processing system using intra-molecular BRET

NASA Astrophysics Data System (ADS)

Otsuji, Tomomi; Okuda-Ashitaka, Emiko; Kojima, Satoshi; Akiyama, Hidehumi; Ito, Seiji; Ohmiya, Yoshihiro

2003-07-01

Luciferases are used as the reporter gene for promoter activity, whereas a green fluorescent protein (GFP) is used as marker for cellular function and localization. Recently, bioluminescence resonance energy transfer (BRET) between luciferase and YFP is used for analysis of inter-molecular reaction such as ligand-receptor in the living cells. The neuropeptides nocistatin (NST) and nociceptin/orphanin FQ (Noc/OFQ) are derived from the same precursor protein, while NST exhibits antagonism against Noc/OFQ-actions. In this study, we attempt an intra-molecular BRET system for monitoring dynamic biological process of the production of NST and Noc/OFQ in the living cells. At first, we constructed a fusion protein (Rluc-GFP) covalently linking luciferase (Renilla luciferase; Rluc) to Aequorea GFP as an intra-molecular BRET partner. Furthermore, we inserted constructs of mouse NST and Noc/OFQ (Rluc-m-GFP) or bovine NST and Noc/OFQ (Rluc-b-GFP) containing a proteolytic cleavage motif (Lys-Arg) within Rluc-GFP. When these constructions were transfected into Cos7 cells, all fusion proteins had luciferase activity and specific fluorescence. Luminescence spectra of Rluc-GFP, Rluc-m-GFP and Rluc-b-GFP fusion proteins with DeepBlueC as a substrate showed two peaks centered at 400 nm and 510 nm, whereas Rluc showed one peak centered at 400 nm. These results indicate that the proteolytic cleavage motif inserted fusion proteins between luciferase and GFP are available for intra-molecular BRET systems at first step.

2-(3-Cyano-4-{3-[1-(2-hy-droxy-eth-yl)-3,3-dimethyl-1,3-di-hydro-indol-2-yl-idene]prop-2-en-yl}-5,5-dimethyl-5H-furan-2-yl-idene)malono-nitrile.

PubMed

Gainsford, Graeme J; Bhuiyan, M Delower H; Kay, Andrew J

2014-01-01

The title compound, C25H24N4O2, adopts a cisoid configuration and has twofold orientational disorder of the 2-hy-droxy-ethyl group. The mol-ecule is twisted from planarity so that the dihedral angle between the terminating indol-2-yl-idene and the furan-2-yl-idene moiety mean planes is 12.75 (7)°. Conformational disorder occurs at the indol-2-yl-idene N atom, which results in two orientations for the hy-droxy-ethyl group [occupancy ratio = 0.896 (2):0.104 (2)], and the hy-droxy O atom of the 2-hy-droxy-ethyl group is located over three sites [occupancy ratio = 0.548 (2):0.348 (2):0.104 (2)]. An intra-molecular C-H⋯O hydrogen bond involving the lowest occupancy hy-droxy O atom is observed. In the crystal, the mol-ecules pack in parallel dimeric sheets about centres of symmetry, utilizing O-H⋯N(cyano), C-H⋯N(cyano) and O-H⋯O hydrogen bonds, in two sets parallel to (02-1) and (021) planes.

Removal of furan and phenolic compounds from simulated biomass hydrolysates by batch adsorption and continuous fixed-bed column adsorption methods.

PubMed

Lee, Sang Cheol; Park, Sunkyu

2016-09-01

It has been proposed to remove all potential inhibitors and sulfuric acid in biomass hydrolysates generated from dilute-acid pretreatment of biomass, based on three steps of sugar purification process. This study focused on its first step in which furan and phenolic compounds were selectively removed from the simulated hydrolysates using activated charcoal. Batch adsorption experiments demonstrated that the affinity of activated charcoal for each component was highest in the order of vanillic acid, 4-hydroxybenzoic acid, furfural, acetic acid, sulfuric acid, and xylose. The affinity of activated charcoal for furan and phenolic compounds proved to be significantly higher than that of the other three components. Four separation strategies were conducted with a combination of batch adsorption and continuous fixed-bed column adsorption methods. It was observed that xylose loss was negligible with near complete removal of furan and phenolic compounds, when at least one fixed-bed column adsorption was implemented in the strategy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Intramolecular Benzoin Reaction Catalyzed by Benzaldehyde Lyase from Pseudomonas Fluorescens Biovar I.

PubMed

Hernández, Karel; Parella, Teodor; Petrillo, Giovanna; Usón, Isabel; Wandtke, Claudia M; Joglar, Jesús; Bujons, Jordi; Clapés, Pere

2017-05-02

Intramolecular benzoin reactions catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I (BAL) are reported. The structure of the substrates envisaged for this reaction consists of two benzaldehyde derivatives linked by an alkyl chain. The structural requirements needed to achieve the intramolecular carbon-carbon bond reaction catalyzed by BAL were established. Thus, a linker consisting of a linear alkyl chain of three carbon atoms connected through ether-type bonds to the 2 and 2' positions of two benzaldehyde moieties, which could be substituted with either Cl, Br, or OCH 3 at either the 3 and 3' or 5 and 5' positions, were suitable substrates for BAL. Reactions with 61-84 % yields of the intramolecular product and ee values between 64 and 98 %, were achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

ACB-PCR measurement of spontaneous and furan-induced H-ras codon 61 CAA to CTA and CAA to AAA mutation in B6C3F1 mouse liver.

PubMed

Banda, Malathi; Recio, Leslie; Parsons, Barbara L

2013-10-01

Furan is a rodent liver carcinogen, but the mode of action for furan hepatocarcinogenicity is unclear. H-ras codon 61 mutations have been detected in spontaneous liver tumors of B6C3F1 mice, and the fraction of liver tumors carrying H-ras codon 61 CAA to AAA mutation increased in furan-treated mice. Allele-specific competitive blocker PCR (ACB-PCR) has been used previously to quantify early, carcinogen-induced increases in tumor-associated mutations. The present pilot study investigated whether furan drives clonal expansion of pre-existing H-ras mutant cells in B6C3F1 mouse liver. H-ras codon 61 CAA to CTA and CAA to AAA mutations were measured in DNA isolated from liver tissue of female mice treated with 0, 1, 2, 4, or 8 mg furan/kg body weight, five days per week for three weeks, using five mice per treatment group. Spontaneous levels of mutation were low, with two of five control mice having an H-ras codon 61 CTA or AAA mutant fraction (MF) greater than 10(-5) . Several furan-treated mice had H-ras codon 61 AAA or CTA MFs greater than those measured in control mice and lower bound estimates of induced MF were calculated. However, no statistically-significant differences were observed between treatment groups. Therefore, while sustained exposure to furan is carcinogenic, at the early stage of carcinogenesis examined in this study (three weeks), there was not a significant expansion of H-ras mutant cells. Copyright © 2013 Wiley Periodicals, Inc.

Isotopic substitution of a hydrogen bond: A near infrared study of the intramolecular states in (DF)2

NASA Astrophysics Data System (ADS)

Davis, Scott; Anderson, David T.; Farrell, John T., Jr.; Nesbitt, David J.

1996-06-01

High resolution near infrared spectra of the two high frequency intramolecular modes in (DF)2 have been characterized using a slit-jet infrared spectrometer. In total, four pairs of vibration-rotation-tunneling (VRT) bands are observed, corresponding to K=0 and K=1 excitation of both the ν2 (``bound'') and ν1 (``free'') intramolecular DF stretching modes. Analysis of the rotationally resolved spectra provides vibrational origins, rotational constants, tunneling splittings and upper state predissociation lifetimes for all four states. The rotational constants indicate that the deuterated hydrogen bond contracts and bends upon intramolecular excitation, analogous to what has been observed for (HF)2. The isotope and K dependence of tunneling splittings for (HF)2 and (DF)2 in both intramolecular modes is interpreted in terms of a semiclassical 1-D tunneling model. High resolution line shape measurements reveal vibrational predissociation broadening in (DF)2: 56(2) and 3(2) MHz for the ν2 (bound) and ν1 (free) intramolecular stretching modes, respectively. This 20-fold mode specific enhancement parallels the ≥30-fold enhancement observed between analogous intramolecular modes of (HF)2, further elucidating the role of nonstatistical predissociation dynamics in such hydrogen bonded clusters.

Intramolecular Isotopic Studies: Chemical Enhancements and Alternatives

NASA Astrophysics Data System (ADS)

Hayes, J. M.

2016-12-01

As mass spectroscopic and NMR-based methods now appropriately flourish, chemical techniques should not be forgotten. First, the methods developed by pioneering intramolecular analysts can be reapplied to new samples. Second, they can be extended. The synthesis of intramolecular isotopic standards is particularly important and straightforward. It requires only that a chemical reaction has no secondary products. An example is provided by the addition of carbon dioxide to a Grignard reagent. The reaction proceeds with an isotope effect. The isotopic composition of the carboxyl group in the acid which is produced is thus not equal to that of the starting carbon dioxide but the unconsumed CO2 can be recovered and analyzed. A simple titration can show that all the rest of the CO2 is in the product acid. The isotopic composition of the carboxyl group can then be calculated by difference. The product is an intramolecular isotopic standard, an organic molecule in which the isotopic composition of a specific carbon position is known accurately. Both analysts and reviewers can thus gain invaluable confidence in the accuracy of instrumental results. A second example: the haloform reaction quantitatively degrades methyl ketones, producing a carboxylic acid which can be decarboxylated to determine the isotopic composition of the parent carbonyl and a haloform (CHI3, for example) that can be combusted to determine the isotopic composition of the methyl group. Ketones thus analyzed can be combined with Grignard reagents to yield carbon skeletons in which the isotopic compositions of internal and terminal -CH2- and -CH3 groups are known accurately. In general, analysts accustomed to demanding quantitative reactions should remember the power of mass balances and recognize that many organic-chemical reactions, while not quantitative, lack side products and can be driven to the total consumption of at least one reactant.

Detailed exposure assessment of dietary furan for infants consuming commercially jarred complementary food based on data from the DONALD study.

PubMed

Lachenmeier, Dirk W; Maser, Elena; Kuballa, Thomas; Reusch, Helmut; Kersting, Mathilde; Alexy, Ute

2012-07-01

Furan is a possible human carcinogen regularly occurring in commercially jarred complementary foods. This paper will provide a detailed exposure assessment for babies consuming these foods considering different intake scenarios. The occurrence data on furan in complementary foods were based on our own headspace-gas chromatography/mass spectrometry (HS-GC/MS) analytical results (n = 286). The average furan content in meals and menus was between 20 and 30 µg kg(-1), which is in excellent agreement with results from other European countries. Using measured food consumption data from the Dortmund Nutritional and Anthropometric Longitudinally Designed (DONALD) study, the average exposures for consumers of commercially jarred foods ranged between 182 and 688 ng kg(-1) bw day(-1), with a worst case scenario for P95 consumers ranging between 351 and 1066 ng kg(-1) bw day(-1). The exposure data were then used to characterize risk using the margin of exposure method based on a benchmark dose lower confidence limit for a 10% response (BMDL10) of 1.28 mg kg(-1) bw day(-1) for hepatocellular tumours in rats. The margin of exposures (MOEs) were below the threshold of 10 000, which is often used to define public health risks, in all scenarios, ranging between 7022 and 1861 for average consumers and between 3642 and 1200 for the P95 consumers. Mitigative measures to avoid furan in complementary foods should be of high priority for risk management. © 2010 Blackwell Publishing Ltd.

Furan Fragmentation in the Gas Phase: New Insights from Statistical and Molecular Dynamics Calculations

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

Erdmann, Ewa; Labuda, Marta; Aguirre, Nestor F.

We present a complete exploration of the different fragmentation mechanisms of furan (C 4H 4O) operating at low and high energies. Three different theoretical approaches are combined to determine the structure of all possible reaction intermediates, many of them not described in previous studies, and a large number of pathways involving three types of fundamental elementary mechanisms: isomerization, fragmentation, and H/H 2 loss processes (this last one was not yet explored). Our results are compared with the existing experimental and theoretical investigations for furan fragmentation. At low energies the first processes to appear are isomerization, which always implies the breakingmore » of one C–O bond and one or several hydrogen transfers; at intermediate energies the fragmentation of the molecular skeleton becomes the most relevant mechanism; and H/H 2 loss is the dominant processes at high energy. However, the three mechanisms are active in very wide energy ranges and, therefore, at most energies there is a competition among them.« less

Furan Fragmentation in the Gas Phase: New Insights from Statistical and Molecular Dynamics Calculations

DOE PAGES

Erdmann, Ewa; Labuda, Marta; Aguirre, Nestor F.; ...

2018-03-15

We present a complete exploration of the different fragmentation mechanisms of furan (C 4H 4O) operating at low and high energies. Three different theoretical approaches are combined to determine the structure of all possible reaction intermediates, many of them not described in previous studies, and a large number of pathways involving three types of fundamental elementary mechanisms: isomerization, fragmentation, and H/H 2 loss processes (this last one was not yet explored). Our results are compared with the existing experimental and theoretical investigations for furan fragmentation. At low energies the first processes to appear are isomerization, which always implies the breakingmore » of one C–O bond and one or several hydrogen transfers; at intermediate energies the fragmentation of the molecular skeleton becomes the most relevant mechanism; and H/H 2 loss is the dominant processes at high energy. However, the three mechanisms are active in very wide energy ranges and, therefore, at most energies there is a competition among them.« less

High concentrations of furan fatty acids in organic butter samples from the German market.

PubMed

Wendlinger, Christine; Vetter, Walter

2014-08-27

Furan fatty acids (F-acids) are valuable antioxidants containing a furan moiety in the central part of the molecule. They occur in the lipids of different foodstuffs and plants, with grass being the main source for their presence in milk fat and butter. Because cows from organic farming receive higher portions of grass-based feed, it was tested whether organic butter samples (n = 26) contain more F-acids than conventional ones (n = 25) in Germany. For this purpose, samples were melted, and the lipid phase was separated and transesterified into methyl esters, which were enriched using silver ion chromatography and analyzed by GC-EI/MS in the selected ion monitoring (SIM) mode. Levels of F-acids in butter were higher in summer than in winter, and in both seasons, organic samples contained significantly higher levels of F-acids than conventional ones (one-way ANOVA: p < 0.001). Furthermore, the daily intake of F-acids via milk fat and other foodstuffs was calculated.

Quantitative relation between intermolecular and intramolecular binding of pro-rich peptides to SH3 domains.

PubMed

Zhou, Huan-Xiang

2006-11-01

Flexible linkers are often found to tether binding sequence motifs or connect protein domains. Here we analyze three usages of flexible linkers: 1), intramolecular binding of proline-rich peptides (PRPs) to SH3 domains for kinase regulation; 2), intramolecular binding of PRP for increasing the folding stability of SH3 domains; and 3), covalent linking of PRPs and other ligands for high-affinity bivalent binding. The basis of these analyses is a quantitative relation between intermolecular and intramolecular binding constants. This relation has the form K(i) = K(e0)p for intramolecular binding and K(e) = K(e01)K(e02)p for bivalent binding. The effective concentration p depends on the length of the linker and the distance between the linker attachment points in the bound state. Several applications illustrate the usefulness of the quantitative relation. These include intramolecular binding to the Itk SH3 domain by an internal PRP and to a circular permutant of the alpha-spectrin SH3 domain by a designed PRP, and bivalent binding to the two SH3 domains of Grb2 by two linked PRPs. These and other examples suggest that flexible linkers and sequence motifs tethered to them, like folded protein domains, are also subject to tight control during evolution.

Novel biobased photo-crosslinked polymer networks prepared from vegetable oil and 2,5-furan diacrylate

USDA-ARS?s Scientific Manuscript database

Novel biobased crosslinked polymer networks were prepared from vegetable oil with 2,5-furan diacrylate as a difunctional stiffener through UV photopolymerization, and the mechanical properties of the resulting films were evaluated. The vegetable oil raw materials used were acrylated epoxidized soybe...

Catalytic hydrolysis of cellulose into furans

NASA Astrophysics Data System (ADS)

Shi, Chengmei; Tao, Furong; Cui, Yuezhi

2016-12-01

Chromium chloride in 4-(3-methylimidazolium-1-yl)butane-1-sulfonic acid hydrogen sulfate (IL-1) was found to effectively catalyze the hydrolysis of microcrystalline cellulose (MCC) at 150°C for 300 min to achieve 87.8% conversion to a slate of products. With a catalytic amount of CrCl3, the yields of 5-hydroxymethyl furfural (HMF) and furfural were up to 32.4 and 15.2%, respectively, small molecules levulinic acid (LA, 10.8%) and the total reducing sugars (TRS, 10.7%) were also generated. Through LC-MSD analysis and mass spectra, dimer of furan compounds as the main by-products were speculated, and the components of gas products were methane, ethane, CO, CO2, and H2. We suggested that IL-1 and CrCl3 exhibited a coordination interaction; the formation of the intermediate via the hydride shift played a key role in the formation of HMF. The catalyst was recycled and exhibited constant activity for five successive trials.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part III: 2,5-Dimethylfuran.

PubMed

Togbé, Casimir; Tran, Luc-Sy; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2014-03-01

This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model.

Intramolecular aggregation and optical limiting properties of triazine-linked mono-, bis- and tris-phthalocyanines.

PubMed

Chen, Jun; Zhang, Tao; Wang, Shuangqing; Hu, Rui; Li, Shayu; Ma, Jin Shi; Yang, Guoqiang

2015-10-05

A series of triazine-linked mono-, bis- and tris-phthalocyanines are synthesized, intramolecular aggregation is found in bis- and tris-phthalocyanines via π-π stacking interaction. Theoretical and experimental studies reveal the formation of the intramolecular aggregation. The spectrographic, photophysical and nonlinear optical properties of these compounds are adjusted for the formation of the intramolecular aggregation. The bis-phthalocyanine dimer presents smaller fluorescence quantum yield, lower triplet formation yield and the triplet-minus-ground state extinction coefficient, which causes poorer optical limiting performance. It is interesting that the tris-phthalocyanine is composed of a mono-phthalocyanine part and a bis-phthalocyanine part, the optical limiting property of the tris-phthalocyanine is similar to that of mono-phthalocyanine. Copyright © 2015 Elsevier B.V. All rights reserved.

Covalently Linked Tandem Lesions in DNA

PubMed Central

Patrzyc, Helen B.; Dawidzik, Jean B.; Budzinski, Edwin E.; Freund, Harold G.; Wilton, John H.; Box, Harold C.

2013-01-01

Reactive oxygen species (ROS) generate a type of DNA damage called tandem lesions, two adjacent nucleotides both modified. A subcategory of tandem lesions consists of adjacent nucleotides linked by a covalent bond. Covalently linked tandem lesions generate highly characteristic liquid chromotography-tandem mass spectrometry (LC-MS/MS) elution profiles. We have used this property to comprehensively survey X-irradiated DNA for covalently linked tandem lesions. A total of 15 tandem lesions were detected in DNA irradiated in deoxygenated aqueous solution, five tandem lesions were detected in DNA that was irradiated in oxygenated solution. PMID:23106212

Raman and surface enhanced Raman scattering study of the orientation of cruciform 9,10-anthracene thiophene and furan derivatives deposited on a gold colloidal surface

NASA Astrophysics Data System (ADS)

Muñoz-Pérez, J.; Leyton, P.; Paipa, C.; Soto, J. P.; Brunet, J.; Gómez-Jeria, J. S.; Campos-Vallette, M. M.

2016-10-01

The 9,10-di(thiophen-2-yl)anthracene (TAT), 9,10-di(furan-2-yl)anthracene (FAF) and 2-[(10-(thiophen-2-yl)anthracen-9-yl)]furan (TAF) cruciform molecular systems were synthesized using one-step coupling reactions and structurally characterized via Raman, infrared, 1H NMR, 13C NMR and mass spectroscopies. The orientation of the analytes on a gold colloidal surface was inferred from a surface-enhanced Raman scattering (SERS) study. The metal surface interaction was driven by the S and O atoms of the thiophene and furan α-substituents, and the plane of the anthracene fragment remained parallel to the surface. Theoretical calculations based on a simplified molecular model for the analyte-surface interaction provide a good representation of the experimental data.

Regio-Selective Intramolecular Hydrogen/Deuterium Exchange in Gas-Phase Electron Transfer Dissociation

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo

2017-05-01

Protein backbone amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) typically utilizes enzymatic digestion after the exchange reaction and before MS analysis to improve data resolution. Gas-phase fragmentation of a peptic fragment prior to MS analysis is a promising technique to further increase the resolution. The biggest technical challenge for this method is elimination of intramolecular hydrogen/deuterium exchange (scrambling) in the gas phase. The scrambling obscures the location of deuterium. Jørgensen's group pioneered a method to minimize the scrambling in gas-phase electron capture/transfer dissociation. Despite active investigation, the mechanism of hydrogen scrambling is not well-understood. The difficulty stems from the fact that the degree of hydrogen scrambling depends on instruments, various parameters of mass analysis, and peptide analyzed. In most hydrogen scrambling investigations, the hydrogen scrambling is measured by the percentage of scrambling in a whole molecule. This paper demonstrates that the degree of intramolecular hydrogen/deuterium exchange depends on the nature of exchangeable hydrogen sites. The deuterium on Tyr amide of neurotensin (9-13), Arg-Pro-Tyr-Ile-Leu, migrated significantly faster than that on Ile or Leu amides, indicating the loss of deuterium from the original sites is not mere randomization of hydrogen and deuterium but more site-specific phenomena. This more precise approach may help understand the mechanism of intramolecular hydrogen exchange and provide higher confidence for the parameter optimization to eliminate intramolecular hydrogen/deuterium exchange during gas-phase fragmentation.

Regio-Selective Intramolecular Hydrogen/Deuterium Exchange in Gas-Phase Electron Transfer Dissociation.

PubMed

Hamuro, Yoshitomo

2017-05-01

Protein backbone amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) typically utilizes enzymatic digestion after the exchange reaction and before MS analysis to improve data resolution. Gas-phase fragmentation of a peptic fragment prior to MS analysis is a promising technique to further increase the resolution. The biggest technical challenge for this method is elimination of intramolecular hydrogen/deuterium exchange (scrambling) in the gas phase. The scrambling obscures the location of deuterium. Jørgensen's group pioneered a method to minimize the scrambling in gas-phase electron capture/transfer dissociation. Despite active investigation, the mechanism of hydrogen scrambling is not well-understood. The difficulty stems from the fact that the degree of hydrogen scrambling depends on instruments, various parameters of mass analysis, and peptide analyzed. In most hydrogen scrambling investigations, the hydrogen scrambling is measured by the percentage of scrambling in a whole molecule. This paper demonstrates that the degree of intramolecular hydrogen/deuterium exchange depends on the nature of exchangeable hydrogen sites. The deuterium on Tyr amide of neurotensin (9-13), Arg-Pro-Tyr-Ile-Leu, migrated significantly faster than that on Ile or Leu amides, indicating the loss of deuterium from the original sites is not mere randomization of hydrogen and deuterium but more site-specific phenomena. This more precise approach may help understand the mechanism of intramolecular hydrogen exchange and provide higher confidence for the parameter optimization to eliminate intramolecular hydrogen/deuterium exchange during gas-phase fragmentation. Graphical Abstract ᅟ.

Benzothiazole-Based AIEgen with Tunable Excited-State Intramolecular Proton Transfer and Restricted Intramolecular Rotation Processes for Highly Sensitive Physiological pH Sensing.

PubMed

Li, Kai; Feng, Qi; Niu, Guangle; Zhang, Weijie; Li, Yuanyuan; Kang, Miaomiao; Xu, Kui; He, Juan; Hou, Hongwei; Tang, Ben Zhong

2018-04-23

In this work, a benzothiazole-based aggregation-induced emission luminogen (AIEgen) of 2-(5-(4-carboxyphenyl)-2-hydroxyphenyl)benzothiazole (3) was designed and synthesized, which exhibited multifluorescence emissions in different dispersed or aggregated states based on tunable excited-state intramolecular proton transfer (ESIPT) and restricted intramolecular rotation (RIR) processes. 3 was successfully used as a ratiometric fluorescent chemosensor for the detection of pH, which exhibited reversible acid/base-switched yellow/cyan emission transition. More importantly, the pH jump of 3 was very precipitous from 7.0 to 8.0 with a midpoint of 7.5, which was well matched with the physiological pH. This feature makes 3 very suitable for the highly sensitive detection of pH fluctuation in biosamples and neutral water samples. 3 was also successfully used as a ratiometric fluorescence chemosensor for the detection of acidic and basic organic vapors in test papers.

Intramolecular BSSE and dispersion affect the structure of a dipeptide conformer

NASA Astrophysics Data System (ADS)

Hameed, Rabia; Khan, Afsar; van Mourik, Tanja

2018-05-01

B3LYP and MP2 calculations with the commonly-used 6-31+G(d) basis set predict qualitatively different structures for the Tyr-Gly conformer book1, which is the most stable conformer identified in a previous study. The structures differ mainly in the ψtyr Ramachandran angle (138° in the B3LYP structure and 120° in the MP2 structure). The causes for the discrepant structures are attributed to missing dispersion in the B3LYP calculations and large intramolecular BSSE in the MP2 calculations. The correct ψtyr value is estimated to be 130°. The MP2/6-31+G(d) profile identified an additional conformer, not present on the B3LYP surface, with a ψtyr value of 96° and a more folded structure. This minimum is, however, likely an artefact of large intramolecular BSSE values. We recommend the use of basis sets of at least quadruple-zeta quality in density functional theory (DFT), DFTaugmented with an empirical dispersion term (DFT-D) and second-order Møller-Plesset perturbation theory (MP2 ) calculations in cases where intramolecular BSSE is expected to be large.

Regulation of interleukin-4 signaling by extracellular reduction of intramolecular disulfides

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

Curbo, Sophie; Gaudin, Raphael; Carlsten, Mattias

2009-12-25

Interleukin-4 (IL-4) contains three structurally important intramolecular disulfides that are required for the bioactivity of the cytokine. We show that the cell surface of HeLa cells and endotoxin-activated monocytes can reduce IL-4 intramolecular disulfides in the extracellular space and inhibit binding of IL-4 to the IL-4R{alpha} receptor. IL-4 disulfides were in vitro reduced by thioredoxin 1 (Trx1) and protein disulfide isomerase (PDI). Reduction of IL-4 disulfides by the cell surface of HeLa cells was inhibited by auranofin, an inhibitor of thioredoxin reductase that is an electron donor to both Trx1 and PDI. Both Trx1 and PDI have been shown tomore » be located at the cell surface and our data suggests that these enzymes are involved in catalyzing reduction of IL-4 disulfides. The pro-drug N-acetylcysteine (NAC) that promotes T-helper type 1 responses was also shown to mediate the reduction of IL-4 disulfides. Our data provides evidence for a novel redox dependent pathway for regulation of cytokine activity by extracellular reduction of intramolecular disulfides at the cell surface by members of the thioredoxin enzyme family.« less

High-level ab initio enthalpies of formation of 2,5-dimethylfuran, 2-methylfuran, and furan.

PubMed

Feller, David; Simmie, John M

2012-11-29

A high-level ab initio thermochemical technique, known as the Feller-Petersen-Dixon method, is used to calculate the total atomization energies and hence the enthalpies of formation of 2,5-dimethylfuran, 2-methylfuran, and furan itself as a means of rationalizing significant discrepancies in the literature. In order to avoid extremely large standard coupled cluster theory calculations, the explicitly correlated CCSD(T)-F12b variation was used with basis sets up to cc-pVQZ-F12. After extrapolating to the complete basis set limit and applying corrections for core/valence, scalar relativistic, and higher order effects, the final Δ(f)H° (298.15 K) values, with the available experimental values in parentheses are furan -34.8 ± 3 (-34.7 ± 0.8), 2-methylfuran -80.3 ± 5 (-76.4 ± 1.2), and 2,5-dimethylfuran -124.6 ± 6 (-128.1 ± 1.1) kJ mol(-1). The theoretical results exhibit a compelling internal consistency.

Sky-blue emitting bridged diiridium complexes: beneficial effects of intramolecular π-π stacking.

PubMed

Congrave, Daniel G; Hsu, Yu-Ting; Batsanov, Andrei S; Beeby, Andrew; Bryce, Martin R

2018-02-06

The potential of intramolecular π-π interactions to influence the photophysical properties of diiridium complexes is an unexplored topic, and provides the motivation for the present study. A series of diarylhydrazide-bridged diiridium complexes functionalised with phenylpyridine (ppy)-based cyclometalating ligands is reported. It is shown by NMR studies in solution and single crystal X-ray analysis that intramolecular π-π interactions between the bridging and cyclometalating ligands rigidify the complexes leading to high luminescence quantum efficiencies in solution and in doped films. Fluorine substituents on the phenyl rings of the bridge promote the intramolecular π-π interactions. Notably, these non-covalent interactions are harnessed in the rational design and synthesis of the first examples of highly emissive sky-blue diiridium complexes featuring conjugated bridging ligands, for which they play a vital role in the structural and photophysical properties. Experimental results are supported by computational studies.

Direct carbon-carbon coupling of furanics with acetic acid over Brønsted zeolites

PubMed Central

Gumidyala, Abhishek; Wang, Bin; Crossley, Steven

2016-01-01

Effective carbon-carbon coupling of acetic acid to form larger products while minimizing CO2 emissions is critical to achieving a step change in efficiency for the production of transportation fuels from sustainable biomass. We report the direct acylation of methylfuran with acetic acid in the presence of water, all of which can be readily produced from biomass. This direct coupling limits unwanted polymerization of furanics while producing acetyl methylfuran. Reaction kinetics and density functional theory calculations illustrate that the calculated apparent barrier for the dehydration of the acid to form surface acyl species is similar to the experimentally measured barrier, implying that this step plays a significant role in determining the net reaction rate. Water inhibits the overall rate, but selectivity to acylated products is not affected. We show that furanic species effectively stabilize the charge of the transition state, therefore lowering the overall activation barrier. These results demonstrate a promising new route to C–C bond–forming reactions for the production of higher-value products from biomass. PMID:27652345

Simultaneous detoxification and bioethanol fermentation of furans-rich synthetic hydrolysate by digestate-based pyrochar.

PubMed

Sambusiti, C; Monlau, F; Antoniou, N; Zabaniotou, A; Barakat, A

2016-12-01

Pyrolysis is a sustainable pathway to transform renewable biomasses into both biofuels and advanced carbonaceous materials (i.e. pyrochar) which can be used as adsorbent of furan compounds. In particular, the aim of this study was to: i) evaluate the effect of vibro-ball milling on physical characteristics of pyrochar and its consequent performance on solely detoxification of a synthetic medium, containing furans and soluble sugars; ii) study the simultaneous detoxification and bioethanol fermentation, by adding activated pyrochar into fermentation medium. Results demonstrated that, compared to untreated pyrochar, the use of milled pyrochar increased by 52% furfural removal from the synthetic medium. Furfural removal rate was also increased (adsorption kinetic constant increased from 0.015 min -1 up to 0.215 min -1 ), at a pyrochar loading of 40 g L -1 . Although, the simultaneous addition of pyrochar into the fermentation medium did not improve the bioethanol yield of the synthetic medium, it has significantly increased the bioethanol production rate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Visible-Light Photocatalytic Intramolecular Cyclopropane Ring Expansion.

PubMed

Luis-Barrera, Javier; Laina-Martín, Víctor; Rigotti, Thomas; Peccati, Francesca; Solans-Monfort, Xavier; Sodupe, Mariona; Mas-Ballesté, Rubén; Liras, Marta; Alemán, José

2017-06-26

Described herein is a new visible-light photocatalytic strategy for the synthesis of enantioenriched dihydrofurans and cyclopentenes by an intramolecular nitro cyclopropane ring expansion reaction. Mechanistic studies and DFT calculations are used to elucidate the key factors in this new ring expansion reaction, and the need for the nitro group on the cyclopropane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part III: 2,5-Dimethylfuran

PubMed Central

Togbé, Casimir; Tran, Luc-Sy; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2013-01-01

This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model. PMID:24518851

Intramolecular stable isotope distributions detect plant metabolic responses on century time scales

NASA Astrophysics Data System (ADS)

Schleucher, Jürgen; Ehlers, Ina; Augusti, Angela; Betson, Tatiana

2014-05-01

Plants respond to environmental changes on a vast range of time scales, and plant gas exchanges constitute important feedback mechanisms in the global C cycle. Responses on time scales of decades to centuries are most important for climate models, for prediction of crop productivity, and for adaptation to climate change. Unfortunately, responses on these timescale are least understood. We argue that the knowledge gap on intermediate time scales is due to a lack of adequate methods that can bridge between short-term manipulative experiments (e.g. FACE) and paleo research. Manipulative experiments in plant ecophysiology give information on metabolism on time scales up to years. However, this information cannot be linked to results from retrospective studies in paleo research, because little metabolic information can be derived from paleo archives. Stable isotopes are prominent tools in plant ecophysiology, biogeochemistry and in paleo research, but in all applications to date, isotope ratios of whole molecules are measured. However, it is well established that stable isotope abundance varies among intramolecular groups of biochemical metabolites, that is each so-called "isotopomer" has a distinct abundance. This intramolecular variation carries information on metabolic regulation, which can even be traced to individual enzymes (Schleucher et al., Plant, Cell Environ 1999). Here, we apply intramolecular isotope distributions to study the metabolic response of plants to increasing atmospheric [CO2] during the past century. Greenhouse experiments show that the deuterium abundance among the two positions in the C6H2 group of photosynthetic glucose depends on [CO2] during growth. This is observed for all plants using C3 photosynthesis, and reflects the metabolic flux ratio between photorespiration and photosynthesis. Photorespiration is a major C flux that limits assimilation in C3 plants, which encompass the overwhelming fraction of terrestrial photosynthesis and the

Green oxidations of furans--initiated by molecular oxygen--that give key natural product motifs.

PubMed

Montagnon, Tamsyn; Noutsias, Dimitris; Alexopoulou, Ioanna; Tofi, Maria; Vassilikogiannakis, Georgios

2011-04-07

In this article, we explore how changes in the positioning of pendant hydroxyl functionalities in the photooxygenation substrate dramatically alter the course of furan oxidations that are initiated by singlet oxygen; and, how these different reactivities can be harnessed through cascade reaction sequences to access, rapidly and effectively, a broad range of important natural product motifs.

Expeditious construction of (+)-mintlactone via intramolecular hetero-Pauson-Khand reaction.

PubMed

Gao, Peng; Xu, Peng-Fei; Zhai, Hongbin

2009-03-20

(+)-Mintlactone, a bicyclic monoterpene natural product, has been efficiently assembled from (-)-citronellol in three steps. The synthesis features nitrous acid-induced formal isopropylidene "demethanation" and the molybdenum-mediated intramolecular hetero-Pauson-Khand reaction.

THE CONCENTRATION AND DISTRIBUTION OF 2,3,7,8-DIBENZO-P-DIOXINS / - FURANS IN CHICKENS

EPA Science Inventory

The concentrations of 2,3,7,8-Cl substituted dibenzo-p-dioxins/-furans (PCDDs/PCDFs) were determined in the edible tissues of whole chicken fryers and compared with the values found in their abdominal fat. The values are presented both on a whole weight basis and on a lipid-adju...

Orthogonal tandem catalysis

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

Lohr, Tracy L.; Marks, Tobin J.

2015-05-20

Tandem catalysis is a growing field that is beginning to yield important scientific and technological advances toward new and more efficient catalytic processes. 'One-pot' tandem reactions, where multiple catalysts and reagents, combined in a single reaction vessel undergo a sequence of precisely staged catalytic steps, are highly attractive from the standpoint of reducing both waste and time. Orthogonal tandem catalysis is a subset of one-pot reactions in which more than one catalyst is used to promote two or more mechanistically distinct reaction steps. This Perspective summarizes and analyses some of the recent developments and successes in orthogonal tandem catalysis, withmore » particular focus on recent strategies to address catalyst incompatibility. We also highlight the concept of thermodynamic leveraging by coupling multiple catalyst cycles to effect challenging transformations not observed in single-step processes, and to encourage application of this technique to energetically unfavourable or demanding reactions.« less

CHLOROBENZENES, CHLOROPHENOLS, PHAS AND LOW CHLORINATED DIOXIN/FURAN POST-BOILER TOXICITY INDICATORS IN MUNICIPAL SOLID WASTE INCINERATORS

EPA Science Inventory

Research has sought indicator compounds for fast and less costly predictive monitoring of polychlorinated dibenzo-p-dioxin and furans, PCDD/F, toxic equivalent concentrations or TEQs. Studies have shown chlorobenzenes and chlorophenols had a good correlation with TEQ, suggesting ...

Electronic Excitation of Furan by Low Energy Electrons

NASA Astrophysics Data System (ADS)

Hargreaves, Leigh R.; Khakoo, Murtadha A.; Lopes, Maria Cristina A.; da Costa, Romarly; Bettega, Marcio H. F.; Lima, Marco A. P.

2011-10-01

We present absolute differential cross section (DCS) measurements and calculations of electron impact excitation of the lowest lying triplet 3B2 and 3A1 electronic states of furan. The incident electron energy range of the present study was 5-15eV. The experimental data were normalized to the elastic DCS data of. The cross sections were determined by unfolding electron energy loss spectra, using an open source data analysis package and the spectroscopic assignments of. The calculations employ a Multichannel Schwinger method with a 9-state closed coupling CI configuration including polarized pseudo-potentials. The preliminary theoretical results show reasonable agreement with experiment below 10eV, but differ at higher energies. Funded by the US NSF and the Brazilian funding agencies CNPq, CAPES and FAPESP.

Production of a novel antioxidant furan fatty acid from 7,10-dihydroxy-8(E)-octadecenoic acid

USDA-ARS?s Scientific Manuscript database

Furan fatty acids (F-acids) have gained attention since they are known to play important roles in a variety of biological systems. Specifically F-acids are known to have strong antioxidant activity. Although widely distributed in most biological systems, F-acids are trace components and their biosyn...

The scope and limitations of intramolecular Nicholas and Pauson-Khand reactions for the synthesis of tricyclic oxygen- and nitrogen-containing heterocycles.

PubMed

Closser, Kristina D; Quintal, Miriam M; Shea, Kevin M

2009-05-15

We studied the scope and limitations of a tandem intramolecular Nicholas/Pauson-Khand strategy for the synthesis of tricyclic oxygen- and nitrogen-containing heterocycles. This methodology enables conversion of simple acyclic starting materials into a series of previously unknown heterocyclic architectures. For the preparation of cyclic ethers (Z = O), tricyclic [5,6,5]- through [5,9,5]-systems (m = 1, n = 1-4) are available with the [5,7,5]- and [5,8,5]-systems amenable to quick and efficient synthesis. Tricyclic [5,7,5]- and [5,8,5]-amine-containing (Z = NTs) heterocycles can be successfully prepared. Attempts to make larger ring systems (Z = O, m = 2; Z = O, n = 5; or Z = NTs, n = 4-5) or prepare lactones via Nicholas reactions with carboxylic acid nucleophiles (available via oxidation of alcohol nucleophiles, Z = O) result in decomposition or dimerization. The latter process enables formation of 14-, 16-, and 18-membered ring diolides when using carboxylic acid nucleophiles. We also investigated the use of chiral amine promoters in the Pauson-Khand step but found no asymmetric induction.

Intramolecular oxidative deselenization of acylselenoureas: a facile synthesis of benzoxazole amides and carbonic anhydrase inhibitors.

PubMed

Angeli, A; Peat, T S; Bartolucci, G; Nocentini, A; Supuran, C T; Carta, F

2016-12-28

A mild, efficient and one pot procedure to access benzoxazoles using easily accessible acylselenoureas as starting materials has been discovered. Mechanistic studies revealed a pH dependent intramolecular oxidative deselenization, with ring closure due to an intramolecular nucleophilic attack of a phenoxide ion. All the benzoxazoles herein reported possessed a primary sulfonamide zinc binding group and showed effective inhibitory action on the enzymes, carbonic anhydrases.

Formation of benzo[f]-1-indanone frameworks by regulable intramolecular annulations of gem-dialkylthio trienynes.

PubMed

Fang, Zhongxue; Liu, Ying; Barry, Badru-Deen; Liao, Peiqiu; Bi, Xihe

2015-02-20

An atom-economic route to benzo[f]-1-indanone frameworks has been developed starting from the readily available gem-dialkylthio trienynes by intramolecular annulations. The chemoselectivity of the intramolecular cyclizations can be regulated by both the base and the type of gas atmosphere used in the reaction, thus allowing the divergent synthesis of the corresponding functionalized benzo[f]-1-indanones in good to excellent yields.

The excited-state intramolecular proton transfer in Nsbnd H-type dye molecules with a seven-membered-ring intramolecular hydrogen bond: A theoretical insight

NASA Astrophysics Data System (ADS)

Yuan, Huijuan; Feng, Songyan; Wen, Keke; Guo, Xugeng; Zhang, Jinglai

2018-02-01

Excited-state intramolecular proton transfer (ESIPT) reactions of a series of N(R)sbnd H ⋯ N-type seven-membered-ring hydrogen-bonding compounds were explored by employing density functional theory/time-dependent density functional theory calculations with the PBE0 functional. Our results indicate that the absorption and emission spectra predicted theoretically match very well the experimental findings. Additionally, as the electron-withdrawing strength of R increases, the intramolecular H-bond of the Nsbnd S1 form gradually enhances, and the forward energy barrier along the ESIPT reaction gradually decreases. For compound 4, its ESIPT reaction is found to be a barrierless process due to the involvement of a strong electron-withdrawing COCF3 group. It is therefore a reasonable presumption that the ESIPT efficiency of these N(R)sbnd H ⋯ N-type seven-membered-ring H-bonding systems can be improved when a strong electron-withdrawing group in R is introduced.

Intramolecular amide bonds stabilize pili on the surface of bacilli

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

Budzik, Jonathan M.; Poor, Catherine B.; Faull, Kym F.

Gram-positive bacteria elaborate pili and do so without the participation of folding chaperones or disulfide bond catalysts. Sortases, enzymes that cut pilin precursors, form covalent bonds that link pilin subunits and assemble pili on the bacterial surface. We determined the x-ray structure of BcpA, the major pilin subunit of Bacillus cereus. The BcpA precursor encompasses 2 Ig folds (CNA{sub 2} and CNA{sub 3}) and one jelly-roll domain (XNA) each of which synthesizes a single intramolecular amide bond. A fourth amide bond, derived from the Ig fold of CNA{sub 1}, is formed only after pilin subunits have been incorporated into pili.more » We report that the domains of pilin precursors have evolved to synthesize a discrete sequence of intramolecular amide bonds, thereby conferring structural stability and protease resistance to pili.« less

Sesquiterpene furan compound CJ-01, a novel chitin synthase 2 inhibitor from Chloranthus japonicus SIEB.

PubMed

Yim, Nam Hui; Hwang, Eui Il; Yun, Bong Sik; Park, Ki Duk; Moon, Jae Sun; Lee, Sang Han; Sung, Nack Do; Kim, Sung Uk

2008-05-01

A novel sesquiterpene furan compound CJ-01 was isolated from the methanol extract of the whole plant of Chloranthus japonicus SIEB. by monitoring the inhibitory activity of chitin synthase 2 from Saccharomyces cerevisiae. Based on spectroscopic analysis, the structure of compound CJ-01 was determined as 3,4,8a-trimethyl-4a,7,8,8a-tetrahydro-4a-naphto[2,3-b]furan-9-one. The compound inhibited chitin synthase 2 of Saccharomyces cerevisiae in a dose-dependent manner with an IC50 of 39.6 microg/ml, whereas it exhibited no inhibitory activities against chitin synthase 1 and 3 of S. cerevisiae up to 280 microg/ml. CJ-01 has 1.7-fold stronger inhibitory activity than polyoxin D (IC50=70 microg/ml), a well-known chitin synthase inhibitor. These results indicate that the compound is a specific inhibitor of chitin synthase 2 from S. cerevisiae. In addition, CJ-01 showed antifungal activities against various human and phytopathogenic fungi. Therefore, the compound might be an interesting lead to develop effective antifungal agents.

Furan-2-ylmethylene thiazolidinediones as novel, potent, and selective inhibitors of phosphoinositide 3-kinase gamma.

PubMed

Pomel, Vincent; Klicic, Jasna; Covini, David; Church, Dennis D; Shaw, Jeffrey P; Roulin, Karen; Burgat-Charvillon, Fabienne; Valognes, Delphine; Camps, Montserrat; Chabert, Christian; Gillieron, Corinne; Françon, Bernard; Perrin, Dominique; Leroy, Didier; Gretener, Denise; Nichols, Anthony; Vitte, Pierre Alain; Carboni, Susanna; Rommel, Christian; Schwarz, Matthias K; Rückle, Thomas

2006-06-29

Class I phosphoinositide 3-kinases (PI3Ks), in particular PI3Kgamma, have become attractive drug targets for inflammatory and autoimmune diseases. Here, we disclose a novel series of furan-2-ylmethylene thiazolidinediones as selective, ATP-competitive PI3Kgamma inhibitors. Structure-based design and X-ray crystallography of complexes formed by inhibitors bound to PI3Kgamma identified key pharmacophore features for potency and selectivity. An acidic NH group on the thiazolidinedione moiety and a hydroxy group on the furan-2-yl-phenyl part of the molecule play crucial roles in binding to PI3K and contribute to class IB PI3K selectivity. Compound 26 (AS-252424), a potent and selective small-molecule PI3Kgamma inhibitor emerging from these efforts, was further profiled in three different cellular PI3K assays and shown to be selective for class IB PI3K-mediated cellular effects. Oral administration of 26 in a mouse model of acute peritonitis led to a significant reduction of leukocyte recruitment.

Template engineered biopotent macrocyclic complexes involving furan moiety: Molecular modeling and molecular docking

NASA Astrophysics Data System (ADS)

Rathi, Parveen; Singh, D. P.

2015-08-01

Bioactive cobalt(II), nickel(II), copper(II) and zinc(II) complexes of octaazamacrocycle, 19, 20-dioxa-2,3,5,6,11,12,14,15-octaazatricyclo[14.2.1.1]icosa-1,6,8,10,15,17-hexaene-4,13-dithione, derived from furan-2,5-dione and thiocarbonohydrazide in the mole ratio 2:2:1 have been engineered via template methodology. The synthesized metal complexes have also been structurally characterized in the light of various physicochemical techniques and evaluated for antimicrobial and antioxidant activities. All these studies point toward the formation of divalent macrocyclic complexes possessing distorted octahedral geometry and having significant antimicrobial and antioxidant properties as compared to the starting precursors. Virtual screening of a representative complex was done through docking to the binding site of COX-2 to evaluate the anti-inflammatory activity of the series. Non-electrolytic nature of the complexes has been predicted on the basis of low value of molar conductivity in DMSO. All the complexes were having notable activities against pathogenic microbes as compared to precursors-thiocarbonohydrazide and furan-2,5-dione however, the complex 5, [Ni (C10H8N8O2S2) (NO3)2], shows the best antimicrobial activity.

The hydrodeoxygenation of bioderived furans into alkanes.

PubMed

Sutton, Andrew D; Waldie, Fraser D; Wu, Ruilian; Schlaf, Marcel; Silks, Louis A Pete; Gordon, John C

2013-05-01

The conversion of biomass into fuels and chemical feedstocks is one part of a drive to reduce the world's dependence on crude oil. For transportation fuels in particular, wholesale replacement of a fuel is logistically problematic, not least because of the infrastructure that is already in place. Here, we describe the catalytic defunctionalization of a series of biomass-derived molecules to provide linear alkanes suitable for use as transportation fuels. These biomass-derived molecules contain a variety of functional groups, including olefins, furan rings and carbonyl groups. We describe the removal of these in either a stepwise process or a one-pot process using common reagents and catalysts under mild reaction conditions to provide n-alkanes in good yields and with high selectivities. Our general synthetic approach is applicable to a range of precursors with different carbon content (chain length). This allows the selective generation of linear alkanes with carbon chain lengths between eight and sixteen carbons.

The hydrodeoxygenation of bioderived furans into alkanes

NASA Astrophysics Data System (ADS)

Sutton, Andrew D.; Waldie, Fraser D.; Wu, Ruilian; Schlaf, Marcel; ‘Pete' Silks, Louis A.; Gordon, John C.

2013-05-01

The conversion of biomass into fuels and chemical feedstocks is one part of a drive to reduce the world's dependence on crude oil. For transportation fuels in particular, wholesale replacement of a fuel is logistically problematic, not least because of the infrastructure that is already in place. Here, we describe the catalytic defunctionalization of a series of biomass-derived molecules to provide linear alkanes suitable for use as transportation fuels. These biomass-derived molecules contain a variety of functional groups, including olefins, furan rings and carbonyl groups. We describe the removal of these in either a stepwise process or a one-pot process using common reagents and catalysts under mild reaction conditions to provide n-alkanes in good yields and with high selectivities. Our general synthetic approach is applicable to a range of precursors with different carbon content (chain length). This allows the selective generation of linear alkanes with carbon chain lengths between eight and sixteen carbons.

Synthesis and PGE(2) production inhibition of 1H-furan-2,5-dione and 1H-pyrrole-2,5-dione derivatives.

PubMed

Moon, Jong Taik; Jeon, Ji Young; Park, Hang Ah; Noh, Young-Soo; Lee, Kyung-Tae; Kim, Jungahn; Choo, Dong Joon; Lee, Jae Yeol

2010-01-15

3,4-Diphenyl-substituted 1H-furan-2,5-dione and 1H-pyrrole-2,5-dione derivatives were synthesized and evaluated for the inhibitory activities on LPS-induced PGE(2) production in RAW 264.7 macrophage cells. Both 1H-furan-2,5-dione and 1H-pyrrole-2,5-dione rings as main scaffolds were easily obtained using one of three synthetic methods. Among the compounds investigated, 1H-3-(4-sulfamoylphenyl)-4-phenyl-pyrrole-2,5-dione (6l) showed a strong inhibitory activity (IC(50)=0.61microM) of PGE(2) production. Copyright 2009 Elsevier Ltd. All rights reserved.

Intramolecular interactions regulate SAP97 binding to GKAP

PubMed Central

Wu, Hongju; Reissner, Carsten; Kuhlendahl, Sven; Coblentz, Blake; Reuver, Susanne; Kindler, Stefan; Gundelfinger, Eckart D.; Garner, Craig C.

2000-01-01

Membrane-associated guanylate kinase homologs (MAGUKs) are multidomain proteins found to be central organizers of cellular junctions. In this study, we examined the molecular mechanisms that regulate the interaction of the MAGUK SAP97 with its GUK domain binding partner GKAP (GUK-associated protein). The GKAP–GUK interaction is regulated by a series of intramolecular interactions. Specifically, the association of the Src homology 3 (SH3) domain and sequences situated between the SH3 and GUK domains with the GUK domain was found to interfere with GKAP binding. In contrast, N-terminal sequences that precede the first PDZ domain in SAP97, facilitated GKAP binding via its association with the SH3 domain. Utilizing crystal structure data available for PDZ, SH3 and GUK domains, molecular models of SAP97 were generated. These models revealed that SAP97 can exist in a compact U-shaped conformation in which the N-terminal domain folds back and interacts with the SH3 and GUK domains. These models support the biochemical data and provide new insights into how intramolecular interactions may regulate the association of SAP97 with its binding partners. PMID:11060025

CHLOROBENZENES, CHLOROPHENOLS, PAHS AND LOW CHLORINATED DIOXIN/FURAN AS POST-BOILER TOXICITY INDICATORS IN MUNICIPAL SOLID WASTE INCINERATORS

EPA Science Inventory

Numerous research studies have been conducted to establish indicator compounds for fast and less costly predictive monitoring of polychlorinated dibenzo-p-dioxin and furan (PCDD/F) toxic equivalent concentrations (TEQs). Many studies have shown that chlorobenzenes and chlorophen...

Chemical origin of blue- and redshifted hydrogen bonds: intramolecular hyperconjugation and its coupling with intermolecular hyperconjugation.

PubMed

Li, An Yong

2007-04-21

Upon formation of a H bond Y...H-XZ, intramolecular hyperconjugation n(Z)-->sigma*(X-H) of the proton donor plays a key role in red- and blueshift characters of H bonds and must be introduced in the concepts of hyperconjugation and rehybridization. Intermolecular hyperconjugation transfers electron density from Y to sigma*(X-H) and causes elongation and stretch frequency redshift of the X-H bond; intramolecular hyperconjugation couples with intermolecular hyperconjugation and can adjust electron density in sigma*(X-H); rehybridization causes contraction and stretch frequency blueshift of the X-H bond on complexation. The three factors--intra- and intermolecular hyperconjugations and rehybridization--determine commonly red- or blueshift of the formed H bond. A proton donor that has strong intramolecular hyperconjugation often forms blueshifted H bonds.

Achieving 15% Tandem Polymer Solar Cells

DTIC Science & Technology

2015-06-23

solar cell structures – both polymer only and hybrid tandem cells to constantly pushing the envelope of solution processed solar cell ...performance – 11.6% polymer tandem cell , 7% transparent tandem polymer cell , and over 10% PCE hybrid tandem solar cells were achieved. In addition, AFOSR’s...final support also enabled us to explore novel hybrid perovskite solar cells in depth. For example, single junction cell efficiency

Carbon-hydrogen vs. carbon-halogen oxidative addition of chlorobenzene by a neutral iridium complex explored by DFT.

PubMed

Wu, Hong; Hall, Michael B

2009-08-14

Density functional theory (DFT) is used to explore the competitive C-H and C-Cl oxidative additions (OA) of chlorobenzene to the neutral Ir(i) complex: (PNP)Ir(I) [PNP = bis(Z-2-(dimethylphosphino)vinyl)amino]. Consistent with experimental results, our calculation shows that C-H OA is kinetically favored with an activation free-energy barrier of DeltaG(double dagger) = 17.2 kcal mol(-1) that is significantly lower than that for the C-Cl activation at DeltaG(double dagger) = 24.2 kcal mol(-1). However, C-Cl OA is thermodynamically preferred and the C-Cl OA product is 22.6 kcal mol(-1) more stable than the most stable C-H OA product. The calculations also show that the lowest energy path for the conversion of the C-H OA product to the more stable C-Cl OA product is intramolecular through a "benzyne"-type intermediate.

Pd/NbOPO₄ multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans.

PubMed

Xia, Qi-Neng; Cuan, Qian; Liu, Xiao-Hui; Gong, Xue-Qing; Lu, Guan-Zhong; Wang, Yan-Qin

2014-09-08

Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbO(x)-based catalysts in the hydrodeoxygenation of furan-derived adducts to liquid alkanes. Excellent activity and stability were observed with almost no decrease in octane yield (>90% throughout) in a 256 h time-on-stream test. Experimental and theoretical studies showed that NbO(x) species play the key role in C-O bond cleavage. As a multifunctional catalyst, Pd/NbOPO4 plays three roles in the conversion of aldol adducts into alkanes: 1) The noble metal (in this case Pd) is the active center for hydrogenation; 2) NbO(x) species help to cleave the C-O bond, especially of the tetrahydrofuran ring; and 3) a niobium-based solid acid catalyzes the dehydration, thus enabling the quantitative conversion of furan-derived adducts into alkanes under mild conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Asymmetric Desymmetrization of 1,3-Diketones via Intramolecular Benzoin Reaction.

PubMed

Li, Yuanzhen; Yang, Shuang; Wen, Genfa; Lin, Qiqiao; Zhang, Guoxiang; Qiu, Lin; Zhang, Xiaoyan; Du, Guangfen; Fang, Xinqiang

2016-04-01

A general method for the asymmetric desymmetrization of 1,3-diketone substrates via chiral N-heterocyclic carbene catalyzed intramolecular benzoin reactions was developed. Five- and six-membered cyclic ketones bearing two contiguous fully substituted stereocenters were generated with excellent diastereoselectivities and moderate to excellent enantioselectivities.

Performance evaluation of a continuous-flow bioanode microbial electrolysis cell fed with furanic and phenolic compounds

DOE PAGES

Zeng, Xiaofei; Borole, Abhijeet P.; Pavlostathis, Spyros G.

2016-07-04

Furanic and phenolic compounds, formed during the pretreatment of lignocellulosic biomass, are problematic byproducts in down-stream biofuel processes. A microbial electrolysis cell (MEC) is an alternative technology to handle furanic and phenolic compounds and produce renewable hydrogen (H 2). In this study, we evaluated the performance of a continuous-flow bioanode MEC fed with furanic and phenolic compounds at different operating conditions. All hydraulic retention times (HRTs) tested (6-24 h) resulted in complete transformation of the parent compounds at an organic loading rate (OLR) of 0.2g L -1 per d and applied voltage of 0.6 V. Increasing the OLR to 0.8more » g L -1 per d at an HRT of 6h resulted in an increased H 2 production rate from 0.07 to 0.14 L L anode 1 per d, but an OLR of 3.2 g L -1 per d did not lead to a higher H 2 production rate. Significant methane production was observed at an OLR of 3.2 g L -1 per d. The lack of increased H 2 production at the highest OLR tested was due to a limited rate of exoelectrogenesis but not fermentation, evidenced by the accumulation of high acetate levels and higher growth of fermenters and methanogens over exoelectrogens. Increasing applied voltage from 0.6 to 1.0V at an OLR of 3.2 g L -1 per d and HRT of 6h enhanced exoelectrogenesis and resulted in a 1.7-fold increase of H 2 production. Under all operating conditions, more than 90% of the biomass was biofilm-associated. Lastly, the present study provides new insights into the performance of continuous-flow bioelectrochemical systems fed with complex waste streams resulting from the pretreatment of lignocellulosic biomass.« less

An Asymmetric Furan/Thieno[3,2-b]Thiophene Diketopyrrolopyrrole Building Block for Annealing-Free Green-Solvent Processable Organic Thin-Film Transistors.

PubMed

Ding, Shang; Ni, Zhenjie; Hu, Mengxiao; Qiu, Gege; Li, Jie; Ye, Jun; Zhang, Xiaotao; Liu, Feng; Dong, Huanli; Hu, Wenping

2018-06-21

A new asymmetric furan and thieno[3,2-b]thiophene flanked diketopyrrolopyrrole (TTFDPP) building block for conjugated polymers is designed and used to generate a donor-acceptor semiconducting polymer, poly[3-(furan-2-yl)-2,5-bis(2-octyldodecyl)-6-(thieno[3,2-b]thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-alt-thieno[3,2-b]thiophene] (abbreviated to PTTFDPP-TT), consisting of TTFDPP unit copolymerized with thieno[3,2-b]thiophene comonomer (TT), which is further synthesized. Results demonstrate that PTTFDPP-TT-based thin-film transistors in a bottom-gate bottom-contact device configuration exhibit typical hole-transporting property, with weak temperature dependence for charge carrier mobility from room temperature to 200 °C. In addition, the good solubility of PTTFDPP-TT due to the incorporation of a polar furan unit and an asymmetric conjugated structure makes it able to be solution processed with a less toxic nonchlorinated solvent such as toluene, demonstrating comparable performance with that prepared from chlorinated solution. These results suggest PTTFDPP-TT as a promising organic semiconductor candidate for annealing-free, environmentally benign, and less energy-consuming applications in large-area flexible organic electronic devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen atom scrambling in selectively labeled anionic peptides upon collisional activation by MALDI tandem time-of-flight mass spectrometry.

PubMed

Bache, Nicolai; Rand, Kasper D; Roepstorff, Peter; Ploug, Michael; Jørgensen, Thomas J D

2008-12-01

We have previously shown that peptide amide hydrogens undergo extensive intramolecular migration (i.e., complete hydrogen scrambling) upon collisional activation of protonated peptides (Jørgensen et al. J. Am. Chem. Soc. 2005, 127, 2785-2793). The occurrence of hydrogen scrambling enforces severe limitations on the application of gas-phase fragmentation as a convenient method to obtain information about the site-specific deuterium uptake for proteins and peptides in solution. To investigate whether deprotonated peptides exhibit a lower level of scrambling relative to their protonated counterparts, we have now measured the level of hydrogen scrambling in a deprotonated, selectively labeled peptide using MALDI tandem time-of-flight mass spectrometry. Our results conclusively show that hydrogen scrambling is prevalent in the deprotonated peptide upon collisional activation. The amide hydrogens ((1)H/(2)H) have migrated extensively in the anionic peptide, thereby erasing the original regioselective deuteration pattern obtained in solution.

TANDEM: matching proteins with tandem mass spectra.

PubMed

Craig, Robertson; Beavis, Ronald C

2004-06-12

Tandem mass spectra obtained from fragmenting peptide ions contain some peptide sequence specific information, but often there is not enough information to sequence the original peptide completely. Several proprietary software applications have been developed to attempt to match the spectra with a list of protein sequences that may contain the sequence of the peptide. The application TANDEM was written to provide the proteomics research community with a set of components that can be used to test new methods and algorithms for performing this type of sequence-to-data matching. The source code and binaries for this software are available at http://www.proteome.ca/opensource.html, for Windows, Linux and Macintosh OSX. The source code is made available under the Artistic License, from the authors.

Intramolecular symmetry-adapted perturbation theory with a single-determinant wavefunction

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

Pastorczak, Ewa; Prlj, Antonio; Corminboeuf, Clémence, E-mail: clemence.corminboeuf@epfl.ch

2015-12-14

We introduce an intramolecular energy decomposition scheme for analyzing non-covalent interactions within molecules in the spirit of symmetry-adapted perturbation theory (SAPT). The proposed intra-SAPT approach is based upon the Chemical Hamiltonian of Mayer [Int. J. Quantum Chem. 23(2), 341–363 (1983)] and the recently introduced zeroth-order wavefunction [J. F. Gonthier and C. Corminboeuf, J. Chem. Phys. 140(15), 154107 (2014)]. The scheme decomposes the interaction energy between weakly bound fragments located within the same molecule into physically meaningful components, i.e., electrostatic-exchange, induction, and dispersion. Here, we discuss the key steps of the approach and demonstrate that a single-determinant wavefunction can already delivermore » a detailed and insightful description of a wide range of intramolecular non-covalent phenomena such as hydrogen bonds, dihydrogen contacts, and π − π stacking interactions. Intra-SAPT is also used to shed the light on competing intra- and intermolecular interactions.« less

Intramolecular H-transfer reactions in Si 2H n (for n=3-5)

NASA Astrophysics Data System (ADS)

Ernst, M. C.; Sax, A. F.; Kalcher, J.

1993-12-01

Intramolecular rearrangement reactions for doublet Si 2H 5 and Si 2H 3, quartet Si 2H 3, and singlet Si 2H 4 have been studied. aim of the study was to characterize a series of intramolecular H-transfer reactions in silicon hydrides with vrying degrees of saturation. The transition states belonging to the reactions presented in this work possess a monobridged Si 2H moiety. Structural features of the transition states and relative barrier heights have been examined; the geometry optimizations were performed with the use of CAS-SCF wavefunctions and the barrier height estimates were obtained with single-point CI calculations.

Impact of Stereospecific Intramolecular Hydrogen Bonding on Cell Permeability and Physicochemical Properties

PubMed Central

2014-01-01

Profiling of eight stereoisomeric T. cruzi growth inhibitors revealed vastly different in vitro properties such as solubility, lipophilicity, pKa, and cell permeability for two sets of four stereoisomers. Using computational chemistry and NMR spectroscopy, we identified the formation of an intramolecular NH→NR3 hydrogen bond in the set of stereoisomers displaying lower solubility, higher lipophilicity, and higher cell permeability. The intramolecular hydrogen bond resulted in a significant pKa difference that accounts for the other structure–property relationships. Application of this knowledge could be of particular value to maintain the delicate balance of size, solubility, and lipophilicity required for cell penetration and oral administration for chemical probes or therapeutics with properties at, or beyond, Lipinski’s rule of 5. PMID:24524242

Molecular dynamics and principal components of potassium binding with human telomeric intra-molecular G-quadruplex.

PubMed

Wang, Zhiguo; Chen, Ruping; Hou, Ling; Li, Jianfeng; Liu, Jun-Ping

2015-06-01

Telomere assumes intra-molecular G-quadruplex that is a significant drug target for inhibiting telomerase maintenance of telomeres in cancer. Metal cations have been recognized as playing important roles in stabilizing G-quadruplex, but their binding processes to human telomeric G-quadruplex remain uncharacterized. To investigate the detailed binding procedures, molecular dynamics simulations were conducted on the hybrid [3 + 1] form-one human telomeric intra-molecular G-quadruplex. We show here that the binding of a potassium ion to a G-tetrad core is mediated by two alternative pathways. Principal component analysis illustrated the dominant concerted motions of G-quadruplex occurred at the loop domains. MM-PBSA calculations revealed that binding was energetically favorable and driven by the electrostatic interactions. The lower binding site was found more constructive favorable for binding. Our data provide useful information on a potassium-mediated stable structure of human telomeric intra-molecular G-quadruplex, implicating in ion disorder associated conformational changes and targeted drug design.

Inhibitory Effect of Furanic and Phenolic Compounds on Exoelectrogenesis in a Microbial Electrolysis Cell Bioanode

DOE PAGES

Zeng, Xiaofei; Borole, Abhijeet P.; Pavlostathis, Spyros G.

2016-09-09

Furanic and phenolic compounds are 20 lignocellulose-derived compounds known to inhibit to H2- and ethanol- producing microorganisms in dark fermentation. Bioelectrochemical conversion of furanic and phenolic compounds to electricity or H2 has recently been demonstrated as a productive method to use these compounds. However, potential inhibitory effect of furanic and phenolic compounds on exoelectrogenesis in bioelectrochemical systems is not well understood. This study systematically investigated the inhibitory effect of furfural (FF), 5-hydroxymethylfurfural (HMF), syringic acid (SA), vanillic acid (VA), and 4-hydroxybenzoic acid (HBA) on exoelectrogenesis in the bioanode of a microbial electrolysis cell. A mixture of these five compounds atmore » an increasing initial total concentration from 0.8 to 8.0 g/L resulted in current decrease up to 91%. The observed inhibition primarily affected exoelectrogenesis, instead of non-exoelectrogenic biotransformation pathways (e.g., fermentation) of the five compounds. Furthermore, the parent compounds at a high concentration, as opposed to their biotransformation products, were responsible for the observed inhibition. Tests with individual compounds show that all five parent compounds contributed to the observed inhibition by the mixture. The IC50 (concentration resulting in 50% current decrease) was estimated as 2.7 g/L for FF, 3.0 g/L for HMF, 1.9 g/L for SA, 2.1 g/L for VA and 2.0 g/L for HBA. Nevertheless, these compounds below their non-inhibitory concentrations jointly resulted in significant inhibition as a mixture. Catechol and phenol, which were persistent biotransformation products of the mixture, inhibited exoelectrogens at high concentrations, but to a lesser extent than the parent compounds. Recovery of exoelectrogenesis from inhibition by all compounds was observed, except for catechol, which resulted in irreversible inhibition. The reversibility of inhibition, as well as the observed difference in recovery

Detecting long tandem duplications in genomic sequences.

PubMed

Audemard, Eric; Schiex, Thomas; Faraut, Thomas

2012-05-08

Detecting duplication segments within completely sequenced genomes provides valuable information to address genome evolution and in particular the important question of the emergence of novel functions. The usual approach to gene duplication detection, based on all-pairs protein gene comparisons, provides only a restricted view of duplication. In this paper, we introduce ReD Tandem, a software using a flow based chaining algorithm targeted at detecting tandem duplication arrays of moderate to longer length regions, with possibly locally weak similarities, directly at the DNA level. On the A. thaliana genome, using a reference set of tandem duplicated genes built using TAIR,(a) we show that ReD Tandem is able to predict a large fraction of recently duplicated genes (dS  <  1) and that it is also able to predict tandem duplications involving non coding elements such as pseudo-genes or RNA genes. ReD Tandem allows to identify large tandem duplications without any annotation, leading to agnostic identification of tandem duplications. This approach nicely complements the usual protein gene based which ignores duplications involving non coding regions. It is however inherently restricted to relatively recent duplications. By recovering otherwise ignored events, ReD Tandem gives a more comprehensive view of existing evolutionary processes and may also allow to improve existing annotations.

Examination of the Mechanism of Rh2(II)-Catalyzed Carbazole Formation Using Intramolecular Competition Experiments

PubMed Central

Stokes, Benjamin J.; Richert, Kathleen J.; Driver, Tom G.

2009-01-01

The use of a rhodium(II) carboxylate catalyst enables the mild and stereoselective formation of carbazoles from biaryl azides. Intramolecular competition experiments of triaryl azides suggested the source of the selectivity. A primary intramolecular kinetic isotope effect was not observed and correlation of the product ratios with Hammett σ+-values produced a plot with two intersecting lines with opposite ρ-values. These data suggest that electronic donation by the biaryl π-system accelerates the formation of rhodium nitrenoid and that C–N bond formation occurs through a 4π-electron-5-atom electrocyclization. PMID:19663433

Supercritical water oxidation of dioxins and furans in waste incinerator fly ash, sewage sludge and industrial soil.

PubMed

Zainal, Safari; Onwudili, Jude A; Williams, Paul T

2014-08-01

Three environmental samples containing dioxins and furans have been oxidized in the presence of hydrogen peroxide under supercritical water oxidation conditions. The samples consisted of a waste incinerator fly ash, sewage sludge and contaminated industrial soil. The reactor system was a batch, autoclave reactor operated at temperatures between 350 degrees C and 450degrees C, corresponding to pressures of approximately 20-33.5 MPa and with hydrogen peroxide concentrations from 0.0 to 11.25 vol%. Hydrogen peroxide concentration and temperature/pressure had a strong positive effect on the oxidation of dioxins and furans. At the highest temperatures and pressure of supercritical water oxidation of 4500C and 33.5 MPa and with 11.25 vol% of hydrogen peroxide, the destruction efficiencies of the individual polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) isomers were between 90% and 99%. There did not appear to be any significant differences in the PCDD/PCDF destruction efficiencies in relation to the different sample matrices of the waste incinerator fly ash, sewage sludge and contaminated industrial soil.

Copper(II) acetate promoted intramolecular diamination of unactivated olefins.

PubMed

Zabawa, Thomas P; Kasi, Dhanalakshmi; Chemler, Sherry R

2005-08-17

A concise method for the synthesis of cyclic sulfamides and vicinal diamines is presented. This method is enabled by Cu(OAc)2 and demonstrates a new transformation for this metal. Both five- and six-membered vicinal diamine-containing heterocycles have been synthesized in good to excellent yields, and substrate-based asymmetric induction has been achieved. This is the first reported example of intramolecular diamination of olefins.

Tests for genotoxicity and mutagenicity of furan and its metabolite cis-2-butene-1,4-dial in L5178Y tk+/- mouse lymphoma cells.

PubMed

Kellert, Marco; Brink, Andreas; Richter, Ingrid; Schlatter, Josef; Lutz, Werner K

2008-12-08

Furan is found in various food items and is cytotoxic and carcinogenic in the liver of rats and mice. Metabolism of furan includes the formation of an unsaturated dialdehyde, cis-2-butene-1,4-dial (BDA). In view of the multifunctional electrophilic reactivity of BDA, adduct formation with protein and DNA may explain some of the toxic effects. Short-term tests for genotoxicity of furan in mammalian cells are inconclusive, little is known for BDA. We investigated BDA generated by hydrolysis of 2,5-diacetoxy-2,5-dihydrofuran for genotoxicity in L5178Y tk+/- mouse lymphoma cells using standard procedures for the comet assay, the micronucleus test, and the mouse lymphoma thymidine kinase gene mutation assay, using 4-h incubation periods. Cytotoxicity was remarkable: cell viability at concentrations>or=50 microM was reduced to <50%. In the dose range up to 25 microM, viability was >90%. Measures of comet-tail length and thymidine-kinase mutant frequency were increased 1.6- and 2.4-fold above control, respectively. Analysis of three fully independent replicates with a linear mixed-effects model showed a highly significant increase with concentration for both endpoints. Compared to methyl methanesulfonate used as a positive control, BDA was of similar potency with respect to genotoxicity, but it was much more cytotoxic. Furan added to cell cultures at doses that resulted in time-averaged effective concentrations of up to 3100 microM was neither cytotoxic nor genotoxic. A potential cross-linking activity of BDA was investigated by checking whether gamma radiation-induced DNA migration in the comet assay could be reduced by pre-treatment with BDA. In contrast to the effect of the positive control glutaraldehyde, BDA treatment did not reduce the comet tail length. On the contrary, an increase was observed at >or=100 microM BDA, which was attributable to early apoptotic cells. Although BDA was found to be a relatively potent genotoxic agent in terms of the concentration

One-step production of a biologically active novel furan fatty acid from 7,10-dihydroxy-8(E)-octadecenoic acid

USDA-ARS?s Scientific Manuscript database

Furan fatty acids (F-acids) gain special attentions since they are known to play important roles in biological systems including humans. Specifically F-acids are known to have strong antioxidant activity like radical scavenging activity. Although widely distributed in most biological systems, F-ac...

A Furan-Thiophene-Based Quinoidal Compound: A New Class of Solution-Processable High-Performance n-Type Organic Semiconductor.

PubMed

Xiong, Yu; Tao, Jingwei; Wang, Ruihao; Qiao, Xiaolan; Yang, Xiaodi; Wang, Deliang; Wu, Hongzhuo; Li, Hongxiang

2016-07-01

The furan-thiophene-based quinoidal organic semiconductor, TFT-CN, is designed and synthesized. TFT-CN displays a high electron mobility of 7.7 cm(2) V(-1) s(-1) , two orders of magnitude higher than the corresponding thiophene-based derivative. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploration of zeroth-order wavefunctions and energies as a first step toward intramolecular symmetry-adapted perturbation theory

NASA Astrophysics Data System (ADS)

Gonthier, Jérôme F.; Corminboeuf, Clémence

2014-04-01

Non-covalent interactions occur between and within all molecules and have a profound impact on structural and electronic phenomena in chemistry, biology, and material science. Understanding the nature of inter- and intramolecular interactions is essential not only for establishing the relation between structure and properties, but also for facilitating the rational design of molecules with targeted properties. These objectives have motivated the development of theoretical schemes decomposing intermolecular interactions into physically meaningful terms. Among the various existing energy decomposition schemes, Symmetry-Adapted Perturbation Theory (SAPT) is one of the most successful as it naturally decomposes the interaction energy into physical and intuitive terms. Unfortunately, analogous approaches for intramolecular energies are theoretically highly challenging and virtually nonexistent. Here, we introduce a zeroth-order wavefunction and energy, which represent the first step toward the development of an intramolecular variant of the SAPT formalism. The proposed energy expression is based on the Chemical Hamiltonian Approach (CHA), which relies upon an asymmetric interpretation of the electronic integrals. The orbitals are optimized with a non-hermitian Fock matrix based on two variants: one using orbitals strictly localized on individual fragments and the other using canonical (delocalized) orbitals. The zeroth-order wavefunction and energy expression are validated on a series of prototypical systems. The computed intramolecular interaction energies demonstrate that our approach combining the CHA with strictly localized orbitals achieves reasonable interaction energies and basis set dependence in addition to producing intuitive energy trends. Our zeroth-order wavefunction is the primary step fundamental to the derivation of any perturbation theory correction, which has the potential to truly transform our understanding and quantification of non

Exploration of zeroth-order wavefunctions and energies as a first step toward intramolecular symmetry-adapted perturbation theory

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

Gonthier, Jérôme F.; Corminboeuf, Clémence, E-mail: clemence.corminboeuf@epfl.ch

2014-04-21

Non-covalent interactions occur between and within all molecules and have a profound impact on structural and electronic phenomena in chemistry, biology, and material science. Understanding the nature of inter- and intramolecular interactions is essential not only for establishing the relation between structure and properties, but also for facilitating the rational design of molecules with targeted properties. These objectives have motivated the development of theoretical schemes decomposing intermolecular interactions into physically meaningful terms. Among the various existing energy decomposition schemes, Symmetry-Adapted Perturbation Theory (SAPT) is one of the most successful as it naturally decomposes the interaction energy into physical and intuitivemore » terms. Unfortunately, analogous approaches for intramolecular energies are theoretically highly challenging and virtually nonexistent. Here, we introduce a zeroth-order wavefunction and energy, which represent the first step toward the development of an intramolecular variant of the SAPT formalism. The proposed energy expression is based on the Chemical Hamiltonian Approach (CHA), which relies upon an asymmetric interpretation of the electronic integrals. The orbitals are optimized with a non-hermitian Fock matrix based on two variants: one using orbitals strictly localized on individual fragments and the other using canonical (delocalized) orbitals. The zeroth-order wavefunction and energy expression are validated on a series of prototypical systems. The computed intramolecular interaction energies demonstrate that our approach combining the CHA with strictly localized orbitals achieves reasonable interaction energies and basis set dependence in addition to producing intuitive energy trends. Our zeroth-order wavefunction is the primary step fundamental to the derivation of any perturbation theory correction, which has the potential to truly transform our understanding and quantification of non

Gold(III) chloride catalyzed synthesis of chiral substituted 3-formyl furans from carbohydrates: application in the synthesis of 1,5-dicarbonyl derivatives and furo[3,2-c]pyridine.

PubMed

Mal, Kanchan; Sharma, Abhinandan; Das, Indrajit

2014-09-08

This report describes a gold(III)-catalyzed efficient general route to densely substituted chiral 3-formyl furans under extremely mild conditions from suitably protected 5-(1-alkynyl)-2,3-dihydropyran-4-one using H2 O as a nucleophile. The reaction proceeds through the initial formation of an activated alkyne-gold(III) complex intermediate, followed by either a domino nucleophilic attack/anti-endo-dig cyclization, or the formation of a cyclic oxonium ion with subsequent attack by H2 O. To confirm the proposed mechanistic pathway, we employed MeOH as a nucleophile instead of H2 O to result in a substituted furo[3,2-c]pyran derivative, as anticipated. The similar furo[3,2-c]pyran skeleton with a hybrid carbohydrate-furan derivative has also been achieved through pyridinium dichromate (PDC) oxidation of a substituted chiral 3-formyl furan. The corresponding protected 5-(1-alkynyl)-2,3-dihydropyran-4-one can be synthesized from the monosaccharides (both hexoses and pentose) following oxidation, iodination, and Sonogashira coupling sequences. Furthermore, to demonstrate the potentiality of chiral 3-formyl furan derivatives, a TiBr4 -catalyzed reaction of these derivatives has been shown to offer efficient access to 1,5-dicarbonyl compounds, which on treatment with NH4 OAc in slightly acidic conditions afforded substituted furo[3,2-c]pyridine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dendritic effect in polymer-supported catalysis of the intramolecular Pauson-Khand reaction.

PubMed

Dahan, Adi; Portnoy, Moshe

2002-11-21

A remarkable increase in catalytic activity and selectivity in the intramolecular Pauson-Khand reaction is observed for Co complexes, immobilised on second- and third-generation dendron-functionalized polystyrene, as compared with their analogues on non-dendronized support.

Photochemically Induced Intramolecular Radical Cyclization Reactions with Imines.

PubMed

Lefebvre, Corentin; Michelin, Clément; Martzel, Thomas; Djou'ou Mvondo, Vaneck; Bulach, Véronique; Abe, Manabu; Hoffmann, Norbert

2018-02-16

The photochemically induced intramolecular hydrogen abstraction or hydrogen atom transfer in cyclic imines 8a,b followed by a cyclization is investigated. Two types of products are observed, one resulting from the formation of a C-C bond, the other from the formation of a C-N bond. A computational study reveals that hydrogen is exclusively transferred to the imine nitrogen leading to a triplet diradical intermediate. After intersystem crossing, the resulting zwitterionic intermediate undergoes cyclization leading to the final product.

A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers

DOE PAGES

Fuemmeler, Eric G.; Sanders, Samuel N.; Pun, Andrew B.; ...

2016-05-05

Interest in materials that undergo singlet fission (SF) has been catalyzed by the potential to exceed the Shockley–Queisser limit of solar power conversion efficiency. In conventional materials, the mechanism of SF is an intermolecular process (xSF), which is mediated by charge transfer (CT) states and depends sensitively on crystal packing or molecular collisions. In contrast, recently reported covalently coupled pentacenes yield ~2 triplets per photon absorbed in individual molecules: the hallmark of intramolecular singlet fission (iSF). But, the mechanism of iSF is unclear. Here, using multireference electronic structure calculations and transient absorption spectroscopy, we establish that iSF can occur viamore » a direct coupling mechanism that is independent of CT states. Moreover, we show that a near-degeneracy in electronic state energies induced by vibronic coupling to intramolecular modes of the covalent dimer allows for strong mixing between the correlated triplet pair state and the local excitonic state, despite weak direct coupling.« less

Intramolecular Charge-Transfer Interaction of Donor-Acceptor-Donor Arrays Based on Anthracene Bisimide.

PubMed

Iwanaga, Tetsuo; Ogawa, Marina; Yamauchi, Tomokazu; Toyota, Shinji

2016-05-20

We designed anthracene bisimide (ABI) derivatives having two triphenylamine (TPA) groups as donor units at the 9,10-positions to form a novel π-conjugated donor-acceptor system. These compounds and their analogues with ethynylene linkers were synthesized by Suzuki-Miyaura and Sonogashira coupling reactions, respectively. In UV-vis spectra, the linker-free derivatives showed broad absorption bands arising from intramolecular charge-transfer interactions. Introducing ethynylene linkers resulted in a considerable red shift of the absorption bands. In fluorescence spectra, the ethynylene derivatives showed intense emission bands at 600-650 nm. Their photophysical and electrochemical properties were compared with those of the corresponding mono TPA derivatives on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between the donor and acceptor units.

Insertion of benzene rings into the amide bond: one-step synthesis of acridines and acridones from aryl amides.

PubMed

Pintori, Didier G; Greaney, Michael F

2010-01-01

Insertion of benzene rings into the amide bond using the reactive intermediate benzyne is described. Aromatic amides undergo smooth insertion when treated with O-triflatophenyl silane benzyne precursors, producing versatile aminobenzophenone products in good to excellent yield. The process is entirely metal-free and has been exemplified on the synthesis of biologically active acridones and acridines.

Short Tandem Repeat DNA Internet Database

National Institute of Standards and Technology Data Gateway

SRD 130 Short Tandem Repeat DNA Internet Database (Web, free access)   Short Tandem Repeat DNA Internet Database is intended to benefit research and application of short tandem repeat DNA markers for human identity testing. Facts and sequence information on each STR system, population data, commonly used multiplex STR systems, PCR primers and conditions, and a review of various technologies for analysis of STR alleles have been included.

Copper-catalyzed synthesis of substituted furans and pyrroles by heterocyclodehydration and tandem heterocyclodehydration-hydration of 3-yne-1,2-diols and 1-amino-3-yn-2-ol derivatives.

PubMed

Gabriele, Bartolo; Veltri, Lucia; Plastina, Pierluigi; Mancuso, Raffaella; Vetere, Mabel V; Maltese, Vito

2013-05-17

CuCl2-catalyzed heterocyclodehydration of readily available 3-yne-1,2-diols and 1-amino-3-yn-2-ol derivatives afforded substituted furans and pyrroles, respectively, in good to high yields (53-99%) under mild conditions (MeOH as the solvent, 80-100 °C, 1-24 h). In the case of 2,2-dialkynyl-1,2-diols, bearing an additional alkynyl substituent at C-2, a cascade process, corresponding to copper-catalyzed heterocyclodehydration followed by acid-catalyzed hydration of the triple bond, was realized when the reaction was carried out in the presence of both CuCl2 and TsOH, leading to 3-acylfurans in one step and high yields (75-84%). Under the same conditions, N-Boc-2-alkynyl-1-amino-3-yn-2-ols were converted into the corresponding N-unsubstituted 3-acylpyrroles in low to fair yields (19-59%). However, working in the presence of added water and a large excess of CO2 (40 atm), in addition to CuCl2 and TsOH, caused a significant improvement of the yields of 3-acylpyrroles (68-87%), thus making the method of general synthetic applicability.

Development of a Passive Multisampling Method to Measure Dioxins/Furans and Other Contaminant Bioavailability in Aquatic Sediments

DTIC Science & Technology

2016-11-01

A.; Weinstein, M. P.; Lohmann, R. Trophodynamic behavior of hydrophobic organic contaminants in the aquatic food web of a tidal river. Environ. Sci...FINAL REPORT Development of a Passive Multisampling Method to Measure Dioxins/Furans and Other Contaminant Bioavailability in Aquatic...trade name, trademark, manufacturer , or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the

Stereodivergent Synthesis of Chromanones and Flavanones via Intramolecular Benzoin Reaction.

PubMed

Wen, Genfa; Su, Yingpeng; Zhang, Guoxiang; Lin, Qiqiao; Zhu, Yujin; Zhang, Qianqian; Fang, Xinqiang

2016-08-19

The strategy of stereodivergent reactions on racemic mixtures (stereodivergent RRM) was employed for the first time in intramolecular benzoin reactions and led to the rapid access of chromanones/flavanones with two consecutive stereocenters. The easily separable stereoisomers of the products were obtained with moderate to excellent enantioselectivities in a single step. Catechol type additives proved crucial in achieving the desired diastereo- and enantioselectivities.

TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4‧-dimethylaminoflavonol in ethanol solvent

NASA Astrophysics Data System (ADS)

Wang, Ye; Shi, Ying; Cong, Lin; Li, Hui

2015-02-01

Time-dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate the intramolecular and intermolecular hydrogen bonding dynamics in the first excited (S1) state of 4‧-dimethylaminoflavonol (DMAF) monomer and in ethanol solution. In the DMAF monomer, we demonstrated that the intramolecular charge transfer (ICT) takes place in the S1 state. This excited state ICT process was followed by intramolecular proton transfer. Our calculated results are in good agreement with the mechanism proposed in experimental work. For the hydrogen-bonded DMAF-EtOH complex, it was demonstrated that the intermolecular hydrogen bonds can induce the formation of the twisted intramolecular charge transfer (TICT) state and the conformational twisting is along the C3-C4 bond. Moreover, the intermolecular hydrogen bonds can also facilitate the intermolecular double proton transfer in the TICT state. A stepwise intermolecular double proton transfer process was revealed. Therefore, the intermolecular hydrogen bonds can alter the mechanism of intramolecular charge transfer and proton transfer in the excited state for the DMAF molecule.

Cross sections for electron scattering from furan molecules: Measurements and calculations

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

Szmytkowski, Czeslaw; Mozejko, Pawel; Ptasinska-Denga, Elzbieta

Electron-scattering cross sections have been determined for the furan (C{sub 4}H{sub 4}O) molecule, both experimentally and theoretically. An absolute total cross section (TCS) has been measured over energies from 0.6 to 400 eV using a linear electron-transmission method. The TCS energy function is dominated with a very broad enhancement, between 1.2 and 9 eV; on the low-energy side, some resonant structures are visible. Integral elastic (ECS) and ionization (ICS) cross sections have been also calculated up to 4 keV in the additivity rule approximation and the binary-encounter-Bethe approach, respectively. Their sum, ECS+ICS, is in a very good agreement with themore » measured TCS above 70 eV.« less

Tandem Organic Light-Emitting Diodes.

PubMed

Fung, Man-Keung; Li, Yan-Qing; Liao, Liang-Sheng

2016-12-01

A tandem organic light-emitting diode (OLED) is an organic optoelectronic device that has two or more electroluminescence (EL) units connected electrically in series with unique intermediate connectors within the device. Researchers have studied this new OLED architecture with growing interest and have found that the current efficiency of a tandem OLED containing N EL units (N > 1) should be N times that of a conventional OLED containing only a single EL unit. Therefore, this new architecture is potentially useful for constructing high-efficiency, high-luminance, and long-lifetime OLED displays and organic solid-state lighting sources. In a tandem OLED, the intermediate connector plays a crucial role in determining the effectiveness of the stacked EL units. The interfaces in the connector control the inner charge generation and charge injection into the adjacent EL units. Meanwhile, the transparency and the thickness of the connector affect the light output of the device. Therefore, the intermediate connector should be made to meet both the electrical and optical requirements for achieving optimal performance. Here, recent advances in the research of the tandem OLEDs is discussed, with the main focus on material selection and interface studies in the intermediate connectors, as well as the optical design of the tandem OLEDs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unusual para-substituent effects on the intramolecular hydrogen-bond in hydrazone-based switches.

PubMed

Su, Xin; Lõkov, Märt; Kütt, Agnes; Leito, Ivo; Aprahamian, Ivan

2012-11-04

A "V"-shaped Hammett plot shows that resonance-assisted hydrogen bonding does not dictate the strength of the intramolecular hydrogen bond in the E isomers of hydrazone-based switches because it involves an aromatic pyridyl ring.

Spectral and photophysical properties of intramolecular charge transfer fluorescence probe: 4'-Dimethylamino-2,5-dihydroxychalcone

NASA Astrophysics Data System (ADS)

Xu, Zhicheng; Bai, Guan; Dong, Chuan

2005-12-01

The spectral and photophysical properties of a new intramolecular charge transfer (ICT) probe, namely 4'-dimethylamino-2,5-dihydroxychalcone (DMADHC) were studied in different solvents by using steady-state absorption and emission spectroscopy. Whereas the absorption spectrum undergoes minor change with increasing polarity of the solvents, the fluorescence spectrum experiences a distinct bathochromic shift in the band position and the fluorescence quantum yield increases reaching a maximum before decrease with increasing the solvent polarity. The magnitude of change in the dipole moment was calculated based on the Lippert-Mataga equation. These results give the evidence about the intramolecular charge transfer character in the emitting singlet state of this compound.

Spectral and photophysical properties of intramolecular charge transfer fluorescence probe: 4'-dimethylamino-2,5-dihydroxychalcone.

PubMed

Xu, Zhicheng; Bai, Guan; Dong, Chuan

2005-12-01

The spectral and photophysical properties of a new intramolecular charge transfer (ICT) probe, namely 4'-dimethylamino-2,5-dihydroxychalcone (DMADHC) were studied in different solvents by using steady-state absorption and emission spectroscopy. Whereas the absorption spectrum undergoes minor change with increasing polarity of the solvents, the fluorescence spectrum experiences a distinct bathochromic shift in the band position and the fluorescence quantum yield increases reaching a maximum before decrease with increasing the solvent polarity. The magnitude of change in the dipole moment was calculated based on the Lippert-Mataga equation. These results give the evidence about the intramolecular charge transfer character in the emitting singlet state of this compound.

2-Oxo promoted hydrophosphonylation & aerobic intramolecular nucleophilic displacement reaction.

PubMed

Battula, Satyanarayana; Battini, Narsaiah; Singh, Deepika; Ahmed, Qazi Naveed

2015-08-28

Highly efficient catalyst free methods for the synthesis of α-hydroxy-β-oxophosphonates and α-oxoesters have been described. The existence of a 2-oxo group in α-oxoaldehydes is a key factor in promoting the reaction of the tervalent phosphite form towards 2-oxoaldehydes in the synthesis of α-hydroxy-β-oxophosphonates. The in situ activated α-C-H atom of α-hydroxy-β-oxophosphonates sustains aerobic intramolecular nucleophilic displacement in a curious way to produce α-oxoester.

Intramolecular ketenimine-ketenimine [2 + 2] and [4 + 2] cycloadditions.

PubMed

Alajarín, Mateo; Bonillo, Baltasar; Sanchez-Andrada, Pilar; Vidal, Angel; Bautista, Delia

2007-07-20

Bis(ketenimines), in which the two heterocumulenic functions are placed in close proximity on a carbon skeleton to allow their mutual interaction, show a rich and not easily predictable chemistry. Intramolecular [2 + 2] or [4 + 2] cycloadditions are, respectively, observed when both ketenimine functions are supported on either ortho-benzylic or 2,2'-biphenylenic scaffolds. In addition, nitrogen-to-carbon [1,3] and [1,5] shifts of arylmethyl groups in N-arylmethyl-C,C-diphenyl ketenimines are also disclosed.

Backbone dynamics in an intramolecular prolylpeptide-SH3 complex from the diphtheria toxin repressor, DtxR

PubMed Central

Bhattacharya, Nilakshee; Yi, Myunggi; Zhou, Huan-Xiang; Logan, Timothy M.

2008-01-01

Summary The diphtheria toxin repressor contains an SH3-like domain that forms an intramolecular complex with a proline-rich (Pr) peptide segment and stabilizes the inactive state of the repressor. Upon activation of DtxR by transition metals, this intramolecular complex must dissociate as the SH3 domain and Pr segment form different interactions in the active repressor. In this study we investigate the dynamics of this intramolecular complex using backbone amide nuclear spin relaxation rates determined using NMR spectroscopy and molecular dynamics trajectories. The SH3 domain in the unbound and bound states showed typical dynamics in that the secondary structures were fairly ordered with high generalized order parameters and low effective correlation times while residues in the loops connecting β-strands exhibited reduced generalized order parameters and required additional motional terms to adequately model the relaxation rates. Residues forming the Pr segment exhibited low order parameters with internal rotational correlation times on the order of 0.6 – 1 ns. Further analysis showed that the SH3 domain was rich in millisecond timescale motions while the Pr segment was rich in motions on the 100s μs timescale. Molecular dynamics simultations indicated structural rearrangements that may contribute to the observed relaxation rates and, together with the observed relaxation rate data, suggested that the Pr segment exhibits a binding ↔ unbinding equilibrium. The results of this study provide new insights into the nature of the intramolecular complex and provide a better understanding of the biological role of the SH3 domain in regulating DtxR activity. PMID:17976643

Chromophore-Dependent Intramolecular Exciton-Vibrational Coupling in the FMO Complex: Quantification and Importance for Exciton Dynamics.

PubMed

Padula, Daniele; Lee, Myeong H; Claridge, Kirsten; Troisi, Alessandro

2017-11-02

In this paper, we adopt an approach suitable for monitoring the time evolution of the intramolecular contribution to the spectral density of a set of identical chromophores embedded in their respective environments. We apply the proposed method to the Fenna-Matthews-Olson (FMO) complex, with the objective to quantify the differences among site-dependent spectral densities and the impact of such differences on the exciton dynamics of the system. Our approach takes advantage of the vertical gradient approximation to reduce the computational demands of the normal modes analysis. We show that the region of the spectral density that is believed to strongly influence the exciton dynamics changes significantly in the timescale of tens of nanoseconds. We then studied the impact of the intramolecular vibrations on the exciton dynamics by considering a model of FMO in a vibronic basis and neglecting the interaction with the environment to isolate the role of the intramolecular exciton-vibration coupling. In agreement with the assumptions in the literature, we demonstrate that high frequency modes at energy much larger than the excitonic energy splitting have negligible influence on exciton dynamics despite the large exciton-vibration coupling. We also find that the impact of including the site-dependent spectral densities on exciton dynamics is not very significant, indicating that it may be acceptable to apply the same spectral density on all sites. However, care needs to be taken for the description of the exciton-vibrational coupling in the low frequency part of intramolecular modes because exciton dynamics is more susceptible to low frequency modes despite their small Huang-Rhys factors.

Kinetics of lisinopril intramolecular cyclization in solid phase monitored by Fourier transform infrared microscopy.

PubMed

Widjaja, Effendi; Tan, Wei Jian

2008-08-01

The solid-state intramolecular cyclization of lisinopril to diketopiperazine was investigated by in situ Fourier transform infrared (FT-IR) microscopy. Using a controllable heating cell, the isothermal transformation was monitored in situ at 147.5, 150, 152.5, 155, and 157.5 degrees C. The collected time-dependent FT-IR spectra at each isothermal temperature were preprocessed and analyzed using a multivariate chemometric approach. The pure component spectra of the observable component (lisinopril and diketopiperazine) were resolved and their time-dependent relative contributions were also determined. Model-free and various model fitting methods were implemented in the kinetic analysis to estimate the activation energy of the intramolecular cyclization reaction. Arrhenius plots indicate that the activation energy is circa 327 kJ/mol.

High voltage series connected tandem junction solar battery

DOEpatents

Hanak, Joseph J.

1982-01-01

A high voltage series connected tandem junction solar battery which comprises a plurality of strips of tandem junction solar cells of hydrogenated amorphous silicon having one optical path and electrically interconnected by a tunnel junction. The layers of hydrogenated amorphous silicon, arranged in a tandem configuration, can have the same bandgap or differing bandgaps. The tandem junction strip solar cells are series connected to produce a solar battery of any desired voltage.

A simple and versatile design concept for fluorophore derivatives with intramolecular photostabilization

NASA Astrophysics Data System (ADS)

van der Velde, Jasper H. M.; Oelerich, Jens; Huang, Jingyi; Smit, Jochem H.; Aminian Jazi, Atieh; Galiani, Silvia; Kolmakov, Kirill; Guoridis, Giorgos; Eggeling, Christian; Herrmann, Andreas; Roelfes, Gerard; Cordes, Thorben

2016-01-01

Intramolecular photostabilization via triple-state quenching was recently revived as a tool to impart synthetic organic fluorophores with `self-healing' properties. To date, utilization of such fluorophore derivatives is rare due to their elaborate multi-step synthesis. Here we present a general strategy to covalently link a synthetic organic fluorophore simultaneously to a photostabilizer and biomolecular target via unnatural amino acids. The modular approach uses commercially available starting materials and simple chemical transformations. The resulting photostabilizer-dye conjugates are based on rhodamines, carbopyronines and cyanines with excellent photophysical properties, that is, high photostability and minimal signal fluctuations. Their versatile use is demonstrated by single-step labelling of DNA, antibodies and proteins, as well as applications in single-molecule and super-resolution fluorescence microscopy. We are convinced that the presented scaffolding strategy and the improved characteristics of the conjugates in applications will trigger the broader use of intramolecular photostabilization and help to emerge this approach as a new gold standard.

A simple and versatile design concept for fluorophore derivatives with intramolecular photostabilization

PubMed Central

van der Velde, Jasper H. M.; Oelerich, Jens; Huang, Jingyi; Smit, Jochem H.; Aminian Jazi, Atieh; Galiani, Silvia; Kolmakov, Kirill; Gouridis, Giorgos; Eggeling, Christian; Herrmann, Andreas; Roelfes, Gerard; Cordes, Thorben

2016-01-01

Intramolecular photostabilization via triple-state quenching was recently revived as a tool to impart synthetic organic fluorophores with ‘self-healing’ properties. To date, utilization of such fluorophore derivatives is rare due to their elaborate multi-step synthesis. Here we present a general strategy to covalently link a synthetic organic fluorophore simultaneously to a photostabilizer and biomolecular target via unnatural amino acids. The modular approach uses commercially available starting materials and simple chemical transformations. The resulting photostabilizer–dye conjugates are based on rhodamines, carbopyronines and cyanines with excellent photophysical properties, that is, high photostability and minimal signal fluctuations. Their versatile use is demonstrated by single-step labelling of DNA, antibodies and proteins, as well as applications in single-molecule and super-resolution fluorescence microscopy. We are convinced that the presented scaffolding strategy and the improved characteristics of the conjugates in applications will trigger the broader use of intramolecular photostabilization and help to emerge this approach as a new gold standard. PMID:26751640

Mo(CO)6-mediated intramolecular Pauson-Khand reaction of substituted diethyl 3-allyloxy-1-propynylphosphonates.

PubMed

Moradov, Dorit; Al Quntar, Abed Al Aziz; Youssef, Manar; Smoum, Reem; Rubinstein, Abraham; Srebnik, Morris

2009-02-06

Cyclisation of diethyl 3-allyloxy-1-propynylphosphonates with Mo(CO)(6) under PK conditions to give 3-substituted-5-oxo-3,5,6,6a-tetrahydro-1H-cyclopenta[c]furan-4-ylphosphonate, 2a-h, in 45-88% isolated yields was done. The R groups are always syn with H(b) (where applicable). The stereochemistry was determined via both NMR and crystal X-ray analysis.

Synthesis, anticancer activity, and iron affinity of the Actinoplanes metabolite 7,8-dihydroxy-1-methylnaphtho[2,3-c]furan-4,9-dione.

PubMed

Breyer, Sandra; Effenberger-Neidnicht, Katharina; Knauer, Sebastian; Schobert, Rainer

2011-02-01

The first synthesis of 7,8-dihydroxy-1-methylnaphtho[2,3-c]furan-4,9-dione (1), an isofuranonaphthoquinone produced by an Actinoplanes strain is described. Lactone ring opening of 6-methylfuro[3,4-c]furan-1(3H)-one (4) with ortho-lithiated veratrole (3), oxidation of product alcohol 5, and Friedel-Crafts acylation of the resulting aroylcarboxylic acid 7 afforded the mono methyl ether 2 of the target compound. The latter was obtained by demethylation of 2 with BBr(3) in 14% overall yield. While mono ether 2 was distinctly more cytotoxic than catechol 1 against a panel of five cancer cell lines, only the latter showed a siderophore-like binding affinity for Fe(III) with a complex dissociation constant K(D) of approximately 10(-29) M(3) (pM = 25.9). Copyright © 2010 Elsevier Ltd. All rights reserved.

Distance dependence in photoinduced intramolecular electron transfer. Additional remarks and calculations

NASA Astrophysics Data System (ADS)

Larsson, Sven; Volosov, Andrey

1987-12-01

Rate constants for photoinduced intramolecular electron transfer are calculated for four of the molecules studied by Hush et al. The electronic factor is obtained in quantum chemical calculations using the CNDO/S method. The results agree reasonably well with experiments for the forward reaction. Possible reasons for the disagreement for the charge recombination process are offered.

Synthesis of a ketone analogue of biotin via the intramolecular Pauson-Khand reaction.

PubMed

McNeill, Eric; Chen, Irwin; Ting, Alice Y

2006-09-28

We report an improved synthesis of 5-(5-oxohexahydrocyclopenta[c]thiophen-1-yl)pentanoic acid (ketone biotin, 1) based on the intramolecular Pauson-Khand cyclization. The synthesis proceeds in eight steps and in 2.7% overall yield from cyclohexene.

Contrasting intermolecular and intramolecular exciplex formation of a 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad.

PubMed

Imoto, Mitsutaka; Ikeda, Hiroshi; Fujii, Takayuki; Taniguchi, Hisaji; Tamaki, Akihiro; Takeda, Motonori; Mizuno, Kazuhiko

2010-05-07

An intramolecular exciplex is formed upon excitation of the cyclohexane solution of the 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad, but little if any intramolecular CT complex exists in the ground state of this substance in solution. In contrast, in the crystalline state, the dyad forms an intermolecular mixed-stack CT complex in the ground state and an intermolecular exciplex when it is photoexcited.

Effect of Furan Fatty Acids and 3-Methyl-2,4-nonanedione on Light-Induced Off-Odor in Soybean Oil.

PubMed

Sano, Takashi; Okabe, Ryo; Iwahashi, Maiko; Imagi, Jun; Sato, Toshiro; Yamashita, Toshiyuki; Fukusaki, Eiichiro; Bamba, Takeshi

2017-03-15

Soybean oil is one of the most widely consumed vegetable oils. However, under photooxidative conditions, this oil develops a beany and green off-odor through a mechanism that has not yet been elucidated. Upon photooxidation, 3-methyl-2,4-nonanedione (3-MND) produces a strong aroma. In this study, the effect of furan fatty acids and 3-MND on odor reversion in soybean oil was investigated. Our findings suggest that the observed light-induced off-odor was likely attributable to the furan fatty acids present in the oil through the generation of 3-MND. While 3-MND may not be directly responsible for the development of light-induced off-odor, this compound appears to be involved because off-odor was detected in canola oil samples containing added 3-MND. In addition, in the present work, 3-hydroxy-3-methyl-2,4-nonanedione, which is derived from 3-MND, was identified for the first time in light-exposed soybean oil and shown to be one of the compounds responsible for odor reversion.

Multivariate Analysis and Prediction of Dioxin-Furan ...

EPA Pesticide Factsheets

Peer Review Draft of Regional Methods Initiative Final Report Dioxins, which are bioaccumulative and environmentally persistent, pose an ongoing risk to human and ecosystem health. Fish constitute a significant source of dioxin exposure for humans and fish-eating wildlife. Current dioxin analytical methods are costly, time-consuming, and produce hazardous by-products. A Danish team developed a novel, multivariate statistical methodology based on the covariance of dioxin-furan congener Toxic Equivalences (TEQs) and fatty acid methyl esters (FAMEs) and applied it to North Atlantic Ocean fishmeal samples. The goal of the current study was to attempt to extend this Danish methodology to 77 whole and composite fish samples from three trophic groups: predator (whole largemouth bass), benthic (whole flathead and channel catfish) and forage fish (composite bluegill, pumpkinseed and green sunfish) from two dioxin contaminated rivers (Pocatalico R. and Kanawha R.) in West Virginia, USA. Multivariate statistical analyses, including, Principal Components Analysis (PCA), Hierarchical Clustering, and Partial Least Squares Regression (PLS), were used to assess the relationship between the FAMEs and TEQs in these dioxin contaminated freshwater fish from the Kanawha and Pocatalico Rivers. These three multivariate statistical methods all confirm that the pattern of Fatty Acid Methyl Esters (FAMEs) in these freshwater fish covaries with and is predictive of the WHO TE

The influence of dielectric relaxation on intramolecular electron transfer

NASA Astrophysics Data System (ADS)

Heitele, H.; Michel-Beyerle, M. E.; Finckh, P.

1987-07-01

An unusually strong temperature dependence on the intramolecular electron-transfer rate has been observed for bridged donor-acceptor compounds in propylene glycol solution. In the frame of recent electron-transfer theories this effect reflects the influence of dielectric relaxation dynamics on electron transfer. With increasing dielectric relaxation time a smooth transition from non-adiabatic to solvent-controlled adiabatic behaviour is observed. The electron transfer rate in the solvent-controlled adiabatic limit is dominated by an inhomogeneous distribution of relaxation times.

Synthesis of a ketone analog of biotin via the intramolecular Pauson-Khand reaction

PubMed Central

McNeill, Eric; Chen, Irwin; Ting, Alice Y.

2008-01-01

We report an improved synthesis of 5-(5-oxohexahydrocyclopenta[c]thiophen-1-yl)pentanoic acid (ketone biotin, 1) based on the intramolecular Pauson-Khand cyclization. The synthesis proceeds in 8 steps and in 2.7% overall yield from cyclohexene. PMID:16986958

Estimation of dioxin and furan elimination rates with a pharmacokinetic model.

PubMed

Van der Molen, G W; Kooijman, B A; Wittsiepe, J; Schrey, P; Flesch-Janys, D; Slob, W

2000-01-01

Quantitative description of the pharmacokinetics of dioxins and furans in humans can be of great help for the assessment of health risks posed by these compounds. To that the elimination rates of sixteen 2,3,7,8-chlorinated dibenzodioxins and dibenzofurans are estimated from both a longitudinal and a cross-sectional data set using the model of Van der Molen et al. [Van der Molen G.W., Kooijman S.A.L.M., and Slob W. A generic toxicokinetic model for persistent lipophilic compounds in humans: an application to TCDD. Fundam Appl Toxicol 1996: 31: 83-94]. In this model the elimination rate is given by the (constant) specific elimination rate multiplied with the ratio between the lipid weight of the liver and total body lipid weight. Body composition, body weight and intake are assumed to depend on age. The elimination rate is, therefore, not constant. For 49-year-old males, the elimination rate estimates range between 0.03 per year for 1,2,3,6,7,8-hexaCDF to 1.0 per year for octaCDF. The elimination rates of the most toxic congeners, 2,3,7,8-tetraCDD, 1,2,3,7,8-pentaCDD, and 2,3,4,7,8-pentaCDF, were estimated at 0.09, 0.06, and 0.07, respectively, based on the cross-sectional data, and 0.11, 0.09, and 0.09 based on the longitudinal data. The elimination rates of dioxins decrease with age between 0.0011 per year for 1,2,3,6,7,8-hexaCDD and 0.0035 per year for 1,2,3,4,6,7,8-heptaCDD. For furans the average decrease is 0.0033 per year. The elimination rates were estimated both from a longitudinal and a cross-sectional data set, and agreed quite well with each other, after taking account of historical changes in average intake levels.

47 CFR 69.129 - Signalling for tandem switching.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 47 Telecommunication 3 2011-10-01 2011-10-01 false Signalling for tandem switching. 69.129 Section... (CONTINUED) ACCESS CHARGES Computation of Charges § 69.129 Signalling for tandem switching. A charge that is... provision of signalling for tandem switching. [59 FR 32930, June 27, 1994] ...

47 CFR 69.129 - Signalling for tandem switching.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 47 Telecommunication 3 2010-10-01 2010-10-01 false Signalling for tandem switching. 69.129 Section... (CONTINUED) ACCESS CHARGES Computation of Charges § 69.129 Signalling for tandem switching. A charge that is... provision of signalling for tandem switching. [59 FR 32930, June 27, 1994] ...

47 CFR 69.129 - Signalling for tandem switching.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 47 Telecommunication 3 2013-10-01 2013-10-01 false Signalling for tandem switching. 69.129 Section... (CONTINUED) ACCESS CHARGES Computation of Charges § 69.129 Signalling for tandem switching. A charge that is... provision of signalling for tandem switching. [59 FR 32930, June 27, 1994] ...

47 CFR 69.129 - Signalling for tandem switching.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 47 Telecommunication 3 2012-10-01 2012-10-01 false Signalling for tandem switching. 69.129 Section... (CONTINUED) ACCESS CHARGES Computation of Charges § 69.129 Signalling for tandem switching. A charge that is... provision of signalling for tandem switching. [59 FR 32930, June 27, 1994] ...

DISTRIBUTION OF DIOXINS, FURANS, AND COPLANAR ...

EPA Pesticide Factsheets

The United States Environmental Protection Agency (EPA) and the United States Department of Agriculture (USDA) recently collaborated on a statistically-based, national survey of dioxin-like compounds, including dioxins, furans, and coplanar PCBs, in the back fat from slaughtered cattle. Back fat was selected because it was a matrix that could easily be sampled by the veterinarians at the slaughter establishments. Also, since it was a matrix that was very high in fat content (in the range of 60-90% lipid), the ability to measure the dioxin-like compounds with a given sample volume was maximized. A principal use of the results of the national beef survey is to evaluate the exposure of individuals in the United States to these compounds through consumption of beef. In order to use the data for this purpose, an assumption needs to be made regarding the relationship between lipid concentrations of these compounds in back fat compared to the concentrations in meat products. However, data on the concentrations of these compounds in different cattle fat reservoirs to derive the proper assumption are sparse. There is some information on compounds with similar properties (lipophilic, persistent), including residues of HCB, PBB, and DDT, and these data do suggest that their lipid-based concentrations in various fat reservoirs in cattle are similar. In order to evaluate whether the same can be said of the dioxin-like compounds, the EPA and USDA collaborated on a seco

Substituent effects on the relaxation dynamics of furan, furfural and β-furfural: a combined theoretical and experimental approach.

PubMed

Oesterling, Sven; Schalk, Oliver; Geng, Ting; Thomas, Richard D; Hansson, Tony; de Vivie-Riedle, Regina

2017-01-18

For the series furan, furfural and β-furfural we investigated the effect of substituents and their positioning on the photoinduced relaxation dynamics in a combined theoretical and experimental approach. Using time resolved photoelectron spectroscopy with a high intensity probe pulse, we can, for the first time, follow the whole deactivation process of furan through a two photon probe signal. Using the extended 2-electron 2-orbital model [Nenov et al., J. Chem. Phys., 2011, 135, 034304] we explain the formation of one central conical intersection and predict the influence of the aldehyde group of the derivatives on its geometry. This, as well as the relaxation mechanisms from photoexcitation to the final outcome was investigated using a variety of theoretical methods. Complete active space self consistent field was used for on-the-fly calculations while complete active space perturbation theory and coupled cluster theory were used to accurately describe critical configurations. Experiment and theory show the relaxation dynamics of furfural and β-furfural to be slowed down, and together they disclose an additional deactivation pathway, which is attributed to the n O lonepair state introduced with the aldehyde group.

Unimolecular thermal fragmentation of ortho-benzene.

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

Zhang, X.; Maccarone, A. T.; Nimlos, M. R.

2007-01-01

The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments o-C{sub 6}H{sub 4}{sup +} {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4}{sup +}{Delta}{yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimental {Delta}{sub rxn}H{submore » 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of

Analysis of mexicanolide- and phragmalin-type limonoids from Heynea trijuga using high-performance liquid chromatography/electrospray tandem mass spectrometry.

PubMed

Yang, Wei; Fang, Dong-Mei; He, Hong-Ping; Hao, Xiao-Jiang; Wu, Zhi-Jun; Zhang, Guo-Lin

2013-06-15

Limonoids, a class of tetranortriterpenoids, exhibit various biological effects, including acting as potent antifeedants and insect growth-regulators against various pests. The analysis of phragmalin- and mexicanolide-type limonoids by collision-induced dissociation tandem mass spectrometry (CID-MS/MS) has not been reported. A high-performance liquid chromatography/electrospray ionization (HPLC/ESI)-MS/MS method was developed to investigate the fragmentation patterns of [M+NH4 ](+) ions for nine reference phragmalin- and mexicanolide-type limonoids. The method was also used in the identification of limonoid compounds in botanic extracts of Heynea trijuga. The losses of side chains and the furan part were the major fragmentation patterns. However, there was variation in the relative abundances of product ions resulting from the same fragmentation pathways. A total of 89 phragmalin- and mexicanolide-type limonoids in botanic extracts of Heynea trijuga were detected and 50 of these compounds were identified or tentatively characterized based on elemental constituents, fragmentation pathways, and the profile of the major product ions of reference compounds. In addition, the isomers could be tentatively distinguished. An HPLC/ESI-MS/MS method was developed and could be used to simultaneously identify and screen phragmalin- and mexicanolide-type limonoids in botanic extracts of Heynea trijuga. Copyright © 2013 John Wiley & Sons, Ltd.

Phenanthridine synthesis through iron-catalyzed intramolecular N-arylation of O-acetyl oxime.

PubMed

Deb, Indubhusan; Yoshikai, Naohiko

2013-08-16

O-Acetyl oximes derived from 2'-arylacetophenones undergo N-O bond cleavage/intramolecular N-arylation in the presence of a catalytic amount of iron(III) acetylacetonate in acetic acid. In combination with the conventional cross-coupling or directed C-H arylation, the reaction offers a convenient route to substituted phenanthridines.

Quantifying stickiness: thermodynamic characterization of intramolecular domain interactions to guide the design of förster resonance energy transfer sensors.

PubMed

Lindenburg, Laurens H; Malisauskas, Mantas; Sips, Tari; van Oppen, Lisanne; Wijnands, Sjors P W; van de Graaf, Stan F J; Merkx, Maarten

2014-10-14

The introduction of weak, hydrophobic interactions between fluorescent protein domains (FPs) can substantially increase the dynamic range (DR) of Förster resonance energy transfer (FRET)-based sensor systems. Here we report a comprehensive thermodynamic characterization of the stability of a range of self-associating FRET pairs. A new method is introduced that allows direct quantification of the stability of weak FP interactions by monitoring intramolecular complex formation as a function of urea concentration. The commonly used S208F mutation stabilized intramolecular FP complex formation by 2.0 kCal/mol when studied in an enhanced cyan FP (ECFP)-linker-enhanced yellow FP (EYFP) fusion protein, whereas a significantly weaker interaction was observed for the homologous Cerulean/Citrine FRET pair (ΔG0(o-c) = 0.62 kCal/mol). The latter effect could be attributed to two mutations in Cerulean (Y145A and H148D) that destabilize complex formation with Citrine. Systematic analysis of the contribution of residues 125 and 127 at the dimerization interface in mOrange.linker.mCherry fusion proteins yielded a toolbox of new mOrange-mCherry combinations that allowed tuning of their intramolecular interaction from very weak (ΔG0(o-c) = .0.39 kCal/mol) to relatively stable (ΔG0(o-c) = 2.2 kCal/mol). The effects of these mutations were also studied by monitoring homodimerization of mCherry variants using fluorescence anisotropy. These mutations affected intramolecular and intermolecular domain interactions similarly, although FP interactions were found to be stronger in the latter. The knowledge thus obtained allowed successful construction of a red-shifted variant of the bile acid FRET sensor BAS-1 by replacement of the self-associating Cerulean-Citrine pair by mOrange.mCherry variants with a similar intramolecular affinity. Our findings thus allow a better understanding of the subtle but important role of intramolecular domain interactions in current FRET sensors and help

Bond formations by intermolecular and intramolecular trappings of acylketenes and their applications in natural product synthesis†

PubMed Central

Reber, Keith P.; Tilley, S. David

2011-01-01

The reactive intermediates known as acylketenes exhibit a rich chemistry and have been extensively utilized for many types of inter- and intramolecular bond-forming reactions within the field of organic synthesis. Characteristic reactions of acylketenes include cycloadditions, carbon–carbon bond-forming reactions, and nucleophilic capture with alcohols or amines to give β-keto acid derivatives. In particular, the intramolecular capture of acylketene intermediates with pendant nucleophiles represents a powerful method for forming both medium-sized rings and macrocycles, often in high yield. This tutorial review examines the history, generation, and reactivity of acylketenes with a special focus on their applications in the synthesis of natural products. PMID:19847338

Iron(II)-catalyzed intramolecular aminohydroxylation of olefins with functionalized hydroxylamines.

PubMed

Liu, Guan-Sai; Zhang, Yong-Qiang; Yuan, Yong-An; Xu, Hao

2013-03-06

A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.

Naphtho[1,2-b]furan-4,5-dione is a potent anti-MRSA agent against planktonic, biofilm and intracellular bacteria.

PubMed

Yang, Shih-Chun; Yen, Feng-Lin; Wang, Pei-Wen; Aljuffali, Ibrahim A; Weng, Yi-Han; Tseng, Chih-Hua; Fang, Jia-You

2017-09-01

Naphtho[1,2-b]furan-4,5-dione (N12D) and naphtho[2,3-b]furan-4,9-dione (N23D) are furanonaphthoquinone derivatives from natural resources. We examined the antimicrobial activity of N12D and N23D against drug-resistant Staphylococcus aureus. Minimum inhibitory concentration, minimum bactericidal concentration, bacterial viability and agar diffusion assay were conducted against methicillin-resistant S. aureus (MRSA) and clinical isolates of vancomycin-resistant S. aureus. The minimum inhibitory concentration of N12D and N23D against MRSA was 4.9-9.8 and 39 μM, respectively. With regard to the agar diffusion test, the inhibition zone of the quinone compounds was threefold larger than that of oxacillin. N12D was found to inhibit MRSA biofilm thickness from 24 to 16 μm as observed by confocal microscopy. N12D showed a significant reduction of the intracellular MRSA burden without decreasing the macrophage viability. The antibacterial mechanisms of N12D may be bacterial wall/membrane damage and disturbance of gluconeogenesis and the tricarboxylic acid cycle.

Chlorinated Dioxins and Furans from Kelp and Copper Sulfate ...

EPA Pesticide Factsheets

In 2002, dioxins were discovered in animal feed ingredients during a random sampling by Irish officials and subsequently traced to particular mineral supplements produced at a Minnesota plant in the United States. These products sold under the names of SQM Mineral Products and Carbosan Mineral Products provide trace minerals complexed to polysaccharides for delivery of trace minerals. The products were voluntarily recalled by the company until the source of the dioxins could be identified and the dioxins eliminated from the supplements. Preliminary investigations by the company and federal agencies indicated that the dioxins were apparently produced during the manufacturing process of supplements containing copper, zinc, manganese, magnesium and iron. Additional studies were initiated to identify the specific ingredients required for dioxin formation and to provide further insight into the conditions necessary for their production. Citation: Ferrario, J.; Byrne, C.; Winters, D.; Boone, T.; Vigo, C.; Dupuy, A.; 2003. Chlorinated Dioxins and Furans from Kelp and Copper Sulfate: Initial Investigations of Dioxin Formation in Mineral Feed Supplements. Organohalogen Compounds 63, 183-186.

Tandem Translation Classroom: A Case Study

ERIC Educational Resources Information Center

Kim, Dohun; Koh, Taejin

2018-01-01

The transition to student-centred learning, advances in teleconferencing tools, and active international student exchange programmes have stimulated tandem learning in many parts of the world. This pedagogical model is based on a mutual language exchange between tandem partners, where each student is a native speaker in the language the…

Intramolecular Hydrogen Bond Activation: Thiourea-Organocatalyzed Enantioselective 1,3-Dipolar Cycloaddition of Salicylaldehyde-Derived Azomethine Ylides with Nitroalkenes.

PubMed

Esteban, Francisco; Cieślik, Wioleta; Arpa, Enrique M; Guerrero-Corella, Andrea; Díaz-Tendero, Sergio; Perles, Josefina; Fernández-Salas, José A; Fraile, Alberto; Alemán, José

2018-03-02

An organocatalytic strategy for the synthesis of tetrasubstituted pyrrolidines with monoactivated azomethine ylides in high enantiomeric excess and excellent exo/endo selectivity is presented. The key to success is the intramolecular activation via hydrogen bonding through an o -hydroxy group, which allows the dipolar cycloaddition to take place in the presence of azomethine ylides bearing only one activating group. The intramolecular hydrogen bond in the azomethine ylide and the intermolecular hydrogen bond with the catalyst have been demonstrated by DFT calculations and mechanistic proofs to be crucial for the reaction to proceed.

A readily prepared neutral heterobimetallic titanium(IV)-rhodium(I) catalyst for intramolecular hydroacylation.

PubMed

Morgan, John P; Kundu, Kousik; Doyle, Michael P

2005-07-14

The combination of HOCMe2CH2PPh2, Ti(OiPr)4, and [Rh(cod)Cl]2 (3:1:1) in either benzene or dichloromethane produces a discrete species (tentatively formulated as complex) that is an active catalyst for intramolecular hydroacylation reactions of 3-substituted pentenals.

Reaction Paths and Chemical Activation Reactions of 2-Methyl-5-Furanyl Radical with 3O2.

PubMed

Hudzik, Jason M; Bozzelli, Joseph W

2017-10-05

Interest in high-energy substituted furans has been increasing due to their occurrence in biofuel production and their versatility in conversion to other useful products. Methylfurans are the simplest substituted furans and understanding their reaction pathways, thermochemical properties, including intermediate species stability, and chemical kinetics would aid in the study of larger furans. Furan ring C-H bonds have been shown to be extremely strong, approximately 120 kcal mol -1 , due in part to the placement of the oxygen atom and aromatic-like resonance, both within the ring. The thermochemistry and kinetics of the oxidation of 2-methyfuran radical at position 5 of the furan ring, 2-methyl-5-furanyl radical (2MF5j), is analyzed. The resulting chemically activated species, 2MF5OOj radical, has a well depth of 51 kcal mol -1 below the 2MF5j + O 2 reactants; this is 4-5 kcal mol -1 deeper than that of phenyl and vinyl radical plus O 2 , with both of these reactions known to undergo chain branching. Important, low-energy reaction pathways include chain branching dissociations, intramolecular abstractions, group transfers, and radical oxygen additions. Enthalpies of formation, entropies, and heat capacities for the stable molecules, radicals, and transition-state species are analyzed using computational methods. Calculated ΔH ° f 298 values were determined using an isodesmic work reaction from the CBS-QB3 composite method. Elementary rate parameters are from saddle point transition-state structures and compared to variational transition-state analysis for the barrierless reactions. Temperature- and pressure-dependent rate constants which are calculated using QRRK and master equation analysis is used for falloff and stabilization.

Thermodynamic characterization of tandem mismatches found in naturally occurring RNA

PubMed Central

Christiansen, Martha E.; Znosko, Brent M.

2009-01-01

Although all sequence symmetric tandem mismatches and some sequence asymmetric tandem mismatches have been thermodynamically characterized and a model has been proposed to predict the stability of previously unmeasured sequence asymmetric tandem mismatches [Christiansen,M.E. and Znosko,B.M. (2008) Biochemistry, 47, 4329–4336], experimental thermodynamic data for frequently occurring tandem mismatches is lacking. Since experimental data is preferred over a predictive model, the thermodynamic parameters for 25 frequently occurring tandem mismatches were determined. These new experimental values, on average, are 1.0 kcal/mol different from the values predicted for these mismatches using the previous model. The data for the sequence asymmetric tandem mismatches reported here were then combined with the data for 72 sequence asymmetric tandem mismatches that were published previously, and the parameters used to predict the thermodynamics of previously unmeasured sequence asymmetric tandem mismatches were updated. The average absolute difference between the measured values and the values predicted using these updated parameters is 0.5 kcal/mol. This updated model improves the prediction for tandem mismatches that were predicted rather poorly by the previous model. This new experimental data and updated predictive model allow for more accurate calculations of the free energy of RNA duplexes containing tandem mismatches, and, furthermore, should allow for improved prediction of secondary structure from sequence. PMID:19509311

Selecting tandem partners for silicon solar cells [Selecting tandem partners for silicon solar cells using spectral efficiency

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

Yu, Zhengshan; Leilaeioun, Mehdi; Holman, Zachary

Combining silicon and other materials in tandem solar cells is one approach to enhancing the overall power conversion efficiency of the cells. Here, we argue that top cell partners for silicon tandem solar cells should be selected on the basis of their spectral efficiency — their efficiency resolved by wavelength.

Selecting tandem partners for silicon solar cells [Selecting tandem partners for silicon solar cells using spectral efficiency

DOE PAGES

Yu, Zhengshan; Leilaeioun, Mehdi; Holman, Zachary

2016-09-26

Combining silicon and other materials in tandem solar cells is one approach to enhancing the overall power conversion efficiency of the cells. Here, we argue that top cell partners for silicon tandem solar cells should be selected on the basis of their spectral efficiency — their efficiency resolved by wavelength.

Assembly of the Isoindolinone Core of Muironolide A by Asymmetric Intramolecular Diels-Alder Cycloaddition

PubMed Central

Flores, Beatris; Molinski, Tadeusz F.

2011-01-01

The hexahydro-1H-isoindolin-1-one core of muironolide A was prepared by asymmetric intramolecular Diels Alder cycloaddition using a variant of the MacMillan organocatalyst which sets the C4,C5 and C11 stereocenters. PMID:21751773

Tandem junction amorphous silicon solar cells

DOEpatents

Hanak, Joseph J.

1981-01-01

An amorphous silicon solar cell has an active body with two or a series of layers of hydrogenated amorphous silicon arranged in a tandem stacked configuration with one optical path and electrically interconnected by a tunnel junction. The layers of hydrogenated amorphous silicon arranged in tandem configuration can have the same bandgap or differing bandgaps.

Substantial Intramolecular Charge Transfer Induces Long Emission Wavelengths and Mega Stokes Shifts in 6-Aminocoumarins

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

Liu, Xiaogang; Cole, Jacqueline M.; Xu, Zhaochao

Coumarins are deployed in numerous bioimaging and biosensing applications. Among various coumarin derivatives, 6-aminocoumarins attract increasing attention for their red-shifted emissions, mega Stokes shifts, and significant solvatochromism. These spectral characteristics together with weak emission intensities have historically been ascribed to the formation of the twisted intramolecular charge transfer (TICT) state in 6-aminocoumarins. In this work, we demonstrate that it is actually substantial intramolecular charge transfer (ICT) that is responsible for these fluorescent properties. Based on this new understanding, we reanalyzed the sensing mechanism of a 6-aminocouarmin based fluorescent probe and obtained close agreement with experimental data. Lastly, our results leadmore » to a deeper understanding of the photophysics of 6-aminocoumarins and will inspire the rational development of novel fluorescent probes.« less

Substantial Intramolecular Charge Transfer Induces Long Emission Wavelengths and Mega Stokes Shifts in 6-Aminocoumarins

DOE PAGES

Liu, Xiaogang; Cole, Jacqueline M.; Xu, Zhaochao

2017-06-01

Coumarins are deployed in numerous bioimaging and biosensing applications. Among various coumarin derivatives, 6-aminocoumarins attract increasing attention for their red-shifted emissions, mega Stokes shifts, and significant solvatochromism. These spectral characteristics together with weak emission intensities have historically been ascribed to the formation of the twisted intramolecular charge transfer (TICT) state in 6-aminocoumarins. In this work, we demonstrate that it is actually substantial intramolecular charge transfer (ICT) that is responsible for these fluorescent properties. Based on this new understanding, we reanalyzed the sensing mechanism of a 6-aminocouarmin based fluorescent probe and obtained close agreement with experimental data. Lastly, our results leadmore » to a deeper understanding of the photophysics of 6-aminocoumarins and will inspire the rational development of novel fluorescent probes.« less

High-Efficiency Polycrystalline Thin Film Tandem Solar Cells.

PubMed

Kranz, Lukas; Abate, Antonio; Feurer, Thomas; Fu, Fan; Avancini, Enrico; Löckinger, Johannes; Reinhard, Patrick; Zakeeruddin, Shaik M; Grätzel, Michael; Buecheler, Stephan; Tiwari, Ayodhya N

2015-07-16

A promising way to enhance the efficiency of CIGS solar cells is by combining them with perovskite solar cells in tandem devices. However, so far, such tandem devices had limited efficiency due to challenges in developing NIR-transparent perovskite top cells, which allow photons with energy below the perovskite band gap to be transmitted to the bottom cell. Here, a process for the fabrication of NIR-transparent perovskite solar cells is presented, which enables power conversion efficiencies up to 12.1% combined with an average sub-band gap transmission of 71% for photons with wavelength between 800 and 1000 nm. The combination of a NIR-transparent perovskite top cell with a CIGS bottom cell enabled a tandem device with 19.5% efficiency, which is the highest reported efficiency for a polycrystalline thin film tandem solar cell. Future developments of perovskite/CIGS tandem devices are discussed and prospects for devices with efficiency toward and above 27% are given.

Highly Efficient Thermally Activated Delayed Fluorescence from an Excited-State Intramolecular Proton Transfer System

PubMed Central

2017-01-01

Thermally activated delayed fluorescence (TADF) materials have shown great potential for highly efficient organic light-emitting diodes (OLEDs). While the current molecular design of TADF materials primarily focuses on combining donor and acceptor units, we present a novel system based on the use of excited-state intramolecular proton transfer (ESIPT) to achieve efficient TADF without relying on the well-established donor–acceptor scheme. In an appropriately designed acridone-based compound with intramolecular hydrogen bonding, ESIPT leads to separation of the highest occupied and lowest unoccupied molecular orbitals, resulting in TADF emission with a photoluminescence quantum yield of nearly 60%. High external electroluminescence quantum efficiencies of up to 14% in OLEDs using this emitter prove that efficient triplet harvesting is possible with ESIPT-based TADF materials. This work will expand and accelerate the development of a wide variety of TADF materials for high performance OLEDs. PMID:28776019

A Diastereoselective Intramolecular Pauson-Khand Approach to the Construction of the BC Ring System in Tuberostemoninol.

PubMed

Jia, Xiangna; Williams, Robert M

2008-12-12

Herein we describe an asymmetric approach to the synthesis of a BC-ring synthon in tuberostemoninol via an intramolecular Pauson-Khand reaction stereocontrolled by a commercially available chiral glycinate.

Photodynamics of intramolecular proton transfer in polar and nonpolar biflavonoid solutions

NASA Astrophysics Data System (ADS)

Bondarev, S. L.; Knyukshto, V. N.; Tikhomirov, S. A.; Buganov, O. V.; Pyrko, A. N.

2012-10-01

Using methods of steady state luminescence and femtosecond spectroscopy, we have studied the mechanism of intramolecular proton transfer in synthesized 3,7-dihydroxy-2,8-di(4-methoxyphenyl)-4H,6H-pyrano[3,2- g]chromen-4,6-dion in polar and nonpolar solutions, films, and polycrystals at 293 and 77 K. In an excited singlet state, intramolecular proton transfer occurs in two stages. At the first stage, a tautomer with one transferred proton (OTP tautomer) is formed from the Franck-Condon state within τ1 = 0.6 ps. At the second stage, the second proton is transferred within τ2 = 3.1 ps and a tautomer with two transferred protons (TTP tautomer) is formed, which fluoresces in toluene at 293 K with a high quantum yield, Φ f = 0.66, and the fluorescence spectrum of which is characterized by a large Stokes shift, 9900 cm-1. At 293 K, polar solvents (dimethylformamide, dimethyl sulfoxide, ethanol, etc.) solvate the BFV molecule in the ground state, while, in the excited state, an OTP tautomer is mainly formed. In polar ethanol at 77 K, a dual fluorescence spectrum is observed, which is caused by the fluorescence emission of polysolvates with λ{max/ f } = 460 nm and TTP phototautomers at λ{max/ f }= 610 nm.

Intramolecular Long-Distance Electron Transfer in Organic Molecules

NASA Astrophysics Data System (ADS)

Closs, Gerhard L.; Miller, John R.

1988-04-01

Intramolecular long-distance electron transfer (ET) has been actively studied in recent years in order to test existing theories in a quantitative way and to provide the necessary constants for predicting ET rates from simple structural parameters. Theoretical predictions of an ``inverted region,'' where increasing the driving force of the reaction will decrease its rate, have begun to be experimentally confirmed. A predicted nonlinear dependence of ET rates on the polarity of the solvent has also been confirmed. This work has implications for the design of efficient photochemical charge-separation devices. Other studies have been directed toward determining the distance dependence of ET reactions. Model studies on different series of compounds give similar distance dependences. When different stereochemical structures are compared, it becomes apparent that geometrical factors must be taken into account. Finally, the mechanism of coupling between donor and acceptor in weakly interacting systems has become of major importance. The theoretical and experimental evidence favors a model in which coupling is provided by the interaction with the orbitals of the intervening molecular fragments, although more experimental evidence is needed. Studies on intramolecular ET in organic model compounds have established that current theories give an adequate description of the process. The separation of electronic from nuclear coordinates is only a convenient approximation applied to many models, but in long-distance ET it works remarkably well. It is particularly gratifying to see Marcus' ideas finally confirmed after three decades of skepticism. By obtaining the numbers for quantitative correlations between rates and distances, these experiments have shown that saturated hydrocarbon fragments can ``conduct'' electrons over tens of angstroms. A dramatic demonstration of this fact has recently been obtained by tunneling electron microscopy on Langmuir-Blodgett films, showing in a

Brönsted Acid-Catalyzed One-Pot Synthesis of Indoles from o-Aminobenzyl Alcohols and Furans

PubMed Central

Kuznetsov, Alexey; Makarov, Anton; Rubtsov, Alexandr E.; Butin, Alexander V.; Gevorgyan, Vladimir

2013-01-01

Brönsted acid-catalyzed one-pot synthesis of indoles from o-aminobenzyl alcohols and furans has been developed. This method operates via the in situ formation of aminobenzylfuran, followed by its recyclization into the indole core. The method proved to be efficient for substrates possessing different functional groups, including -OMe, -CO2Cy, and -Br. The resulting indoles can easily be transformed into diverse scaffolds, including 2,3- and 1,2-fused indoles, and indole possessing an α,β-unsaturated ketone moiety at the C-2 position. PMID:24255969

Removal of dioxins and furans from flue gases by non-flammable adsorbents in a fixed bed.

PubMed

Fell, H J; Tuczek, M

1998-01-01

The presented adsorption--process KOMBISORBON is applied for high efficient off-gas purification, preferably of polychlorinated dioxins and furans from off-gas of incineration plants, which are generated, when these are operated under unfavourable conditions [2]. This off-gas purification process complies with german laws, which limit the concentration of these substances to less than 0.1 ng toxicity equivalents (TE) per cubic metre of gas [1]. The adsorbent, the adsorption process and its plant concept (fixed bed) is described in detail including economics and obtained operation results. Alternative removal technologies are briefly outlined.

Form-Focused Interaction in Online Tandem Learning

ERIC Educational Resources Information Center

O'Rourke, Breffni

2005-01-01

Tandem language learning--a configuration involving pairs of learners with complementary target/native languages--is an underexploited but potentially very powerful use of computer-mediated communication (CMC) in second-language pedagogy. Tandem offers the benefits of authentic, culturally grounded interaction, while also promoting a pedagogical…

A Diastereoselective Intramolecular Pauson-Khand Approach to the Construction of the BC Ring System in Tuberostemoninol

PubMed Central

Jia, Xiangna; Williams, Robert M

2009-01-01

Herein we describe an asymmetric approach to the synthesis of a BC-ring synthon in tuberostemoninol via an intramolecular Pauson-Khand reaction stereocontrolled by a commercially available chiral glycinate. PMID:19779590

Intramolecular cation-π interactions in protonated phenylalanine derivatives.

PubMed

Fu, Weiqiang; Carr, Patrick J J; Lecours, Michael J; Burt, Michael; Marta, Rick A; Steinmetz, Vincent; Fillion, Eric; McMahon, Terrance B; Hopkins, W Scott

2016-12-21

The structures and properties of a series of phenylalanine (Phe) derivatives have been investigated in a joint computational and experimental infrared multiple photon dissociation (IRMPD) study. IRMPD spectra in the 1000-2000 cm -1 region show that protonation is localized on the amine group in all cases. Intramolecular cation-π interactions between the ammonium group and the phenyl ring heavily influence molecular geometries and properties such as gas phase basicity and proton affinity. By varying substituents on the phenyl ring, one can sensitively tune the cation-π interaction and, therefore, the molecular structure and properties. Variations in molecular structures and properties as a function of phenyl ring substitution are shown to correlate with substituent Hammett parameters.

The hexadehydro-Diels-Alder reaction.

PubMed

Hoye, Thomas R; Baire, Beeraiah; Niu, Dawen; Willoughby, Patrick H; Woods, Brian P

2012-10-11

Arynes (aromatic systems containing, formally, a carbon-carbon triple bond) are among the most versatile of all reactive intermediates in organic chemistry. They can be 'trapped' to give products that are used as pharmaceuticals, agrochemicals, dyes, polymers and other fine chemicals. Here we explore a strategy that unites the de novo generation of benzynes-through a hexadehydro-Diels-Alder reaction-with their in situ elaboration into structurally complex benzenoid products. In the hexadehydro-Diels-Alder reaction, a 1,3-diyne is engaged in a [4+2] cycloisomerization with a 'diynophile' to produce the highly reactive benzyne intermediate. The reaction conditions for this simple, thermal transformation are notable for being free of metals and reagents. The subsequent and highly efficient trapping reactions increase the power of the overall process. Finally, we provide examples of how this de novo benzyne generation approach allows new modes of intrinsic reactivity to be revealed.

Impact of undamped and damped intramolecular vibrations on the efficiency of photosynthetic exciton energy transfer

NASA Astrophysics Data System (ADS)

Juhász, Imre Benedek; Csurgay, Árpád I.

2018-04-01

In recent years, the role of molecular vibrations in exciton energy transfer taking place during the first stage of photosynthesis attracted increasing interest. Here, we present a model formulated as a Lindblad-type master equation that enables us to investigate the impact of undamped and especially damped intramolecular vibrational modes on the exciton energy transfer, particularly its efficiency. Our simulations confirm the already reported effects that the presence of an intramolecular vibrational mode can compensate the energy detuning of electronic states, thus promoting the energy transfer; and, moreover, that the damping of such a vibrational mode (in other words, vibrational relaxation) can further enhance the efficiency of the process by generating directionality in the energy flow. As a novel result, we show that this enhancement surpasses the one caused by pure dephasing, and we present its dependence on various system parameters (time constants of the environment-induced relaxation and excitation processes, detuning of the electronic energy levels, frequency of the intramolecular vibrational modes, Huang-Rhys factors, temperature) in dimer model systems. We demonstrate that vibrational-relaxation-enhanced exciton energy transfer (VREEET) is robust against the change of these characteristics of the system and occurs in wide ranges of the investigated parameters. With simulations performed on a heptamer model inspired by the Fenna-Matthews-Olson (FMO) complex, we show that this mechanism can be even more significant in larger systems at T = 300 K. Our results suggests that VREEET might be prevalent in light-harvesting complexes.

Role of Intramolecular Aromatic π-π Interactions in the Self-Assembly of Di-l-Phenylalanine Dipeptide Driven by Intermolecular Interactions: Effect of Alanine Substitution.

PubMed

Reddy, Samala Murali Mohan; Shanmugam, Ganesh

2016-09-19

Although the role of intermolecular aromatic π-π interactions in the self-assembly of di-l-phenylalanine (l-Phe-l-Phe, FF), a peptide that is known for hierarchical structure, is well established, the influence of intramolecular π-π interactions on the morphology of the self-assembled structure of FF has not been studied. Herein, the role of intramolecular aromatic π-π interactions is investigated for FF and analogous alanine (Ala)-containing dipeptides, namely, l-Phe-l-Ala (FA) and l-Ala-l-Phe (AF). The results reveal that these dipeptides not only form self-assemblies, but also exhibit remarkable differences in structural morphology. The morphological differences between FF and the analogues indicate the importance of intramolecular π-π interactions, and the structural difference between FA and AF demonstrates the crucial role of the nature of intramolecular side-chain interactions (aromatic-aliphatic or aliphatic-aromatic), in addition to intermolecular interactions, in deciding the final morphology of the self-assembled structure. The current results emphasise that intramolecular aromatic π-π interaction may not be essential to induce self-assembly in smaller peptides, and π (aromatic)-alkyl or alkyl-π (aromatic) interactions may be sufficient. This work also illustrates the versatility of aromatic and a combination of aromatic and aliphatic residues in dipeptides in the formation of structurally diverse self-assembled structures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Control of intramolecular π-π stacking interaction in cationic iridium complexes via fluorination of pendant phenyl rings.

PubMed

He, Lei; Ma, Dongxin; Duan, Lian; Wei, Yongge; Qiao, Juan; Zhang, Deqiang; Dong, Guifang; Wang, Liduo; Qiu, Yong

2012-04-16

Intramolecular π-π stacking interaction in one kind of phosphorescent cationic iridium complexes has been controlled through fluorination of the pendant phenyl rings on the ancillary ligands. Two blue-green-emitting cationic iridium complexes, [Ir(ppy)(2)(F2phpzpy)]PF(6) (2) and [Ir(ppy)(2)(F5phpzpy)]PF(6) (3), with the pendant phenyl rings on the ancillary ligands substituted with two and five fluorine atoms, respectively, have been synthesized and compared to the parent complex, [Ir(ppy)(2)(phpzpy)]PF(6) (1). Here Hppy is 2-phenylpyridine, F2phpzpy is 2-(1-(3,5-difluorophenyl)-1H-pyrazol-3-yl)pyridine, F5phpzpy is 2-(1-pentafluorophenyl-1H-pyrazol-3-yl)-pyridine, and phpzpy is 2-(1-phenyl-1H-pyrazol-3-yl)pyridine. Single crystal structures reveal that the pendant phenyl rings on the ancillary ligands stack to the phenyl rings of the ppy ligands, with dihedral angles of 21°, 18°, and 5.0° between least-squares planes for complexes 1, 2, and 3, respectively, and centroid-centroid distances of 3.75, 3.65, and 3.52 Å for complexes 1, 2, and 3, respectively, indicating progressively reinforced intramolecular π-π stacking interactions from complexes 1 to 2 and 3. Compared to complex 1, complex 3 with a significantly reinforced intramolecular face-to-face π-π stacking interaction exhibits a significantly enhanced (by 1 order of magnitude) photoluminescent efficiency in solution. Theoretical calculations reveal that in complex 3 it is unfavorable in energy for the pentafluorophenyl ring to swing by a large degree and the intramolecular π-π stacking interaction remains on the lowest triplet state. © 2012 American Chemical Society

Generation of N-Heterocycles via Tandem Reactions of N '-(2-Alkynylbenzylidene)hydrazides.

PubMed

Qiu, Guanyinsheng; Wu, Jie

2016-02-01

As a powerful synthon, N '-(2-alkynylbenzylidene)hydrazides have been utilized efficiently for the construction of N-heterocycles. Since N '-(2-alkynylbenzylidene)hydrazides can easily undergo intramolecular 6-endo cyclization promoted by silver triflate or electrophiles, the resulting isoquinolinium-2-yl amides can proceed through subsequent transformations including [3 + 2] cycloaddition, nucleophilic addition, and [3 + 3] cycloaddition. Several unexpected rearrangements via radical processes were observed in some cases, which afforded nitrogen-containing heterocycles with molecular complexity. Reactive partners including internal alkynes, arynes, ketenimines, ketenes, allenoates, and activated alkenes reacted through [3 + 2] cycloaddition and subsequent aromatization, leading to diverse H-pyrazolo[5,1-a]isoquinolines with high efficiency. Nucleophilic addition to the in situ generated isoquinolinium-2-yl amide followed by aromatization also produced H-pyrazolo[5,1-a]isoquinoline derivatives when terminal alkynes, carbonyls, enamines, and activated methylene compounds were used as nucleophiles. Isoquinoline derivatives were obtained when indoles or phosphites were employed as nucleophiles in the reactions of N '-(2-alkynylbenzylidene)hydrazides. A tandem 6-endo cyclization and [3 + 3] cycloaddition of cyclopropane-1,1-dicarboxylates with N '-(2-alkynylbenzylidene)hydrazides was observed as well. Small libraries of these compounds were constructed. Biological evaluation suggested that some compounds showed promising activities for inhibition of CDC25B, TC-PTP, HCT-116, and PTP1B. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic Tandem Language Learning (eTandem): A Third Approach to Second Language Learning for the 21st Century

ERIC Educational Resources Information Center

Cziko, Gary A.

2004-01-01

Tandem language learning occurs when two learners of different native languages work together to help each other learn the other language. First used in face-to-face contexts, Tandem is now increasingly being used by language-learning partners located in different countries who are linked via various forms of electronic communication, a context…

Total synthesis of solanoeclepin A

NASA Astrophysics Data System (ADS)

Tanino, Keiji; Takahashi, Motomasa; Tomata, Yoshihide; Tokura, Hiroshi; Uehara, Taketo; Narabu, Takashi; Miyashita, Masaaki

2011-06-01

Cyst nematodes are troublesome parasites that live on, and destroy, a range of important host vegetable plants. Damage caused by the potato cyst nematode has now been reported in over 50 countries. One approach to eliminating the problem is to stimulate early hatching of the nematodes, but key hatching stimuli are not naturally available in sufficient quantities to do so. Here, we report the first chemical synthesis of solanoeclepin A, the key hatch-stimulating substance for potato cyst nematode. The crucial steps in our synthesis are an intramolecular cyclization reaction for construction of the highly strained tricyclo[5.2.1.01,6]decane skeleton (DEF ring system) and an intramolecular Diels-Alder reaction of a furan derivative for the synthesis of the ABC carbon framework. The present synthesis has the potential to contribute to addressing one of the critical food issues of the twenty-first century.

Laser flash photolysis experiments on the effects of freezing and salt addition on intramolecular electron transfer within one-electron reduced ascorbate oxidase.

PubMed

Hazzard, J T; Maritano, S; Tollin, G; Marchesini, A

1997-03-01

Laser flash photolysis has been used to investigate the effects of freezing protein solutions and of adding various salts on the kinetics of one-electron photoreduction by 5-deazariboflavin semiquinone (5-DRFH.) of oxidized ascorbate oxidase (AO) from zucchini in 100 mM phosphate buffer (pH 7.0). The initial reaction between oxidized AO and 5-DRFH. is quite rapid (k approximately 10(8) M-1 s-1) and occurs at the blue Type I Cu center. Subsequent to this, a slower, protein concentration-independent intramolecular reoxidation of the Type I Cu is observed, with kET approximately 150 s-1, resulting in 40-50% reoxidation of the blue Cu center and the establishment of an electron transfer (ET) equilibrium between the various Cu centers in AO. When such a sample of AO was frozen overnight at -30 degrees C, flash photolysis of the thawed sample showed no effect on the kinetics of reduction of the Type I Cu by 5-DRFH. However, the rate constant for intramolecular ET decreased to a value of 2.7 s-1, with only 20% reoxidation of the Type I center. Reduction of the enzyme with ascorbic acid, followed by O2 oxidation, resulted in restoration of rapid intramolecular reoxidation (kET = 130 s-1), with 33% of the Type I Cu reduced by 5-DRFH. being reoxidized. These results are consistent with previous work which showed that samples of AO with initially low activity can be reactivated by ascorbic acid turnover in the presence of O2. When AO was frozen in the presence of ascorbic acid, similar inhibition of intramolecular ET was obtained, whereas upon turnover of this sample by further addition of ascorbic acid and exposure to O2, activity was not restored. The effects of addition of (NH4)2SO4, Na2SO4, NH4Cl, NaCl, KCl, and KF on the kinetics of Type I Cu reduction by 5-deazariboflavin semiquinone and on the subsequent intramolecular ET were also examined. A twofold increase in the bimolecular rate constant for reduction of the Type I Cu was observed for the two sodium salts at high

Dynamic intramolecular regulation of the histone chaperone nucleoplasmin controls histone binding and release

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

Warren, Christopher; Matsui, Tsutomu; Karp, Jerome M.

Here, nucleoplasmin (Npm) is a highly conserved histone chaperone responsible for the maternal storage and zygotic release of histones H2A/H2B. Npm contains a pentameric N-terminal core domain and an intrinsically disordered C-terminal tail domain. Though intrinsically disordered regions are common among histone chaperones, their roles in histone binding and chaperoning remain unclear. Using an NMR-based approach, here we demonstrate that the Xenopus laevis Npm tail domain controls the binding of histones at its largest acidic stretch (A2) via direct competition with both the C-terminal basic stretch and basic nuclear localization signal. NMR and small-angle X-ray scattering (SAXS) structural analyses allowedmore » us to construct models of both the tail domain and the pentameric complex. Functional analyses demonstrate that these competitive intramolecular interactions negatively regulate Npm histone chaperone activity in vitro. Together these data establish a potentially generalizable mechanism of histone chaperone regulation via dynamic and specific intramolecular shielding of histone interaction sites.« less

Dynamic intramolecular regulation of the histone chaperone nucleoplasmin controls histone binding and release

DOE PAGES

Warren, Christopher; Matsui, Tsutomu; Karp, Jerome M.; ...

2017-12-20

Here, nucleoplasmin (Npm) is a highly conserved histone chaperone responsible for the maternal storage and zygotic release of histones H2A/H2B. Npm contains a pentameric N-terminal core domain and an intrinsically disordered C-terminal tail domain. Though intrinsically disordered regions are common among histone chaperones, their roles in histone binding and chaperoning remain unclear. Using an NMR-based approach, here we demonstrate that the Xenopus laevis Npm tail domain controls the binding of histones at its largest acidic stretch (A2) via direct competition with both the C-terminal basic stretch and basic nuclear localization signal. NMR and small-angle X-ray scattering (SAXS) structural analyses allowedmore » us to construct models of both the tail domain and the pentameric complex. Functional analyses demonstrate that these competitive intramolecular interactions negatively regulate Npm histone chaperone activity in vitro. Together these data establish a potentially generalizable mechanism of histone chaperone regulation via dynamic and specific intramolecular shielding of histone interaction sites.« less

[Development of boomerang-type intramolecular cascade reactions and application to natural product synthesis].

PubMed

Takasu, K

2001-12-01

Intramolecular cascade reaction has received much attention as a powerful methodology to construct a polycyclic framework in organic synthesis. We have been developing "boomerang-type cascade reaction" to construct a variety of polycyclic skeletons efficiently. In the above reactions, a nucleophilic function of substrates changes the character into an electrophile after the initial reaction, and the electrophilic group acts as a nucleophile in the second reaction. That is, the reaction center stepwise moves from one functional group back to the same one via other functional groups. The stream of the electron concerning the cascade reaction is like a locus of boomerang. We show here three different boomerang-type reactions via ionic species or free radicals. 1) Diastereoselective Michael-aldol reaction based on the chiral auxiliary method and enantioselective Michael-aldol reaction by the use of external chiral sources. 2) Short and efficient total syntheses of longifolane sesquiterpenes utilizing intramolecular double Michael addition as a key step. 3) Development of boomerang-type radical cascade reaction of halopolyenes to construct terpenoid skeletons and its regioselectivity.

Gold-catalyzed sequential annulations towards 3,4-fused bi/tri-cyclic furans involving a [3+2+2]-cycloaddition.

PubMed

Liu, Suna; Yang, Pu; Peng, Shiyong; Zhu, Chenghao; Cao, Shengyu; Li, Jian; Sun, Jiangtao

2017-01-17

A gold-catalyzed sequential annulation reaction to prepare 3,4-fused bicyclic furan compounds has been realized by employing 2-(1-alkynyl)-2-alken-1-ones and 1,3,5-triazines as the starting materials under mild reaction conditions. This protocol features multiple bond formation in a single operation with the incorporation of two nitrogen and two carbon atoms into the final products. A mechanistic investigation reveals that the sequential annulations involved an unprecedented stepwise [3+2+2]-cycloaddition.

47 CFR 69.111 - Tandem-switched transport and tandem charge.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., geographically averaged on a study-area-wide basis, that the incumbent local exchange carrier experiences based... exchange carrier experiences based on the prior year's annual use. Tandem-switched transport transmission..., geographically averaged on a study-area-wide basis, that the incumbent local exchange carrier experiences based...

Pyrrolidine and Piperidine Formation Via Copper(II) Carboxylate Promoted Intramolecular Carboamination of Unactivated Olefins: Diastereoselectivity and Mechanism

PubMed Central

Sherman, Eric S.; Fuller, Peter H.; Kasi, Dhanalakshmi; Chemler, Sherry R.

2008-01-01

An expanded substrate scope and in depth analysis of the reaction mechanism of the copper(II) carboxylate promoted intramolecular carboamination of unactivated alkenes is described. This method provides access to N-functionalized pyrrolidines and piperidines. Both aromatic and aliphatic γ- and δ-alkenyl N-arylsulfonamides undergo the oxidative cyclization reaction efficiently. N-Benzoyl-2-allylaniline also underwent the oxidative cyclization. The terminal olefin substrates examined were more reactive than those with internal olefins, and the latter terminated in elimination rather than carbon-carbon bond formation. The efficiency of the reaction was enhanced by the use of more organic soluble copper(II) carboxylate salts, copper(II) neodecanoate in particular. The reaction times were reduced by the use of microwave heating. High levels of diastereoselectivity were observed in the synthesis of 2,5-disubstituted pyrrolidines, wherein the cis substitution pattern predominates. The mechanism of the reaction is discussed in the context of the observed reactivity and in comparison to analogous reactions promoted by other reagents and conditions. Our evidence supports a mechanism wherein the N-C bond is formed via intramolecular syn aminocupration and the C-C bond is formed via intramolecular addition of a primary carbon radical to an aromatic ring. PMID:17428100

Loss of intramolecular electrostatic interactions and limited conformational ensemble may promote self-association of cis-tau peptide.

PubMed

Barman, Arghya; Hamelberg, Donald

2015-03-01

Self-association of proteins can be triggered by a change in the distribution of the conformational ensemble. Posttranslational modification, such as phosphorylation, can induce a shift in the ensemble of conformations. In the brain of Alzheimer's disease patients, the formation of intra-cellular neurofibrillary tangles deposition is a result of self-aggregation of hyper-phosphorylated tau protein. Biochemical and NMR studies suggest that the cis peptidyl prolyl conformation of a phosphorylated threonine-proline motif in the tau protein renders tau more prone to aggregation than the trans isomer. However, little is known about the role of peptidyl prolyl cis/trans isomerization in tau aggregation. Here, we show that intra-molecular electrostatic interactions are better formed in the trans isomer. We explore the conformational landscape of the tau segment containing the phosphorylated-Thr(231)-Pro(232) motif using accelerated molecular dynamics and show that intra-molecular electrostatic interactions are coupled to the isomeric state of the peptidyl prolyl bond. Our results suggest that the loss of intra-molecular interactions and the more restricted conformational ensemble of the cis isomer could favor self-aggregation. The results are consistent with experiments, providing valuable complementary atomistic insights and a hypothetical model for isomer specific aggregation of the tau protein. © 2014 Wiley Periodicals, Inc.

Intramolecular ferro- and antiferromagnetic interactions in oxo-carboxylate bridged digadolinium(III) complexes.

PubMed

Cañadillas-Delgado, Laura; Fabelo, Oscar; Pasán, Jorge; Delgado, Fernando S; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

2010-08-21

Two new digadolinium(III) complexes with monocarboxylate ligands, [Gd2(pac)6(H2O)4] (1) and [Gd2(tpac)6(H2O)4] (2) (Hpac = pentanoic acid and Htpac = 3-thiopheneacetic acid), have been prepared and their structures determined by X-ray diffraction on single crystals. Their structures consist of neutral and isolated digadolinium(III) units, containing six monocarboxylate ligands and four coordinated water molecules, the bridging skeleton being built by a muO(1):kappa2O(1)O(2) framework. This structural pattern has already been observed in the parent acetate-containing compound [Gd2(ac)6(H2O)4] x 4 H2O (3) whose structure and magnetic properties were reported elsewhere (L. Cañadillas-Delgado, O. Fabelo, J. Cano, J. Pasán, F. S. Delgado, M. Julve, F. Lloret and C. Ruiz-Pérez, CrystEngComm, 2009, 11, 2131). Each gadolinium(III) ion in 1 and 2 is nine-coordinated with seven carboxylate-oxygen atoms from four pac (1)/tpac (2) ligands and two water molecules (1 and 2) building a distorted monocapped square antiprism. The values of the intramolecular gadolinium-gadolinium separation are 4.1215(5) (1), 4.1255(6) (2) and 4.1589(3) A (3) and those of the angle at the oxo-carboxylate bridge (theta) are 113.16(13) (1), 112.5(2) (2) and 115.47(7) degrees (3). Magnetic susceptibility measurements in the temperature range 1.9-300 K reveal the occurrence of a weak intramolecular antiferromagnetic interaction [J = -0.032(1) (1) and -0.012(1) cm(-1) (2), the Hamiltonian being defined as H = -JS(A) x S(B)] in contrast with the intramolecular ferromagnetic coupling which occurs in 3 (J = +0.031(1) cm(-1)). The magneto-structural data of 1-3 show the relevance of the geometrical parameters at the muO(1):kappa2O(1)O(2) bridge on the nature of the magnetic coupling between two gadolinium(III) ions.

An Extended Ab Initio and Theoretical Thermodynamics Studies of the Bergman Reaction and the Energy Splitting of the Singlet Ortho-, Meta-, and Para-Benzynes

NASA Technical Reports Server (NTRS)

Lindh, Roland; Lee, Timothy J.; Bernhardsson, Anders; Persson, B. Joakim; Karlstroem, Gunnar; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The autoaromatization of (Z)-hex-3-ene-1,5-diyne to the singlet biradical para-benzyne has been reinvestigated by state of the art ab initio methods. Previous CCSD(T)/6-31G(d,p) and CASPT2[0]/ANO[C(5s4p2d1f)/H(3s2p)] calculations estimated the the reaction heat at 298 K to be 8-10 and 4.9 plus or minus 3.2 kcal/mol, respectively. Recent NO- and oxygen-dependent trapping experiments and collision-induced dissociation threshold energy experiments estimate the heat of reaction to be 8.5 plus or minus 1.0 at 470 K (recomputed to 9.5 plus or minus 1.0 at 298 K) and 8.4 plus or minus 3.0 kcal/mol at 298 K, respectively. New theoretical estimates at 298 K predict the values at the basis set limit for the CCSD(T) and CASPT2(g1) methods to be 12.7 plus or minus 2.0 and 5.4 plus or minus 2.0 kcal/mol, respectively. The experimentally predicted electronic contribution to the heat of activation is 28.6 kcal/mol. This can be compared with 25.5 and 29.8 kcal/mol from the CASPT2[g1] and the CCSD(T) methods, respectively. The new study has in particular improved on the one-particle basis set for the CCSD(T) method as compared to earlier studies. For the CASPT2 investigation the better suited CASPT2[g1] approximation is utilized. The original CASPT2 method, CASPT2[0], systematically favors open shell systems relative to closed shell systems. This was previously corrected empirically. The study shows that the energy difference between CCSD(T) and CASPT2[g1] at the basis set limit is estimated to be 7 plus or minus 2 kcal/mol. The study also demonstrates that the estimated heat of reaction is very sensitive to the quality of the basis set.

Dioxins, furans, biphenyls, arsenic, thorium and uranium in natural and anthropogenic sources of phosphorus and calcium used in agriculture.

PubMed

Avelar, A C; Ferreira, W M; Pemberthy, D; Abad, E; Amaral, M A

2016-05-01

The aim of this study was to assess the presence of dioxins, furans and biphenyls, and the inorganic contaminants such as arsenic (As), thorium (Th) and uranium (U) in three main products used in Agriculture in Brazil: feed grade dicalcium phosphate, calcined bovine bone meal and calcitic limestone. The first two are anthropogenic sources of phosphorus and calcium, while calcitic limestone is a natural unprocessed mineral. Regarding to dioxin-like substances, all samples analyzed exhibited dioxins (PCDD) and furans (PCDF) and dioxin-like polychlorinated biphenyls (dl-PCBs) concentrations below limit of detection (LOD). In general, achieved is in accordance with regulation in Brazil where is established a maximum limit in limestone used in the citric pulp production (0.50pg WHO-TEQ g(-1)). In addition, reported data revealed very low levels for limestone in comparison with similar materials reported by European legislation. As result for toxic metals, achieved data were obtained using Instrumental Neutron Activation Analysis (INAA). On one hand, limestone sample exhibits the largest arsenic concentration. On another hand, dicalcium phosphate exhibited the largest uranium concentration, which represents a standard in animal nutrition. Therefore, it is phosphorus source in the animal feed industry can be a goal of concern in the feed field. Copyright © 2016 Elsevier B.V. All rights reserved.

Tandem catalysis: a new approach to polymers.

PubMed

Robert, Carine; Thomas, Christophe M

2013-12-21

The creation of polymers by tandem catalysis represents an exciting frontier in materials science. Tandem catalysis is one of the strategies used by Nature for building macromolecules. Living organisms generally synthesize macromolecules by in vivo enzyme-catalyzed chain growth polymerization reactions using activated monomers that have been formed within cells during complex metabolic processes. However, these biological processes rely on highly complex biocatalysts, thus limiting their industrial applications. In order to obtain polymers by tandem catalysis, homogeneous and enzyme catalysts have played a leading role in the last two decades. In the following feature article, we will describe selected published efforts to achieve these research goals.

Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

NASA Astrophysics Data System (ADS)

Chang, Hao

A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1

Peptide Analysis Using Tandem Mass Spectrometry

DTIC Science & Technology

1989-06-01

to give pyroglutamic acid during storage, eliminating ammonia. It is almost absent in the spectrum of a freshly-prepared sample and is not seen in...USING TANDEM MASS SPECTROMETRY INTRODUCTION S The objective of the project was to determine the complete amino acid sequence of the large polypeptide...Ubiquitin by use of fast atom bombardment (FAB) ionization and tandem mass spectrometry. The peptide containing 76 amino acid residues was available

Deactivation via ring opening: A quantum chemical study of the excited states of furan and comparison to thiophene

NASA Astrophysics Data System (ADS)

Gavrilov, Nemanja; Salzmann, Susanne; Marian, Christel M.

2008-06-01

Minimum nuclear arrangements of the ground and low-lying excited electronic states of furan were obtained by means of (time dependent) Kohn-Sham density functional theory. A combined density functional/multi-reference configuration interaction method (DFT/MRCI) was employed to compute the spectral properties at these points. Multiple minima were found on the first excited singlet (S 1) potential energy hypersurface with electronic structures S1, S2, S3 corresponding to the 1 1A 2 (π → 3s-Ryd), 1 1B 2 (π → π ∗), and 2 1A 1 (π → π ∗) states in the vertical absorption spectrum, respectively. In analogy to recently published studies in thiophene [S. Salzmann, M. Kleinschmidt, J. Tatchen, R. Weinkauf, C.M. Marian, Phys. Chem. Chem. Phys. 10 (2008) 380] a deactivation mechanism for electronically excited furan was detected that involves the opening of the pentacyclic ring. We found a nearly barrierless relaxation pathway from the Franck-Condon region along a C-O bond-breaking coordinate. Hereby the initially excited 1B 2 (π → π ∗) state undergoes a conical intersection with a 1B 1 (π → σ ∗) state. The system can return to the electronic ground state through a second conical intersection of the 1(π → σ ∗) state before the minimum of that B 1 state is reached.

Usnic Acid and the Intramolecular Hydrogen Bond: A Computational Experiment for the Organic Laboratory

ERIC Educational Resources Information Center

Green, Thomas K.; Lane, Charles A.

2006-01-01

A computational experiment is described for the organic chemistry laboratory that allows students to estimate the relative strengths of the intramolecular hydrogen bonds of usnic and isousnic acids, two related lichen secondary metabolites. Students first extract and purify usnic acid from common lichens and obtain [superscript 1]H NMR and IR…

An intramolecular crossed-benzoin reaction based KCN fluorescent probe in aqueous and biological environments.

PubMed

Lee, Jae Hong; Jang, Joo Hee; Velusamy, Nithya; Jung, Hyo Sung; Bhuniya, Sankarprasad; Kim, Jong Seung

2015-05-04

A turn-on fluorescent probe was designed for selective cyanide anion sensing in aqueous and biological environments. The probe underwent an intramolecular crossed-benzoin reaction in the presence of KCN to expel the fluorophore resorufin. This probe was sensitive to KCN concentrations as low as 4 nM in aqueous media.

Understanding perovskite formation through the intramolecular exchange method in ambient conditions

NASA Astrophysics Data System (ADS)

Szostak, Rodrigo; Castro, Jhon A. P.; Marques, Adriano S.; Nogueira, Ana F.

2017-04-01

Among the methods to prepare hybrid organic-inorganic perovskite films, the intramolecular exchange method was the first one that made possible to prepare perovskite solar cells with efficiencies higher than 20%. However, perovskite formation by this method is not completely understood, especially in ambient conditions. In this work, perovskite films were prepared by the intramolecular exchange method in ambient conditions. The spin coating speed and the frequency of the MAI solution dripping onto PbI2(DMSO) were varied during the deposition steps. With the combination of these two parameters, a rigid control of the solvent drying was possible. Thus, depending on the chosen conditions, the intermediate MAPb3I8·2DMSO was formed with residual PbI2. Otherwise, direct formation of perovskite film was attained. A mechanism for the direct formation of bulk perovskite was proposed. We also investigated how the posterior thermal annealing affects the crystallinity and defects in perovskite films. With prolonged thermal annealing, the excess of MAI can be avoided, increasing the efficiency and decreasing the hysteresis of the solar cells. The best perovskite solar cell achieved a stabilized power output of 12.9%. The findings of this work pave the way for realizing the fabrication of efficient perovskite solar cells in ambient atmosphere, a very desirable condition for cost-efficient large scale manufacturing of this technology.

Rate of intramolecular reduction of oxyferryl iron in horse heart myoglobin

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

Fenwick, C.; Marmor, S.; Govindaraju, K.

1994-04-06

Like heme peroxidases and other heme enzymes, myoglobin forms oxyferryl (Fe[sup IV][triple bond]O) on reaction with peroxides. We have recently observed slow intramolecular electron transfer (ET) to the oxyferryl heme of cytochrome c peroxidase (CCP) from a[sub 5]Ru[sup II] (a[sub 5]Ru = pentaammineruthenium) bound at His60 and proposed a large reorganizational energy ([lambda]) for oxyferryl heme. An obvious test of this large postulated [lambda] is to directly compare intramolecular ET rates between oxyferryl and a[sub 5]Ru centers in myoglobin with the corresponding rates in zinc-substituted sperm whale (SWMb) and recombinant human myoglobins (RHMb). Since the oxyferryl heme of horse heartmore » myoglobin (HHMb) is significantly more stable than that of SWMb, the former protein was chosen for this study. A a[sub 5]Ru group was attached to the surface His48 of HHMb, and rates of ET over the 12.7-angstrom distance between the a[sub 5]Ru center and the ferric and oxyferryl hemes were measured by pulse radiolysis at Brookhaven National Laboratory. HHMb (0.5-10 [mu]M) solutions were prepared in N[sub 2]O-saturated sodium phosphate buffer at pH 7.0 (40 mM) containing 12 mM HCOONa to generate CO[sub 2][sup .[minus

Asymmetric total synthesis of (+)-fusarisetin A via the intramolecular Pauson-Khand reaction.

PubMed

Huang, Jun; Fang, Lichao; Long, Rong; Shi, Li-Li; Shen, Hong-Juan; Li, Chuang-chuang; Yang, Zhen

2013-08-02

An asymmetic total synthesis of (+)-fusarisetin A has been achieved. The essential to our strategy was the application of the intramolecular Pauson-Khand reaction for the stereoselective construction of the trans-decalin subunit of (+)-fusarisetin A with a unique C16 quarternary chiral center. The developed chemistry offers an alternative to the IMDA reaction that has been used for fusarisetin A, and is applicable to analogue synthesis for biological evaluation.

TRedD—A database for tandem repeats over the edit distance

PubMed Central

Sokol, Dina; Atagun, Firat

2010-01-01

A ‘tandem repeat’ in DNA is a sequence of two or more contiguous, approximate copies of a pattern of nucleotides. Tandem repeats are common in the genomes of both eukaryotic and prokaryotic organisms. They are significant markers for human identity testing, disease diagnosis, sequence homology and population studies. In this article, we describe a new database, TRedD, which contains the tandem repeats found in the human genome. The database is publicly available online, and the software for locating the repeats is also freely available. The definition of tandem repeats used by TRedD is a new and innovative definition based upon the concept of ‘evolutive tandem repeats’. In addition, we have developed a tool, called TandemGraph, to graphically depict the repeats occurring in a sequence. This tool can be coupled with any repeat finding software, and it should greatly facilitate analysis of results. Database URL: http://tandem.sci.brooklyn.cuny.edu/ PMID:20624712

Antibody-mediated fluorescence enhancement based on shifting the intramolecular dimer<-->monomer equilibrium of fluorescent dyes.

PubMed

Wei, A P; Blumenthal, D K; Herron, J N

1994-05-01

A novel concept is described for directly coupling fluorescence emission to protein-ligand binding. It is based on shifting the intramolecular monomer<-->dimer equilibrium of two fluorescent dyes linked by a short spacer. A 13-residue peptide, recognized by a monoclonal antibody against human chorionic gonadotrophin (hCG), was labeled with fluorescein (F) and tetramethylrhodamine (T) at its N- and C-terminus, respectively. Spectral evidence suggests that when the conjugate is free in solution, F and T exist as an intramolecular dimer. Fluorescence quenching of fluorescein and rhodamine is approximately 98% and approximately 90%, respectively, due to dimerization. When the double-labeled peptide is bound to anti-hCG, however, the rhodamine fluorescence increases by up to 7.8-fold, depending upon the excitation wavelength. This is attributed to the dissociation of intramolecular dimers brought about by conformational changes of the conjugate upon binding. Fluorescein fluorescence, on the other hand, was still quenched because of excited-state energy transfer and residual ground-state interactions. Antibody binding also resulted in a approximately 3.4-fold increase in fluorescence anisotropy of the peptide. These changes in intensity and anisotropy allow direct measurement of antigen-antibody binding with a fluorescence plate reader or a polarization analyzer, without the need for separation steps and labeling antibodies. Because recent advances in peptide technology have allowed rapid and economical identification of antigen-mimicking peptides, the double-labeled peptide approach offers many opportunities for developing new diagnostic assays and screening new therapeutic drugs. It also has many potential applications to techniques involving recombinant antibodies, biosensors, cell sorting, and DNA probes.

Empirical solvent-mediated potentials hold for both intra-molecular and inter-molecular inter-residue interactions.

PubMed Central

Keskin, O.; Bahar, I.; Badretdinov, A. Y.; Ptitsyn, O. B.; Jernigan, R. L.

1998-01-01

Whether knowledge-based intra-molecular inter-residue potentials are valid to represent inter-molecular interactions taking place at protein-protein interfaces has been questioned in several studies. Differences in the chain connectivity effect and in residue packing geometry between interfaces and single chain monomers have been pointed out as possible sources of distinct energetics for the two cases. In the present study, the interfacial regions of protein-protein complexes are examined to extract inter-molecular inter-residue potentials, using the same statistical methods as those previously adopted for intra-molecular residue pairs. Two sets of energy parameters are derived, corresponding to solvent-mediation and "average residue" mediation. The former set is shown to be highly correlated (correlation coefficient 0.89) with that previously obtained for inter-residue interactions within single chain monomers, while the latter exhibits a weaker correlation (0.69) with its intra-molecular counterpart. In addition to the close similarity of intra- and inter-molecular solvent-mediated potentials, they are shown to be significantly more residue-specific and thereby discriminative compared to the residue-mediated ones, indicating that solvent-mediation plays a major role in controlling the effective inter-residue interactions, either at interfaces, or within single monomers. Based on this observation, a reduced set of energy parameters comprising 20 one-body and 3 two-body terms is proposed (as opposed to the 20 x 20 tables of inter-residue potentials), which reproduces the conventional 20 x 20 tables with a correlation coefficient of 0.99. PMID:9865952

PTGBase: an integrated database to study tandem duplicated genes in plants.

PubMed

Yu, Jingyin; Ke, Tao; Tehrim, Sadia; Sun, Fengming; Liao, Boshou; Hua, Wei

2015-01-01

Tandem duplication is a wide-spread phenomenon in plant genomes and plays significant roles in evolution and adaptation to changing environments. Tandem duplicated genes related to certain functions will lead to the expansion of gene families and bring increase of gene dosage in the form of gene cluster arrays. Many tandem duplication events have been studied in plant genomes; yet, there is a surprising shortage of efforts to systematically present the integration of large amounts of information about publicly deposited tandem duplicated gene data across the plant kingdom. To address this shortcoming, we developed the first plant tandem duplicated genes database, PTGBase. It delivers the most comprehensive resource available to date, spanning 39 plant genomes, including model species and newly sequenced species alike. Across these genomes, 54 130 tandem duplicated gene clusters (129 652 genes) are presented in the database. Each tandem array, as well as its member genes, is characterized in complete detail. Tandem duplicated genes in PTGBase can be explored through browsing or searching by identifiers or keywords of functional annotation and sequence similarity. Users can download tandem duplicated gene arrays easily to any scale, up to the complete annotation data set for an entire plant genome. PTGBase will be updated regularly with newly sequenced plant species as they become available. © The Author(s) 2015. Published by Oxford University Press.

Mild rhodium(iii)-catalyzed intramolecular annulation of benzamides with allylic alcohols to access azepinone derivatives.

PubMed

Peneau, Augustin; Tricart, Quentin; Guillou, Catherine; Chabaud, Laurent

2018-05-23

Azepinone derivatives are important frameworks of several natural products and bioactive compounds. They are synthetized using a Rh(iii)-catalyzed intramolecular annulation of benzamide-tethered allylic alcohols. The reaction requires mild conditions at room temperature and affords diversely substituted azepinones bearing a quaternary carbon.

Ductile Glass of Polyrotaxane Toughened by Stretch-Induced Intramolecular Phase Separation.

PubMed

Kato, Kazuaki; Nemoto, Kaito; Mayumi, Koichi; Yokoyama, Hideaki; Ito, Kohzo

2017-09-27

A new class of ductile glasses is created from a thermoplastic polyrotaxane. The hard glass, which has a Young's modulus of 1 GPa, shows crazing, necking, and strain hardening with a total elongation of 330%. Stress concentration is prevented through a unique stretch-induced intramolecular phase separation of the cyclic components and the exposed backbone. In situ synchrotron X-ray scattering studies indicate that the backbone polymer chains slip through the cyclic components in the regions where the stress is concentrated.

Isothermal Fourier transform infrared microspectrosopic studies on the stability kinetics of solid-state intramolecular cyclization of aspartame sweetener.

PubMed

Cheng, Y D; Lin, S Y

2000-03-01

A novel Fourier transform infrared (FT-IR) microspectrophotometer equipped with differential scanning calorimetry (DSC) was used to investigate the kinetics of intramolecular cyclization of aspartame (APM) sweetener in the solid state under isothermal conditions. The thermal-dependent changes in the peak intensity of IR spectra at 1543, 1283, and 1259 cm(-1) were examined to explore the reaction. The results support that the intramolecular cyclization process in APM proceeded in three steps: the methoxyl group of ester was first thermolyzed to release methanol, then an acyl cation was attacked by the lone pair of electrons available on nitrogen by an S(N)1 pathway, and finally ring-closure occurred. The intramolecular cyclization of APM determined by this microscopic FT-IR/DSC system was found to follow zero-order kinetics after a brief induction period. The bond cleavage energy (259.38 kJ/mol) of thermolysis for the leaving group of -OCH(3), the bond conversion energy (328.88 kJ/mol) for the amide II NH band to DKP NH band, and the CN bond formation energy (326.93 kJ/mol) of cyclization for the DKP in the APM molecule were also calculated from the Arrhenius equation. The total activation energy of the DKP formation via intramolecular cyclization was 261.33 kJ/mol, calculated by the above summation of the bond energy of cleavage, conversion, and formation, which was near to the value determined by the DSC or TGA method. This indicates that the microscopic FT-IR/DSC system is useful as a potential tool not only to investigate the degradation mechanism of drugs in the solid state but also to directly predict the bond energy of the reaction.

Hybrid Tandem Solar Cells | Photovoltaic Research | NREL

Science.gov Websites

Hybrid Tandem Solar Cells Hybrid Tandem Solar Cells To achieve aggressive cost reductions in photovoltaics (PV) beyond the 6¢/kWh SunShot Initiative 2020 goal, module efficiency must be increased beyond on a silicon platform and that aim to provide viable prototypes for commercialization. PV Research

Monolithic Parallel Tandem Organic Photovoltaic Cell with Transparent Carbon Nanotube Interlayer

NASA Technical Reports Server (NTRS)

Tanaka, S.; Mielczarek, K.; Ovalle-Robles, R.; Wang, B.; Hsu, D.; Zakhidov, A. A.

2009-01-01

We demonstrate an organic photovoltaic cell with a monolithic tandem structure in parallel connection. Transparent multiwalled carbon nanotube sheets are used as an interlayer anode electrode for this parallel tandem. The characteristics of front and back cells are measured independently. The short circuit current density of the parallel tandem cell is larger than the currents of each individual cell. The wavelength dependence of photocurrent for the parallel tandem cell shows the superposition spectrum of the two spectral sensitivities of the front and back cells. The monolithic three-electrode photovoltaic cell indeed operates as a parallel tandem with improved efficiency.

Density functional tight-binding and infrequent metadynamics can capture entropic effects in intramolecular hydrogen transfer reactions

NASA Astrophysics Data System (ADS)

Oliveira, Luiz F. L.; Fu, Christopher D.; Pfaendtner, Jim

2018-04-01

Infrequent metadynamics uses biased simulations to estimate the unbiased kinetics of a system, facilitating the calculation of rates and barriers. Here the method is applied to study intramolecular hydrogen transfer reactions involving peroxy radicals, a class of reactions that is challenging to model due to the entropic contributions of the formation of ring structures in the transition state. Using the self-consistent charge density-functional based tight-binding (DFTB) method, we applied infrequent metadynamics to the study of four intramolecular H-transfer reactions, demonstrating that the method can qualitatively reproduce these high entropic contributions, as observed in experiments and those predicted by transition state theory modeled by higher levels of theory. We also show that infrequent metadynamics and DFTB are successful in describing the relationship between transition state ring size and kinetic coefficients (e.g., activation energies and the pre-exponential factors).

Inverted Three-Junction Tandem Thermophotovoltaic Modules

NASA Technical Reports Server (NTRS)

Wojtczuk, Steven

2012-01-01

An InGaAs-based three-junction (3J) tandem thermophotovoltaic (TPV) cell has been investigated to utilize more of the blackbody spectrum (from a 1,100 C general purpose heat source GPHS) efficiently. The tandem consists of three vertically stacked subcells, a 0.74-eV InGaAs cell, a 0.6- eV InGaAs cell, and a 0.55-eV InGaAs cell, as well as two interconnecting tunnel junctions. A greater than 20% TPV system efficiency was achieved by another group with a 1,040 C blackbody using a single-bandgap 0.6- eV InGaAs cell MIM (monolithic interconnected module) (30 lateral junctions) that delivered about 12 V/30 or 0.4 V/junction. It is expected that a three-bandgap tandem MIM will eventually have about 3 this voltage (1.15 V) and about half the current. A 4 A/cm2 would be generated by a single-bandgap 0.6-V InGaAs MIM, as opposed to the 2 A/cm2 available from the same spectrum when split among the three series-connected junctions in the tandem stack. This would then be about a 50% increase (3xVoc, 0.5xIsc) in output power if the proposed tandem replaced the single- bandgap MIM. The advantage of the innovation, if successful, would be a 50% increase in power conversion efficiency from radioisotope heat sources using existing thermophotovoltaics. Up to 50% more power would be generated for radioisotope GPHS deep space missions. This type of InGaAs multijunction stack could be used with terrestrial concentrator solar cells to increase efficiency from 41 to 45% or more.

The Intramolecular Hydrogen Bond N-H···S in 2,2'-Diaminodiphenyl Disulfide: Experimental and Computational Thermochemistry.

PubMed

Ramos, Fernando; Flores, Henoc; Hernández-Pérez, Julio M; Sandoval-Lira, Jacinto; Camarillo, E Adriana

2018-01-11

The intramolecular hydrogen bond of the N-H···S type has been investigated sparingly by thermochemical and computational methods. In order to study this interaction, the standard molar enthalpies of formation in gaseous phase of diphenyl disulfide, 2,2'-diaminodiphenyl disulfide and 4,4'-diaminodiphenyl disulfide at T = 298.15 K were determined by experimental thermochemical methods and computational calculations. The experimental enthalpies of formation in gas-phase were obtained from enthalpies of formation in crystalline phase and enthalpies of sublimation. Enthalpies of formation in crystalline phase were obtained using rotatory bomb combustion calorimetry. By thermogravimetry, enthalpies of vaporization were obtained, and by combining them with enthalpies of fusion, the enthalpies of sublimation were calculated. The Gaussian-4 procedure and the atomization method were applied to obtain enthalpies of formation in gas-phase of the compounds under study. Theoretical and experimental values are in good agreement. Through natural bond orbital (NBO) analysis and a topological analysis of the electronic density, the intramolecular hydrogen bridge (N-H···S) in the 2,2'-diaminodiphenyl disulfide was confirmed. Finally, an enthalpic difference of 11.8 kJ·mol -1 between the 2,2'-diaminodiphenyl disulfide and 4,4'-diaminodiphenyl disulfide was found, which is attributed to the intramolecular N-H···S interaction.

Dynamic Kinetic Resolution Enabled by Intramolecular Benzoin Reaction: Synthetic Applications and Mechanistic Insights.

PubMed

Zhang, Guoxiang; Yang, Shuang; Zhang, Xiaoyan; Lin, Qiqiao; Das, Deb K; Liu, Jian; Fang, Xinqiang

2016-06-29

The highly enantio-, diastereo-, and regioselective dynamic kinetic resolution of β-ketoesters and 1,3-diketones was achieved via a chiral N-heterocyclic carbene catalyzed intramolecular cross-benzoin reaction. A variety of tetralone derivatives bearing two contiguous stereocenters and multiple functionalities were liberated in moderate to excellent yields and with high levels of stereoselectivity (>95% ee and >20:1 dr in most cases). In addition, the excellent regioselectivity control for aryl/alkyl 1,3-diketones, and the superior electronic differentiation of 1,3-diarylketones were highlighted. Moreover, a set of new mechanistic rationale that differs with the currently widely accepted understanding of intramolecular benzoin reactions was established to demonstrate the superior preference of benzoin over aldol transformation: (1) A coexistence of competitive aldol and benzoin reactions was detected, but a retro-aldol-irreversible benzoin process performs a vital role in the generation of predominant benzoin products. (2) The most essential role of an N-electron-withdrawing substituent in triazolium catalysts was revealed to be accelerating the rate of the benzoin transformation, rather than suppressing the aldol process through reducing the inherent basicity of the catalyst.

Synthesis of furan-3-carboxylic and 4-methylene-4,5-dihydrofuran-3-carboxylic esters by direct palladium iodide catalyzed oxidative carbonylation of 3-yne-1,2-diol derivatives.

PubMed

Gabriele, Bartolo; Mancuso, Raffaella; Maltese, Vito; Veltri, Lucia; Salerno, Giuseppe

2012-10-05

A variety of 3-yne-1,2-diol derivatives 1, bearing a primary or secondary alcoholic group at C-1, have been efficiently converted into high value added furan-3-carboxylic esters 2 in one step by PdI(2)/KI-catalyzed direct oxidative carbonylation, carried out in alcoholic media under relatively mild conditions (100 °C under 40 atm of a 4/1 mixture of CO and air). Carbonylated furans 2 were obtained in fair to excellent isolated yields (56-93%) through a sequential 5-endo-dig heterocyclization-alkoxycarbonylation-dehydration process, using only oxygen as the external oxidant. Under similar conditions, 2-methyl-3-yne-1,2-diols 3, bearing a tertiary alcoholic group, afforded 4-methylene-4,5-dihydrofuran-3-carboxylates 4 in satisfactory yields (58-70%).

Performance of a tandem-rotor/tandem-stator conical-flow compressor designed for a pressure ratio of 3

NASA Technical Reports Server (NTRS)

Wood, J. R.; Owen, A. K.; Schumann, L. F.

1982-01-01

A conical-flow compressor stage with a large radius change through the rotor was tested at three values of rotor tip clearance. The stage had a tandem rotor and a tandem stator. Peak efficiency at design speed was 0.774 at a pressure ratio of 2.613. The rotor was tested without the stator, and detailed survey data were obtained for each rotor blade row. Overall peak rotor efficiency was 0.871 at a pressure ratio of 2.952.

A tandem-based compact dual-energy gamma generator.

PubMed

Persaud, A; Kwan, J W; Leitner, M; Leung, K-N; Ludewigt, B; Tanaka, N; Waldron, W; Wilde, S; Antolak, A J; Morse, D H; Raber, T

2010-02-01

A dual-energy tandem-type gamma generator has been developed at E. O. Lawrence Berkeley National Laboratory and Sandia National Laboratories. The tandem accelerator geometry allows higher energy nuclear reactions to be reached, thereby allowing more flexible generation of MeV-energy gammas for active interrogation applications. Both positively charged ions and atoms of hydrogen are created from negative ions via a gas stripper. In this paper, we show first results of the working tandem-based gamma generator and that a gas stripper can be utilized in a compact source design. Preliminary results of monoenergetic gamma production are shown.

Photoinduced Ultrafast Intramolecular Excited-State Energy Transfer in the Silylene-Bridged Biphenyl and Stilbene (SBS) System: A Nonadiabatic Dynamics Point of View.

PubMed

Wang, Jun; Huang, Jing; Du, Likai; Lan, Zhenggang

2015-07-09

The photoinduced intramolecular excited-state energy-transfer (EET) process in conjugated polymers has received a great deal of research interest because of its important role in the light harvesting and energy transport of organic photovoltaic materials in photoelectric devices. In this work, the silylene-bridged biphenyl and stilbene (SBS) system was chosen as a simplified model system to obtain physical insight into the photoinduced intramolecular energy transfer between the different building units of the SBS copolymer. In the SBS system, the vinylbiphenyl and vinylstilbene moieties serve as the donor (D) unit and the acceptor (A) unit, respectively. The ultrafast excited-state dynamics of the SBS system was investigated from the point of view of nonadiabatic dynamics with the surface-hopping method at the TDDFT level. The first two excited states (S1 and S2) are characterized by local excitations at the acceptor (vinylstilbene) and donor (vinylbiphenyl) units, respectively. Ultrafast S2-S1 decay is responsible for the intramolecular D-A excitonic energy transfer. The geometric distortion of the D moiety play an essential role in this EET process, whereas the A moiety remains unchanged during the nonadiabatic dynamics simulation. The present work provides a direct dynamical approach to understand the ultrafast intramolecular energy-transfer dynamics in SBS copolymers and other similar organic photovoltaic copolymers.

Do fluorescence and transient absorption probe the same intramolecular charge transfer state of 4-(dimethylamino)benzonitrile?

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

Gustavsson, Thomas; Coto, Pedro B.; Serrano-Andres, Luis

2009-07-21

We present here the results of time-resolved absorption and emission experiments for 4-(dimethylamino)benzonitrile in solution, which suggest that the fluorescent intramolecular charge transfer (ICT) state may differ from the twisted ICT (TICT) state observed in transient absorption.

Solar-to-Chemical Energy Conversion with Photoelectrochemical Tandem Cells.

PubMed

Sivula, Kevin

2013-01-01

Efficiently and inexpensively converting solar energy into chemical fuels is an important goal towards a sustainable energy economy. An integrated tandem cell approach could reasonably convert over 20% of the sun's energy directly into chemical fuels like H2 via water splitting. Many different systems have been investigated using various combinations of photovoltaic cells and photoelectrodes, but in order to be economically competitive with the production of H2 from fossil fuels, a practical water splitting tandem cell must optimize cost, longevity and performance. In this short review, the practical aspects of solar fuel production are considered from the perspective of a semiconductor-based tandem cell and the latest advances with a very promising technology - metal oxide photoelectrochemical tandem cells - are presented.

TRAP: automated classification, quantification and annotation of tandemly repeated sequences.

PubMed

Sobreira, Tiago José P; Durham, Alan M; Gruber, Arthur

2006-02-01

TRAP, the Tandem Repeats Analysis Program, is a Perl program that provides a unified set of analyses for the selection, classification, quantification and automated annotation of tandemly repeated sequences. TRAP uses the results of the Tandem Repeats Finder program to perform a global analysis of the satellite content of DNA sequences, permitting researchers to easily assess the tandem repeat content for both individual sequences and whole genomes. The results can be generated in convenient formats such as HTML and comma-separated values. TRAP can also be used to automatically generate annotation data in the format of feature table and GFF files.

Photodetachment of Zwitterions: Probing Intramolecular Coulomb Repulsion and Attraction in the Gas Phase Using Pyridinium Dicarboxylate Anions

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

Wang, Xue B.; Dacres, J E.; Yang, Xin

2003-10-23

Zwitterions are critically important in many biological transformations and are used in numerous chemical processes. The consequences of electrostatic effects on reactivity and physical properties, however, are largely unknown. In this work, we report the results of negative ion photoelectron spectra of nine isomeric pyridinium dicarboxylate zwitterions and three nonzwitterionic methoxycarbonylpyridine carboxylate isomers (-O(2)CPyrCO(2)CH(3)). Information about the intramolecular electrostatic interactions was directly obtained from the photoelectron spectra. The adiabatic and vertical detachment energies were measured and understood in terms of intramolecular Coulombic forces. Calculations at the B3LYP and CCSD(T) level were performed and compared to the experimental electron binding energies.more » Structures, relative stabilities, and the electron detachment sites also were obtained from the calculations.« less

Ligand-controlled, norbornene-mediated, regio- and diastereoselective rhodium-catalyzed intramolecular alkene hydrosilylation reactions.

PubMed

Hua, Yuanda; Nguyen, Hiep H; Scaggs, William R; Jeon, Junha

2013-07-05

Ligand-controlled, norbornene-mediated, regio- and diastereoselective rhodium-catalyzed intramolecular alkene hydrosilylation of homoallyl silyl ethers (1) exploiting either BINAP or 1,6-bis(diphenylphosphino)hexane (dpph) has been developed. This method permits selective access to either trans-oxasilacyclopentanes (trans-2) or oxasilacyclohexanes (3) at will. A substoichiometric amount of norbornene markedly increased both yield and selectivity. A norbornene-mediated hydride shuttle process is discussed.

Synthesis of 2-Ethenylcyclopropyl Aryl Ketones via Intramolecular SN2-like Displacement of an Ester.

PubMed

Jung, Michael E; Sun, Daniel L; Dwight, Timothy A; Yu, Peiyuan; Li, Wei; Houk, K N

2016-10-07

The efficient synthesis of trans-2-ethenylcyclopropyl aryl ketones via an intramolecular S N 2-like displacement of an allylic ester is reported. A novel 1,5-acyl shift process is also observed that contributes to the product mixture. Theoretical calculations provide a rationale for the observed product ratio.

Intramolecular charge transfer effects on 4-hydroxy-3-methoxybenzaldehyde

NASA Astrophysics Data System (ADS)

Rajendiran, N.; Balasubramanian, T.

2008-03-01

The absorption and fluorescence spectral characteristics of 4-hydroxy-3-methoxybenzaldehyde (HMB) have been studied in different solvents, pH and β-cyclodextrin (β-CD) and compared with 4-hydroxy-3,5-dimethoxybenzaldehyde (HDMB). The inclusion complex of HMB with β-CD is analysed by UV-vis, fluorimetry, FT-IR, 1H NMR, SEM and AM1 methods. In HMB, the normal emission (B band) is originates from a locally excited state and the longer emission (A band) is due to intramolecular charge transfer state (ICT). The OH group of HMB is present in the interior part of the β-CD cavity and aldehyde group present in the upper part of the β-CD cavity.

Intramolecular hydrogen-bond activation for the addition of nucleophilic imines: 2-hydroxybenzophenone as a chemical auxiliary.

PubMed

Choubane, Houcine; Garrido-Castro, Alberto F; Alvarado, Cuauhtemoc; Martín-Somer, Ana; Guerrero-Corella, Andrea; Daaou, Mortada; Díaz-Tendero, Sergio; Carmen Maestro, M; Fraile, Alberto; Alemán, José

2018-03-29

The addition of nucleophilic imines, using 2-hydroxybenzophenone as a chemical auxiliary, is presented. An intramolecular six-membered ring via hydrogen bonding that enhances the reactivity and selectivity is the key of this strategy, which is supported by DFT calculations and experimental trials.

Trace Amounts of Furan-2-Carboxylic Acids Determine the Quality of Solid Agar Plates for Bacterial Culture

PubMed Central

Hara, Shintaro; Isoda, Reika; Tahvanainen, Teemu; Hashidoko, Yasuyuki

2012-01-01

Background Many investigators have recognised that a significant proportion of environmental bacteria exist in a viable but non-culturable state on agar plates, and some researchers have also noticed that some of such bacteria clearly recover their growth on matrices other than agar. However, the reason why agar is unsuitable for the growth of some bacteria has not been addressed. Methodology/Principal Findings According to the guide of a bioassay for swarming inhibition, we identified 5-hydroxymethylfuran-2-carboxylic acid (5-HMFA) and furan-2-carboxylic acid (FA) as factors that inhibit bacterial swarming and likely inhibit extracellular polysaccharide production on agar. The furan-2-carboxylic acids 5-HMFA and FA effectively inhibited the swarming and swimming of several environmental bacteria at concentrations of 1.8 and 2.3 µg L−1 (13 and 21 nmol L−1), respectively, which are equivalent to the concentrations of these compounds in 0.3% agar. On Luria-Bertani (LB) plates containing 1.0% agar that had been previously washed with MeOH, a mixture of 5-HMFA and FA in amounts equivalent to their original concentrations in the unwashed agar repressed the swarming of Escherichia coli K12 strain W3110, a representative swarming bacterium. Conclusions/Significance Agar that contains trace amounts of 5-HMFA and FA inhibits the proliferation of some slow-growing or difficult-to-culture bacteria on the plates, but it is useful for single colony isolation due to the ease of identification of swarmable bacteria as the non-swarmed colonies. PMID:22848437

Intramolecular interactions of L-phenylalanine revealed by inner shell chemical shift

NASA Astrophysics Data System (ADS)

Ganesan, Aravindhan; Wang, Feng

2009-07-01

Intramolecular interactions of the functional groups, carboxylic acid, amino, and phenyl in L-phenylalanine have been revealed through inner shell chemical shift. The chemical shift and electronic structures are studied using its derivatives, 2-phenethylamine (PEA) and 3-phenylpropionic acid (PPA), through substitutions of the functional groups on the chiral carbon Cα, i.e., carboxylic acid (-COOH) and amino (-NH2) groups. Inner shell ionization spectra of L-phenylalanine are simulated using density functional theory based B3LYP/TZVP and LB94/et-pVQZ models, which achieve excellent agreement with the most recently available synchrotron sourced x-ray photoemission spectroscopy of L-phenylalanine (Elettra, Italy). The present study reveals insight into behavior of the peptide bond (CO-NH) through chemical shift of the C1-Cα-Cβ(-Cγ) chain and intramolecular interactions with phenyl. It is found that the chemical shift of the carbonyl C1(=O) site exhibits an apparently redshift (smaller energy) when interacting with the phenyl aromatic group. Removal of the amino group (-NH2) from L-phenylalanine (which forms PPA) brings this energy on C1 close to that in L-alanine (δ <0.01 eV). Chemical environment of Cα and Cβ exhibits more significant differences in L-alanine than in the aromatic species, indicating that the phenyl group indeed affects the peptide bond in the amino acid fragment. No direct evidences are found that the carbonyl acid and amino group interact with the phenyl ring through conventional hydrogen bonds.

Fluorescence excitation and excited state intramolecular relaxation dynamics of jet-cooled methyl-2-hydroxy-3-naphthoate

NASA Astrophysics Data System (ADS)

McCarthy, Annemarie; Ruth, Albert A.

2013-11-01

Two distinct S0 → S1 fluorescence excitation spectra of methyl-2-hydroxy-3-napthoate (MHN23) have been obtained by monitoring fluorescence separately in the short (˜410 nm) and long (˜650 nm) wavelength emission bands. The short wavelength fluorescence is assigned to two MHN23 conformers which do not undergo excited state intramolecular proton transfer (ESIPT). Analysis of the 'long wavelength' fluorescence excitation spectrum, which arises from the proton transfer tautomer of MHN23 indicates an average lifetime of τ ⩾ 18 ± 2 fs for the initially excited states. Invoking the results of Catalan et al. [J. Phys. Chem. A, 1999, 103, 10921], who determined the N tautomer to decay predominantly via a fast non-radiative process, the limit of the rate of intramolecular excited proton transfer in MHN23 is calculated as, kpt ⩽ 1 × 1012 s-1.

Targeted tandem duplication of a large chromosomal segment in Aspergillus oryzae.

PubMed

Takahashi, Tadashi; Sato, Atsushi; Ogawa, Masahiro; Hanya, Yoshiki; Oguma, Tetsuya

2014-08-01

We describe here the first successful construction of a targeted tandem duplication of a large chromosomal segment in Aspergillus oryzae. The targeted tandem chromosomal duplication was achieved by using strains that had a 5'-deleted pyrG upstream of the region targeted for tandem chromosomal duplication and a 3'-deleted pyrG downstream of the target region. Consequently,strains bearing a 210-kb targeted tandem chromosomal duplication near the centromeric region of chromosome 8 and strains bearing a targeted tandem chromosomal duplication of a 700-kb region of chromosome 2 were successfully constructed. The strains bearing the tandem chromosomal duplication were efficiently obtained from the regenerated protoplast of the parental strains. However, the generation of the chromosomal duplication did not depend on the introduction of double-stranded breaks(DSBs) by I-SceI. The chromosomal duplications of these strains were stably maintained after five generations of culture under nonselective conditions. The strains bearing the tandem chromosomal duplication in the 700-kb region of chromosome 2 showed highly increased protease activity in solid-state culture, indicating that the duplication of large chromosomal segments could be a useful new breeding technology and gene analysis method.

Intramolecular Aza-Diels-Alder Reactions of ortho-Quinone Methide Imines: Rapid, Catalytic, and Enantioselective Assembly of Benzannulated Quinolizidines.

PubMed

Kretzschmar, Martin; Hofmann, Fabian; Moock, Daniel; Schneider, Christoph

2018-04-16

Aza-Diels-Alder reactions (ADARs) are powerful processes that furnish N-heterocycles in a straightforward fashion. Intramolecular variants offer the additional possibility of generating bi- and polycyclic systems with high stereoselectivity. We report herein a novel Brønsted acid catalyzed process in which ortho-quinone methide imines tethered to the dienophile via the N substituent react in an intramolecular ADAR to form complex quinolizidines and oxazinoquinolines in a one-step process. The reactions proceed under very mild conditions, with very good yields and good to very good diastereo- and enantioselectivities. Furthermore, the process was extended to a domino reaction that efficiently combines substrate synthesis, ortho-quinone methide imine formation, and ADAR. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of dioxins and furans for various solid fuels burnt in 25 kW automatic boiler

NASA Astrophysics Data System (ADS)

Hopan, František; Horák, Jiří; Krpec, Kamil; Kubesa, Petr; Dej, Milan; Laciok, Vendula

2016-06-01

There has been brown coal, black coal and maize straw in a pellet form burnt in an automatic boiler. Production of dibenzodioxins and dibenzofuranes, recomputated through toxicity equivalents, expressed as the emission factor relative to the fuel unit, has differentiated in a range of ca. three orders (0.05 up to 78.9 ng/kg) in dependence on a sort of the used fuel. The measured values have been compared with emission factors used for the emission inventory in the Czech Republic and Poland and with the emission limit applicable for waste incineration plants. The study has proven the influence of chlorine content in fuel on production of dioxins and furanes.

Approach to interfacial and intramolecular electron transfer of the diheme protein cytochrome c4 assembled on Au(111) surfaces.

PubMed

Chi, Qijin; Zhang, Jingdong; Arslan, Taner; Borg, Lotte; Pedersen, Gert W; Christensen, Hans E M; Nazmudtinov, Renat R; Ulstrup, Jens

2010-04-29

Intramolecular electron transfer (ET) between metal centers is a core feature of large protein complexes in photosynthesis, respiration, and redox enzyme catalysis. The number of microscopic redox potentials and ET rate constants is, however, prohibitive for experimental cooperative ET mapping, but two-center proteins are simple enough to offer complete communication networks. At the same time, multicenter redox proteins operate in membrane environments where conformational dynamics may lead to gated ET features different from conditions in homogeneous solution. The bacterial respiratory diheme protein Pseudomonas stutzeri cytochrome c(4) has been a target for intramolecular, interheme ET. We report here voltammetric and in situ scanning tunneling microscopy (STM) data for P. stutzeri cyt c(4) at single-crystal, atomically planar Au(111)-electrode surfaces modified by variable-length omega-mercapto-alkanoic carboxylic acids. As evidenced by in situ STM, the strongly dipolar protein is immobilized in a close to vertical orientation at this surface with the positively charged high-potential heme domain adjacent to the electrode. This orientation gives asymmetric voltammograms with two one-ET peaks in the cathodic direction and a single two-ET peak in the anodic direction. Intramolecular, interheme ET with high, 8,000-30,000 s(-1), rate constants is notably an essential part of this mechanism. The high rate constants are in striking contrast to ET reactions of P. stutzeri cyt c(4) with small reaction partners in homogeneous solution for which kinetic analysis clearly testifies to electrostatic cooperative effects but no intramolecular, interheme ET higher than 0.1-10 s(-1). This difference suggests a strong gating feature of the process. On the basis of the three-dimensional structure of P. stutzeri cyt c(4), gating is understandable due to the through-space, hydrogen-bonded electronic contact between the heme propionates which is highly sensitive to environmental

On the intramolecular origin of the blue shift of A-H stretching frequencies: triatomic hydrides HAX.

PubMed

Karpfen, Alfred; Kryachko, Eugene S

2009-04-30

A series of intermolecular complexes formed between the triatomic hydrides HAX and various interaction partners are investigated computationally aiming (1) to demonstrate that either an appearance or nonappearance of a blue shift of the A-H stretching frequency is directly related to the sign of the intramolecular coupling that exists between the two degrees of freedom, the A-H and A-X bond lengths, and (2) to offer the following conjecture: the theoretical protonation of a triatomic neutral molecule HAX at the site X is a simple and rather efficient probe of a red or blue shift that the stretching frequency nu(A-H) undergoes upon complex formation regardless of whether this bond is directly involved in hydrogen bonding or not. In other words, to predict whether this A-H bond is capable to display a blue or red shift of nu(A-H), it suffices to compare the equilibrium structures and vibrational spectra of a given molecule with its protonated counterpart. The two above goals are achieved invoking a series of 11 triatomic molecules: HNO, HSN, HPO, and HPS characterized by a negative intramolecular coupling; HON and HNS as intermediate cases; and HOF, HOCl, HCN, HNC, and HCP with a positive intramolecular coupling. For these purposes, the latter molecules are investigated at the MP2/6-311++G(2p,2d) level in the neutral and protonated HAXH(+) forms as well as their complexes with H(2)O and with the fluoromethanes H(3)CF, H(2)CF(2), and HCF(3).

Photoionization of furan from the ground and excited electronic states.

PubMed

Ponzi, Aurora; Sapunar, Marin; Angeli, Celestino; Cimiraglia, Renzo; Došlić, Nađa; Decleva, Piero

2016-02-28

Here we present a comparative computational study of the photoionization of furan from the ground and the two lowest-lying excited electronic states. The study aims to assess the quality of the computational methods currently employed for treating bound and continuum states in photoionization. For the ionization from the ground electronic state, we show that the Dyson orbital approach combined with an accurate solution of the continuum one particle wave functions in a multicenter B-spline basis, at the density functional theory (DFT) level, provides cross sections and asymmetry parameters in excellent agreement with experimental data. On the contrary, when the Dyson orbitals approach is combined with the Coulomb and orthogonalized Coulomb treatments of the continuum, the results are qualitatively different. In excited electronic states, three electronic structure methods, TDDFT, ADC(2), and CASSCF, have been used for the computation of the Dyson orbitals, while the continuum was treated at the B-spline/DFT level. We show that photoionization observables are sensitive probes of the nature of the excited states as well as of the quality of excited state wave functions. This paves the way for applications in more complex situations such as time resolved photoionization spectroscopy.

The Rhodium(II) Carbenoid Cyclization-Cycloaddition Cascade of α-Diazo Dihydroindolinones for the Synthesis of Novel Azapolycyclic Ring Systems‡

PubMed Central

England, Dylan B.; Eagan, James M.; Merey, Gokce; Anac, Olcay; Padwa, Albert

2008-01-01

Tandem carbonyl ylide formation-1,3-dipolar cycloaddition of α-diazo N-acetyl-tetrahydro-β-carbolin-1-one derivatives occur efficiently in the presence of a dirhodium catalyst to afford bimolecular cycloadducts in high yield. The Rh(II)-catalyzed reaction also takes place intramolecularly to give products derived from trapping of the carbonyl ylide dipole with a tethered alkene. The power of the intramolecular cascade sequence is that it rapidly assembles a pentacyclic ring system containing three new stereocenters and two adjacent quaternary centers stereospecifically in a single step and in high yield. PMID:18437248

Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

PubMed

Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

2018-02-02

The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

Alpha particle confinement in tandem mirrors

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

Devoto, R.S.; Ohnishi, M.; Kerns, J.

1980-10-10

Mechanisms leading to loss of alpha particles from non-axisymmetric tandem mirrors are considered. Stochastic diffusion due to bounce-drift resonances, which can cause rapid radial losses of high-energy alpha particles, can be suppressed by imposing a 20% rise in axisymmetric fields before the quadrupole transition sections. Alpha particles should then be well-confined until thermal energies when they enter the resonant plateau require. A fast code for computation of drift behavior in reactors is described. Sample calculations are presented for resonant particles in a proposed coil set for the Tandem Mirror Next Step.

Quantification of furanic compounds in coated deep-fried products simulating normal preparation and consumption: optimisation of HS-SPME analytical conditions by response surface methodology.

PubMed

Pérez-Palacios, T; Petisca, C; Melo, A; Ferreira, I M P L V O

2012-12-01

The validation of a method for the simultaneous quantification of furanic compounds in coated deep-fried samples processed and handled as usually consumed is presented. The deep-fried food was grinded using a device that simulates the mastication, and immediately analysed by headspace solid phase microextraction coupled to gas chromatography-mass spectrometry. Parameters affecting the efficiency of HS-SPME procedure were selected by response surface methodology, using a 2(3) full-factorial central composite design. Optimal conditions were achieved using 2g of sample, 3g of NaCl and 40min of absorption time at 37°C. Consistency between predicted and experimented values was observed and quality parameters of the method were established. As a result, furan, 2-furfural, furfuryl alcohol and 2-pentylfuran were, for the first time, simultaneously detected and quantified (5.59, 0.27, 10.48 and 1.77μgg(-1) sample, respectively) in coated deep-fried fish, contributing to a better understanding of the amounts of these compounds in food. Copyright © 2012 Elsevier Ltd. All rights reserved.

Tandem mobile robot system

DOEpatents

Buttz, James H.; Shirey, David L.; Hayward, David R.

2003-01-01

A robotic vehicle system for terrain navigation mobility provides a way to climb stairs, cross crevices, and navigate across difficult terrain by coupling two or more mobile robots with a coupling device and controlling the robots cooperatively in tandem.

On the mechanism of the palladium catalyzed intramolecular Pauson-Khand-type reaction.

PubMed

Lan, Yu; Deng, Lujiang; Liu, Jing; Wang, Can; Wiest, Olaf; Yang, Zhen; Wu, Yun-Dong

2009-07-17

Density functional theory calculations and experimental studies have been carried out on the intramolecular Pauson-Khand-Type reaction mediated by a PdCl(2)-thiourea catalyst, which proceeds under mild reaction conditions and provides a useful alternative to traditional Pauson-Khand reactions. The classical mechanism of the Pauson-Khand reaction involving the alkyne/alkene C-C bond formation as the key step has been found to be energetically unfavorable and is not in line with the experimental observations. A novel reaction mechanism has been proposed for the reaction. The first step involves the cis-halometalation of the alkyne, followed by sequential alkene and carbonyl insertion. The rate-determining fourth step is an intramolecular C-Cl oxidative addition, leading to a Pd(IV) intermediate. A C-C bond formation by reductive elimination completes the reaction. The mechanism is in agreement with the key experimental observations including (1) the need of a chloride for catalytic activity and the absence of catalysis with Pd(OAc)(2) alone; (2) the rate acceleration by the addition of LiCl; both with PdCl(2) and Pd(OAc)(2) catalysts; and (3) the preferred formation of the trans diastereomer in substituted cases. The cis halometalation and the formation and stability of the Pd(IV) intermediate is studied in detail and provides general insights into these novel steps.

QTAIM and Stress Tensor Characterization of Intramolecular Interactions Along Dynamics Trajectories of a Light-Driven Rotary Molecular Motor.

PubMed

Wang, Lingling; Huan, Guo; Momen, Roya; Azizi, Alireza; Xu, Tianlv; Kirk, Steven R; Filatov, Michael; Jenkins, Samantha

2017-06-29

A quantum theory of atoms in molecules (QTAIM) and stress tensor analysis was applied to analyze intramolecular interactions influencing the photoisomerization dynamics of a light-driven rotary molecular motor. For selected nonadiabatic molecular dynamics trajectories characterized by markedly different S 1 state lifetimes, the electron densities were obtained using the ensemble density functional theory method. The analysis revealed that torsional motion of the molecular motor blades from the Franck-Condon point to the S 1 energy minimum and the S 1 /S 0 conical intersection is controlled by two factors: greater numbers of intramolecular bonds before the hop-time and unusually strongly coupled bonds between the atoms of the rotor and the stator blades. This results in the effective stalling of the progress along the torsional path for an extended period of time. This finding suggests a possibility of chemical tuning of the speed of photoisomerization of molecular motors and related molecular switches by reshaping their molecular backbones to decrease or increase the degree of coupling and numbers of intramolecular bond critical points as revealed by the QTAIM/stress tensor analysis of the electron density. Additionally, the stress tensor scalar and vector analysis was found to provide new methods to follow the trajectories, and from this, new insight was gained into the behavior of the S 1 state in the vicinity of the conical intersection.

Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer.

PubMed

Ohara, Taku; Yuan, Tan Chia; Torii, Daichi; Kikugawa, Gota; Kosugi, Naohiro

2011-07-21

In this paper, the molecular mechanisms which determine the thermal conductivity of long chain polymer liquids are discussed, based on the results observed in molecular dynamics simulations. Linear n-alkanes, which are typical polymer molecules, were chosen as the target of our studies. Non-equilibrium molecular dynamics simulations of bulk liquid n-alkanes under a constant temperature gradient were performed. Saturated liquids of n-alkanes with six different chain lengths were examined at the same reduced temperature (0.7T(c)), and the contributions of inter- and intramolecular energy transfer to heat conduction flux, which were identified as components of heat flux by the authors' previous study [J. Chem. Phys. 128, 044504 (2008)], were observed. The present study compared n-alkane liquids with various molecular lengths at the same reduced temperature and corresponding saturated densities, and found that the contribution of intramolecular energy transfer to the total heat flux, relative to that of intermolecular energy transfer, increased with the molecular length. The study revealed that in long chain polymer liquids, thermal energy is mainly transferred in the space along the stiff intramolecular bonds. This finding implies a connection between anisotropic thermal conductivity and the orientation of molecules in various organized structures with long polymer molecules aligned in a certain direction, which includes confined polymer liquids and self-organized structures such as membranes of amphiphilic molecules in water.

Tandem internal models execute motor learning in the cerebellum.

PubMed

Honda, Takeru; Nagao, Soichi; Hashimoto, Yuji; Ishikawa, Kinya; Yokota, Takanori; Mizusawa, Hidehiro; Ito, Masao

2018-06-25

In performing skillful movement, humans use predictions from internal models formed by repetition learning. However, the computational organization of internal models in the brain remains unknown. Here, we demonstrate that a computational architecture employing a tandem configuration of forward and inverse internal models enables efficient motor learning in the cerebellum. The model predicted learning adaptations observed in hand-reaching experiments in humans wearing a prism lens and explained the kinetic components of these behavioral adaptations. The tandem system also predicted a form of subliminal motor learning that was experimentally validated after training intentional misses of hand targets. Patients with cerebellar degeneration disease showed behavioral impairments consistent with tandemly arranged internal models. These findings validate computational tandemization of internal models in motor control and its potential uses in more complex forms of learning and cognition. Copyright © 2018 the Author(s). Published by PNAS.

Quality evaluation of tandem mass spectral libraries.

PubMed

Oberacher, Herbert; Weinmann, Wolfgang; Dresen, Sebastian

2011-06-01

Tandem mass spectral libraries are gaining more and more importance for the identification of unknowns in different fields of research, including metabolomics, forensics, toxicology, and environmental analysis. Particularly, the recent invention of reliable, robust, and transferable libraries has increased the general acceptance of these tools. Herein, we report on results obtained from thorough evaluation of the match reliabilities of two tandem mass spectral libraries: the MSforID library established by the Oberacher group in Innsbruck and the Weinmann library established by the Weinmann group in Freiburg. Three different experiments were performed: (1) Spectra of the libraries were searched against their corresponding library after excluding either this single compound-specific spectrum or all compound-specific spectra prior to searching; (2) the libraries were searched against each other using either library as reference set or sample set; (3) spectra acquired on different mass spectrometric instruments were matched to both libraries. Almost 13,000 tandem mass spectra were included in this study. The MSforID search algorithm was used for spectral matching. Statistical evaluation of the library search results revealed that principally both libraries enable the sensitive and specific identification of compounds. Due to higher mass accuracy of the QqTOF compared with the QTrap instrument, matches to the MSforID library were more reliable when comparing spectra with both libraries. Furthermore, only the MSforID library was shown to be efficiently transferable to different kinds of tandem mass spectrometers, including "tandem-in-time" instruments; this is due to the coverage of a large range of different collision energy settings-including the very low range-which is an outstanding characteristics of the MSforID library.

Nanocrystal assembly for tandem catalysis

DOEpatents

Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

2014-10-14

The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

Synthesis of (±)-Tetrapetalone A-Me Aglycon**

PubMed Central

Carlsen, Peter N.; Mann, Tyler J.; Hoveyda, Amir H.

2014-01-01

The first synthesis of (±)-tetrapetalone A-Me aglycon is described. Key bond-forming reactions include Nazarov cyclization, a ring-closing metathesis (RCM) promoted with complete diastereoselectivity by a chiral Mo-based complex, tandem conjugate reduction-intramolecular aldol cyclization, and oxidative dearomatization. PMID:25045072

Single-task and dual-task tandem gait test performance after concussion.

PubMed

Howell, David R; Osternig, Louis R; Chou, Li-Shan

2017-07-01

To compare single-task and dual-task tandem gait test performance between athletes after concussion with controls on observer-timed, spatio-temporal, and center-of-mass (COM) balance control measurements. Ten participants (19.0±5.5years) were prospectively identified and completed a tandem gait test protocol within 72h of concussion and again 1 week, 2 weeks, 1 month, and 2 months post-injury. Seven uninjured controls (20.0±4.5years) completed the same protocol in similar time increments. Tandem gait test trials were performed with (dual-task) and without (single-task) concurrently performing a cognitive test as whole-body motion analysis was performed. Outcome variables included test completion time, average tandem gait velocity, cadence, and whole-body COM frontal plane displacement. Concussion participants took significantly longer to complete the dual-task tandem gait test than controls throughout the first 2 weeks post-injury (mean time=16.4 [95% CI: 13.4-19.4] vs. 10.1 [95% CI: 6.4-13.7] seconds; p=0.03). Single-task tandem gait times were significantly lower 72h post-injury (p=0.04). Dual-task cadence was significantly lower for concussion participants than controls (89.5 [95% CI: 68.6-110.4] vs. 127.0 [95% CI: 97.4-156.6] steps/minute; p=0.04). Moderately-high to high correlations between tandem gait test time and whole-body COM medial-lateral displacement were detected at each time point during dual-task gait (r s =0.70-0.93; p=0.03-0.001). Adding a cognitive task during the tandem gait test resulted in longer detectable deficits post-concussion compared to the traditional single-task tandem gait test. As a clinical tool to assess dynamic motor function, tandem gait may assist with return to sport decisions after concussion. Copyright © 2017 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Determination of relative assay response factors for toxic chlorinated and bromiated dioxins/furans using an enyme immunoassay (EIA) and a chemically-activated luciferase gene expression cell bioassay (CALUX)

EPA Science Inventory

Determination of dioxin-like activity requires knowledge of both the concentration and toxicity to evaluate the risk of adverse human health and environmental effects. The dioxin-like response of several polybrominated dibenzo-p-dioxins/furans (PBDDs/Fs) and polybrominated/chlori...

Negotiating Multiple Identities through eTandem Learning Experiences

ERIC Educational Resources Information Center

Yang, Se Jeong; Yi, Youngjoo

2017-01-01

Much of eTandem research has investigated either linguistic or cross-cultural aspects of second language (L2) learning, but relatively little is known about issues of identity construction in an eTandem context. Situating the study within theories and research of language learner identity, we examined ways in which two adult L2 learners (a Korean…

Tandem robot control system and method for controlling mobile robots in tandem

DOEpatents

Hayward, David R.; Buttz, James H.; Shirey, David L.

2002-01-01

A control system for controlling mobile robots provides a way to control mobile robots, connected in tandem with coupling devices, to navigate across difficult terrain or in closed spaces. The mobile robots can be controlled cooperatively as a coupled system in linked mode or controlled individually as separate robots.

SYMTRAN - A Time-dependent Symmetric Tandem Mirror Transport Code

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

Hua, D; Fowler, T

2004-06-15

A time-dependent version of the steady-state radial transport model in symmetric tandem mirrors in Ref. [1] has been coded up and first tests performed. Our code, named SYMTRAN, is an adaptation of the earlier SPHERE code for spheromaks, now modified for tandem mirror physics. Motivated by Post's new concept of kinetic stabilization of symmetric mirrors, it is an extension of the earlier TAMRAC rate-equation code omitting radial transport [2], which successfully accounted for experimental results in TMX. The SYMTRAN code differs from the earlier tandem mirror radial transport code TMT in that our code is focused on axisymmetric tandem mirrorsmore » and classical diffusion, whereas TMT emphasized non-ambipolar transport in TMX and MFTF-B due to yin-yang plugs and non-symmetric transitions between the plugs and axisymmetric center cell. Both codes exhibit interesting but different non-linear behavior.« less

Determination of furan precursors and some thermal damage markers in baby foods: ascorbic acid, dehydroascorbic acid, hydroxymethylfurfural and furfural.

PubMed

Mesías-García, Marta; Guerra-Hernández, Eduardo; García-Villanova, Belén

2010-05-26

The presence of ascorbic acid (AA), vitamin C (AA + dehydroascorbic acid (DHAA)) and furfural as potential precursors of furan in commercial fruit and vegetable jarred baby food was studied. Hydroxymethylfurfural (HMF) was also determined and used, together with furfural levels, as markers of thermal damage. AA, calculated DHAA and vitamin C values ranged between 22.4 and 103, 2.9 and 13.8, and 32.1 and 113.2 mg/100 g, respectively, in fruit-based baby food. However, no trace of AA was found in the vegetable-based baby food samples tested, probably because these samples are not enriched in vitamin C and the content of this vitamin in fresh vegetables is destroyed during processing. Furfural values ranged from not detected to 236 microg/100 g, being higher in vegetable samples than in fruit samples possibly because of greater AA degradation favored by a higher pH in the vegetable samples. HMF values (range: not detected-959 microg/100 g), however, were higher in the fruit samples, probably due to greater carbohydrate content degradation and as a consequence of the Maillard reaction, favored by a lower pH in these samples. According to these results, HMF would be the optimum indicator of thermal treatment for fruits, and furfural for vegetables. The higher furfural content of vegetable baby food could be considered an index of greater AA degradation and, therefore, the furan content might be higher in this kind of sample than in fruit-based baby food.

Cooperative cell motility during tandem locomotion of amoeboid cells

PubMed Central

Bastounis, Effie; Álvarez-González, Begoña; del Álamo, Juan C.; Lasheras, Juan C.; Firtel, Richard A.

2016-01-01

Streams of migratory cells are initiated by the formation of tandem pairs of cells connected head to tail to which other cells subsequently adhere. The mechanisms regulating the transition from single to streaming cell migration remain elusive, although several molecules have been suggested to be involved. In this work, we investigate the mechanics of the locomotion of Dictyostelium tandem pairs by analyzing the spatiotemporal evolution of their traction adhesions (TAs). We find that in migrating wild-type tandem pairs, each cell exerts traction forces on stationary sites (∼80% of the time), and the trailing cell reuses the location of the TAs of the leading cell. Both leading and trailing cells form contractile dipoles and synchronize the formation of new frontal TAs with ∼54-s time delay. Cells not expressing the lectin discoidin I or moving on discoidin I–coated substrata form fewer tandems, but the trailing cell still reuses the locations of the TAs of the leading cell, suggesting that discoidin I is not responsible for a possible chemically driven synchronization process. The migration dynamics of the tandems indicate that their TAs’ reuse results from the mechanical synchronization of the leading and trailing cells’ protrusions and retractions (motility cycles) aided by the cell–cell adhesions. PMID:26912787

DNA Damage by Ionizing Radiation: Tandem Double Lesions by Charged Particles

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Chaban, Galina M.; Wang, Dunyou; Dateo, Christopher E.

2005-01-01

Oxidative damages by ionizing radiation are the source of radiation-induced carcinogenesis, damage to the central nervous system, lowering of the immune response, as well as other radiation-induced damages to human health. Monte Carlo track simulations and kinetic modeling of radiation damages to the DNA employ available molecular and cellular data to simulate the biological effect of high and low LET radiation io the DNA. While the simulations predict single and double strand breaks and base damages, so far all complex lesions are the result of stochastic coincidence from independent processes. Tandem double lesions have not yet been taken into account. Unlike the standard double lesions that are produced by two separate attacks by charged particles or radicals, tandem double lesions are produced by one single attack. The standard double lesions dominate at the high dosage regime. On the other hand, tandem double lesions do not depend on stochastic coincidences and become important at the low dosage regime of particular interest to NASA. Tandem double lesions by hydroxyl radical attack of guanine in isolated DNA have been reported at a dosage of radiation as low as 10 Gy. The formation of two tandem base lesions was found to be linear with the applied doses, a characteristic of tandem lesions. However, tandem double lesions from attack by a charged particle have not been reported.

A tandem mirror hybrid plume plasma propulsion facility

NASA Technical Reports Server (NTRS)

Yang, T. F.; Krueger, W. A.; Peng, S.; Urbahn, J.; Chang-Diaz, F. R.

1988-01-01

This paper discusses a novel concept in electrodeless plasma propulsion, in which the materials problems are ameliorated by an electrodeless magnetic confinement scheme borrowed from the tandem mirror approach to controlled thermonuclear fusion. The concept also features a two-stage magnetic nozzle with an annular hypersonic coaxial gas injector near the throat. The nozzle produces hybrid plume by the coaxial injection of hypersonic neutral gas, and the gas layer thus formed protects the material walls from the hot plasma and, through increased collisions, helps detach it from the diverging magnetic field. The tandem mirror plasma propulsion facility is capable of delivering a variable I(sp). The results of numerical simulation of this concept are presented together with those from an experimental tandem-mirror plasma propulsion device.

Investigation into novel thiophene- and furan-based 4-amino-7-chloroquinolines afforded antimalarials that cure mice.

PubMed

Opsenica, Igor M; Verbić, Tatjana Ž; Tot, Mikloš; Sciotti, Richard J; Pybus, Brandon S; Djurković-Djaković, Olgica; Slavić, Ksenija; Šolaja, Bogdan A

2015-05-01

We herein report the design and synthesis of a novel series of thiophene- and furan-based aminoquinoline derivatives which were found to be potent antimalarials and inhibitors of β-hematin polymerization. Tested compounds were 3-71 times more potent in vitro than CQ against chloroquine-resistant (CQR) W2 strain with benzonitrile 30 being as active as mefloquine (MFQ), and almost all synthesized aminoquinolines (22/27) were more potent than MFQ against multidrug-resistant (MDR) strain C235. In vivo experiments revealed that compound 28 showed clearance with recrudescence at 40 mg/kg/day, while 5/5 mice survived in Thompson test at 160 mg/kg/day. Copyright © 2015 Elsevier Ltd. All rights reserved.

Intramolecular Charge Transfer States in the Condensed Phase

NASA Astrophysics Data System (ADS)

Williams, C. F.; Herbert, J. M.

2009-06-01

Time-Dependent Density Functional Theory (TDDFT) with long range corrected functionals can give accurate results for the energies of electronically excited states involving Intramolecular Charge Transfer (ICT) in large molecules. If this is combined with a Molecular Mechanics (MM) representation of the surrounding solvent this technique can be used to interpret the results of condensed phase UV-Vis Spectroscopy. Often the MM region is represented by a set of point charges, however this means that the solvent cannot repolarize to adapt to the new charge distribution as a result of ICT and so the excitation energies to ICT states are overestimated. To solve this problem an algorithm that interfaces TDDFT with the polarizable force-field AMOEBA is presented; the effect of solvation on charge transfer in species such as 4,4'dimethylaminobenzonitrile (DMABN) is discussed. M.A. Rohrdanz, K.M. Martins, and J.M. Herbert, J. Chem. Phys. 130 034107 (2008).

Alternating phenylene and furan/pyrrole/thiophene units-based oligomers: A computational study of the structures and optoelectronic properties

NASA Astrophysics Data System (ADS)

Sahu, Harikrishna; Shukla, Rishabh; Goswami, Juri; Gaur, Priyank; Panda, Aditya N.

2018-01-01

Structural and optoelectronic properties of phenylene-furan, phenylene-pyrrole and phenylene-thiophene oligomers are reported using density functional theory methods. Studies reveal that stabilities of conformers change with increasing chain length, and helical conformers are energetically feasible for large oligomers of the studied systems, due to stacking interactions between adjacent helical turns. Absorption spectra of helices are dominated by multiple number of electronic transitions other than the S0 →S1 , involving orbitals other than the HOMO/LUMO. All studied helices are optically active having similar pattern of negative and positive peaks in the CD spectra.

Monitoring Bilingualism: Pedagogical Implications of the Bilingual Tandem Analyser

ERIC Educational Resources Information Center

Schwienhorst, Klaus; Borgia, Alexandre

2006-01-01

Tandem learning is the collaborative learning partnership of two language learners with complementary language combinations, for example an Irish student learning German and a German student learning English. One of the major principles in tandem learning, apart from reciprocity and learner autonomy, is balanced bilingualism. While learners may…

Low-energy elastic electron scattering from furan

NASA Astrophysics Data System (ADS)

Khakoo, M. A.; Muse, J.; Ralphs, K.; da Costa, R. F.; Bettega, M. H. F.; Lima, M. A. P.

2010-06-01

We report normalized experimental and theoretical differential cross sections for elastic electron scattering by C4H4O (furan) molecules from a collaborative project between several Brazilian theoretical groups and an experimental group at California State Fullerton, USA. The measurements are obtained by using the relative flow method with helium as the standard gas and a thin aperture target gas collimating source. The relative flow method is applied without the restriction imposed by the relative flow pressure condition on helium and the unknown gas. The experimental data were taken at incident electron energies of 1, 1.5, 1.73, 2, 2.7, 3, 5, 7, 10, 20, 30, and 50 eV and covered the angular range between 10° and 130°. The measurements verify observed π* shape resonances at 1.65±0.05eV and 3.10±0.05 eV scattering energies, in good agreement with the transmission electron data of Modelli and Burrow [J. Phys. Chem. AJPCAFH 1089-563910.1021/jp048759a 108, 5721 (2004)]. Furthermore, the present results also indicated both resonances dominantly in the d-wave channel. The differential cross sections are integrated in the standard way to obtain integral elastic cross sections and momentum transfer cross sections. The calculations employed the Schwinger multichannel method with pseudopotentials and were performed in the static-exchange and in the static-exchange plus polarization approximations. The calculated integral and momentum transfer cross sections clearly revealed the presence of two shape resonances located at 1.95 and 3.56 eV and ascribed to the B1 and A2 symmetries of the C2v point group, respectively, in very good agreement with the experimental findings. Overall agreement between theory and experiment regarding the differential, momentum transfer, and integral cross sections is very good, especially for energies below 10 eV.

Acidic resin-catalysed conversion of fructose into furan derivatives in low boiling point solvents.

PubMed

Zhu, Hong; Cao, Quan; Li, Chunhu; Mu, Xindong

2011-09-27

Conversion of fructose into furan derivatives 5-hydroxymethylfurfural (HMF) and 5-methoxymethylfurfural (MMF) is performed in tetrahydrofuran (THF) and methanol-organic solvent systems, catalysed by an acidic resin Amberlyst-15. The melted fructose can be converted into HMF on the surface of the solid resin catalyst in the presence of THF as an extracting phase, which is a good solvent for HMF and other by-products. The solid resin catalyst can be reused eleven times without losing its catalytic ability, with an average HMF yield of approximately 50%. Upon the addition of methanol, the generated HMF can further react with methanol to form MMF, and the total yield of HMF and MMF could be promoted to 65%. GC-MS analysis confirms the formation of a small amount of methyl levulinate in methanolorganic solvent system. Copyright © 2011 Elsevier Ltd. All rights reserved.

High Performance Tandem Perovskite/Polymer Solar Cells

NASA Astrophysics Data System (ADS)

Liu, Yao; Bag, Monojit; Page, Zachariah; Renna, Lawrence; Kim, Paul; Choi, Jaewon; Emrick, Todd; Venkataraman, D.; Russell, Thomas

Combining perovskites with other inorganic materials, such as copper indium gallium diselenide (CIGS) or silicon, is enabling significant improvement in solar cell device performance. Here, we demonstrate a highly efficient hybrid tandem solar cell fabricated through a facile solution deposition approach to give a perovskite front sub-cell and a polymer:fullerene blend back sub-cell. This methodology eliminates the adverse effects of thermal annealing during perovskite fabrication on polymer solar cells. The record tandem solar cell efficiency of 15.96% is 40% greater than the corresponding perovskite-based single junction device and 65% greater than the polymer-based single junction device, while mitigating deleterious hysteresis effects often associated with perovskite solar cells. The hybrid tandem devices demonstrate the synergistic effects arising from the combination of perovskite and polymer-based materials for solar cells. This work was supported by the Department of Energy-supported Energy Frontier Research Center at the University of Massachusetts (DE-SC0001087). The authors acknowledge the W.M. Keck Electron Microscopy.

Molecular structures and intramolecular dynamics of pentahalides

NASA Astrophysics Data System (ADS)

Ischenko, A. A.

2017-03-01

This paper reviews advances of modern gas electron diffraction (GED) method combined with high-resolution spectroscopy and quantum chemical calculations in studies of the impact of intramolecular dynamics in free molecules of pentahalides. Some recently developed approaches to the electron diffraction data interpretation, based on direct incorporation of the adiabatic potential energy surface parameters to the diffraction intensity are described. In this way, complementary data of different experimental and computational methods can be directly combined for solving problems of the molecular structure and its dynamics. The possibility to evaluate some important parameters of the adiabatic potential energy surface - barriers to pseudorotation and saddle point of intermediate configuration from diffraction intensities in solving the inverse GED problem is demonstrated on several examples. With increasing accuracy of the electron diffraction intensities and the development of the theoretical background of electron scattering and data interpretation, it has become possible to investigate complex nuclear dynamics in fluxional systems by the GED method. Results of other research groups are also included in the discussion.

Intramolecular allyl transfer reaction from allyl ether to aldehyde groups: experimental and theoretical studies.

PubMed

Franco, Delphine; Wenger, Karine; Antonczak, Serge; Cabrol-Bass, Daniel; Duñach, Elisabet; Rocamora, Mercè; Gomez, Montserrat; Muller, Guillermo

2002-02-02

The intramolecular transfer of the allyl group of functionalized allyl aryl ethers to an aldehyde group in the presence of Ni0 complexes was studied from chemical, electrochemical and theoretical points of view. The chemical reaction involves the addition of Ni0 to the allyl ether followed by stoichiometric allylation. The electrochemical process is catalytic in nickel and involves the reduction of intermediate eta3-allylnickel(II) complexes.

Biotransformation of Furanic and Phenolic Compounds with Hydrogen Gas Production in a Microbial Electrolysis Cell.

PubMed

Zeng, Xiaofei; Borole, Abhijeet P; Pavlostathis, Spyros G

2015-11-17

Furanic and phenolic compounds are problematic byproducts resulting from the breakdown of lignocellulosic biomass during biofuel production. The capacity of a microbial electrolysis cell (MEC) to produce hydrogen gas (H2) using a mixture of two furanic (furfural, FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA; and 4-hydroxybenzoic acid, HBA) compounds as the substrate in the bioanode was assessed. The rate and extent of biotransformation of the five compounds and efficiency of H2 production, as well as the structure of the anode microbial community, were investigated. The five compounds were completely transformed within 7-day batch runs and their biotransformation rate increased with increasing initial concentration. At an initial concentration of 1200 mg/L (8.7 mM) of the mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The anode Coulombic efficiency was 44-69%, which is comparable to that of wastewater-fed MECs. The H2 yield varied from 0.26 to 0.42 g H2-COD/g COD removed in the anode, and the bioanode volume-normalized H2 production rate was 0.07-0.1 L/L-d. The biotransformation of the five compounds took place via fermentation followed by exoelectrogenesis. The major identified fermentation products that did not transform further were catechol and phenol. Acetate was the direct substrate for exoelectrogenesis. Current and H2 production were inhibited at an initial substrate concentration of 1200 mg/L, resulting in acetate accumulation at a much higher level than that measured in other batch runs conducted with a lower initial concentration of the five compounds. The anode microbial community consisted of exoelectrogens, putative degraders of the five compounds, and syntrophic partners of exoelectrogens. The MEC H2 production demonstrated in this study is an alternative to the currently used process of reforming natural gas to supply H2 needed to upgrade bio-oils to stable

Biotransformation of furanic and phenolic compounds with hydrogen gas production in a microbial electrolysis cell

DOE PAGES

Zeng, Xiaofei; Borole, Abhijeet P.; Pavlostathis, Spyros G.

2015-10-27

In this study, furanic and phenolic compounds are problematic byproducts resulting from the decomposition of lignocellulosic biomass during biofuel production. This study assessed the capacity of a microbial electrolysis cell (MEC) to produce hydrogen gas (H 2) using a mixture of two furanic (furfural, FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA; and 4-hydroxybenzoic acid, HBA) compounds as the sole carbon and energy source in the bioanode. The rate and extent of biotransformation of the five compounds, efficiency of H 2 production, as well as the anode microbial community structure were investigated. The five compoundsmore » were completely transformed within 7-day batch runs and their biotransformation rate increased with increasing initial concentration. At an initial concentration of 1,200 mg/L (8.7 mM) of the mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The anode coulombic efficiency was 44-69%, which is comparable to wastewater-fed MECs. The H 2 yield varied from 0.26 to 0.42 g H 2-COD/g COD removed in the anode, and the bioanode volume-normalized H 2 production rate was 0.07-0.1 L/L-d. The major identified fermentation products that did not transform further were catechol and phenol. Acetate was the direct substrate for exoelectrogenesis. Current and H 2 production were inhibited at an initial substrate concentration of 1,200 mg/L, resulting in acetate accumulation at a much higher level than that measured in other batch runs conducted with a lower initial concentration of the five compounds. The anode microbial community consisted of exoelectrogens, putative degraders of the five compounds, and syntrophic partners of exoelectrogens. The H 2 production route demonstrated in this study has proven to be an alternative to the currently used process of reforming natural gas to supply H 2 needed to upgrade bio-oils to stable hydrocarbon fuels.« less

rTANDEM, an R/Bioconductor package for MS/MS protein identification.

PubMed

Fournier, Frédéric; Joly Beauparlant, Charles; Paradis, René; Droit, Arnaud

2014-08-01

rTANDEM is an R/Bioconductor package that interfaces the X!Tandem protein identification algorithm. The package can run the multi-threaded algorithm on proteomic data files directly from R. It also provides functions to convert search parameters and results to/from R as well as functions to manipulate parameters and automate searches. An associated R package, shinyTANDEM, provides a web-based graphical interface to visualize and interpret the results. Together, those two packages form an entry point for a general MS/MS-based proteomic pipeline in R/Bioconductor. rTANDEM and shinyTANDEM are distributed in R/Bioconductor, http://bioconductor.org/packages/release/bioc/. The packages are under open licenses (GPL-3 and Artistice-1.0). frederic.fournier@crchuq.ulaval.ca or arnaud.droit@crchuq.ulaval.ca Supplementary data are available at Bioinformatics online. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Organochlorine pesticides, PCBs, dibenzodioxin, and furan concentrations in common snapping turtle eggs (Chelydra serpentina serpentina) in Akwesasne, Mohawk Territory, Ontario, Canada.

PubMed

de Solla, S R; Bishop, C A; Lickers, H; Jock, K

2001-04-01

Subsamples of eight clutches of common snapping turtle eggs (Chelydra serpentina serpentina) were collected from four sites from the territory of the Mohawk Nation, Akwesasne, on the shore of the St. Lawrence River. Egg contents were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), dibenzodioxins, and furans. The sites were 2 to 13 km downstream from PCB-contaminated landfill sites. Maximum concentrations of total PCBs in snapping turtle clutches were extremely high, and ranged from 2 378.2 ng/g to 737 683 ng/g (wet weight) and are among the highest recorded in any tissue of a free-ranging animal. Similarly, in a pooled sample of eggs from all four sites, the summed concentrations of non-ortho PCBs (n = 6 congeners) was also very high at 54.54 ng/g and the summed dioxin and furan concentrations (n = 11 congeners) was 85.8 ng/g. Sum organochlorine pesticide levels varied from 28 to 2,264 ng/g among the four sites. The levels of PCBs found in turtle eggs exceed concentrations associated with developmental problems and reduced hatching success in snapping turtles and other species and also exceed the Canadian tissue residue guidelines for toxic equivalency concentrations. The extremely high levels of organochlorine contaminants demonstrate the high degree of contamination in the environment in the Akwesasne area.

Poly(Neopentyl Glycol Furanoate): A Member of the Furan-Based Polyester Family with Smart Barrier Performances for Sustainable Food Packaging Applications

PubMed Central

Munari, Andrea

2017-01-01

In the last decade, there has been an increased interest from the food packaging industry toward the development and application of bioplastics, to contribute to the sustainable economy and to reduce the huge environmental problem afflicting the planet. In the present work, we focus on a new furan-based polyester, poly(neopentyl glycol 2,5-furanoate) (PNF) to be used for sustainable food packaging applications. The aromatic polyester was successfully synthesized with high molecular weight, through a solvent-free process, starting directly from 2,5-furandicarboxylic acid. PNF was revealed to be a material with good thermal stability, characterized by a higher Tg and Tm and a lower RAF fraction compared to poly(propylene 2,5-furanoate) (PPF), ascribable to the two methyl side groups present in PNF glycol-sub-unit. PNF’s mechanical characteristics, i.e., very high elastic modulus and brittle fracture, were found to be similar to those of PPF and PEF. Barrier properties to different gases, temperatures and relative humidity were evaluated. From the results obtained, PNF was showed to be a material with very smart barrier performances, significantly superior with respect to PEF’s ones. Lastly, PNF’s permeability behavior did not appreciably change after contact with food simulants, whereas it got worse with increasing RH, due to the polar nature of furan ring. PMID:28869555

Poly(Neopentyl Glycol Furanoate): A Member of the Furan-Based Polyester Family with Smart Barrier Performances for Sustainable Food Packaging Applications.

PubMed

Genovese, Laura; Lotti, Nadia; Siracusa, Valentina; Munari, Andrea

2017-09-04

In the last decade, there has been an increased interest from the food packaging industry toward the development and application of bioplastics, to contribute to the sustainable economy and to reduce the huge environmental problem afflicting the planet. In the present work, we focus on a new furan-based polyester, poly(neopentyl glycol 2,5-furanoate) (PNF) to be used for sustainable food packaging applications. The aromatic polyester was successfully synthesized with high molecular weight, through a solvent-free process, starting directly from 2,5-furandicarboxylic acid. PNF was revealed to be a material with good thermal stability, characterized by a higher T g and T m and a lower RAF fraction compared to poly(propylene 2,5-furanoate) (PPF), ascribable to the two methyl side groups present in PNF glycol-sub-unit. PNF's mechanical characteristics, i.e., very high elastic modulus and brittle fracture, were found to be similar to those of PPF and PEF. Barrier properties to different gases, temperatures and relative humidity were evaluated. From the results obtained, PNF was showed to be a material with very smart barrier performances, significantly superior with respect to PEF's ones. Lastly, PNF's permeability behavior did not appreciably change after contact with food simulants, whereas it got worse with increasing RH, due to the polar nature of furan ring.

Probing the rate-limiting step for intramolecular transfer of a transcription factor between specific sites on the same DNA molecule by (15)Nz-exchange NMR spectroscopy.

PubMed

Ryu, Kyoung-Seok; Tugarinov, Vitali; Clore, G Marius

2014-10-15

The kinetics of translocation of the homeodomain transcription factor HoxD9 between specific sites of the same or opposite polarities on the same DNA molecule have been studied by (15)Nz-exchange NMR spectroscopy. We show that exchange occurs by two facilitated diffusion mechanisms: a second-order intermolecular exchange reaction between specific sites located on different DNA molecules without the protein dissociating into free solution that predominates at high concentrations of free DNA, and a first-order intramolecular process involving direct transfer between specific sites located on the same DNA molecule. Control experiments using a mixture of two DNA molecules, each possessing only a single specific site, indicate that transfer between specific sites by full dissociation of HoxD9 into solution followed by reassociation is too slow to measure by z-exchange spectroscopy. Intramolecular transfer with comparable rate constants occurs between sites of the same and opposing polarity, indicating that both rotation-coupled sliding and hopping/flipping (analogous to geminate recombination) occur. The half-life for intramolecular transfer (0.5-1 s) is many orders of magnitude larger than the calculated transfer time (1-100 μs) by sliding, leading us to conclude that the intramolecular transfer rates measured by z-exchange spectroscopy represent the rate-limiting step for a one-base-pair shift from the specific site to the immediately adjacent nonspecific site. At zero concentration of added salt, the intramolecular transfer rate constants between sites of opposing polarity are smaller than those between sites of the same polarity, suggesting that hopping/flipping may become rate-limiting at very low salt concentrations.

A Binuclear 1,1'-Bis(boratabenzene) Complex: Unprecedented Intramolecular Metal-Metal Communication through a B-B Bond.

PubMed

Braunschweig, Holger; Demeshko, Serhiy; Ewing, William C; Krummenacher, Ivo; Macha, Bret B; Mattock, James D; Meyer, Franc; Mies, Jan; Schäfer, Marius; Vargas, Alfredo

2016-06-27

We report the synthesis of the first 1,1'-bis(boratabenzene) species by tetrabromodiborane(4)-induced ring-expansion reactions of cobaltocene. Six equivalents of cobaltocene are required as the species plays the dual role of reagent and reductant to yield [{(η(5) -C5 H5 )Co}2 {μ:η(6) ,η(6) -(BC5 H5 )2 }]. The formally dianionic bis(boratabenzene) moiety with a boron-boron single bond can be viewed as a symmetric dimer of the parent boratabenzene anion as well as the first example of a diboron analogue of biphenyl. The solution electrochemistry of the bimetallic complex shows four stepwise redox events, indicating significant intramolecular interaction between the cobalt ions across the 1,1'-bis(boratabenzene) unit. The magnetic properties, as investigated by variable-temperature SQUID magnetometry, reveal weak intramolecular antiferromagnetic interactions. Density functional theory calculations support the experimental results and add insight into the various electronic states of the complex. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

NASA Astrophysics Data System (ADS)

Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C.

2015-03-01

We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH2OO and anti/syn-CH3C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH2OO and anti-CH3C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH3C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C-H bonds. For syn-CH3C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH3 group by the terminal O atom producing CH2C(H)O-OH. At 298 K, the intramolecular insertion process in CH2OO was found to be 600 times faster than the commonly assumed ring-closing reaction.

Semi-transparent perovskite solar cells for tandems with silicon and CIGS

DOE PAGES

Bailie, Colin D.; Christoforo, M. Greyson; Mailoa, Jonathan P.; ...

2014-12-23

A promising approach for upgrading the performance of an established low-bandgap solar technology without adding much cost is to deposit a high bandgap polycrystalline semiconductor on top to make a tandem solar cell. We use a transparent silver nanowire electrode on perovskite solar cells to achieve a semi-transparent device. We place the semi-transparent cell in a mechanically-stacked tandem configuration onto copper indium gallium diselenide (CIGS) and low-quality multicrystalline silicon (Si) to achieve solid-state polycrystalline tandem solar cells with a net improvement in efficiency over the bottom cell alone. Furthermore, this work paves the way for integrating perovskites into a low-costmore » and high-efficiency (>25%) tandem cell.« less

Zinc Chloride Influence on The Resins Furan Polymerization to Foundry Moulds

NASA Astrophysics Data System (ADS)

de Miranda, Leila Figueiredo; Vale, Marcus; Júnior, Antonio Hortêncio Munhoz; Masson, Terezinha Jocelen; de Andrade e Silva, Leonardo Gondin

The resins used in foundry molds developed for the automotive market has led to major changes in the manufacturing method of foundry molds. The polymerization of these resins and a subsequent curing are used to connect to the foundry sand in a rigid structure capable of receiving and holding liquid metal. It is essential to know the process of polymerization of these resins and their impact on the final properties of the obtained molds, especially in the mechanical characteristics. In this work it was studied the influence of the addition of zinc chloride (in solution) in the sand-furan resin mixture, with the aim of reducing the relation between the extraction time intervals and time bench life. The results showed that addition of percentages of the order of 5.0wt% to 7.5wt% zinc chloride solution reduces this ratio between 10% and 17%; this means that the casting model may be extracted from the sand mass in a smaller time interval increasing the productivity of manufacturing molds. It was also observed that there was also an increase of 9% to 18% in bench life intervals.

The concentration and distribution of 2,3,7,8-dibenzo-p-dioxins/-furans in chickens

NASA Technical Reports Server (NTRS)

Ferrario, J.; Byrne, C.

2000-01-01

The concentrations of the 2,3,7,8-Cl substituted dibenzo-p-dioxins/-furans (PCDDs/PCDFs) were determined in the edible tissues of whole chicken fryers and compared with the values found in their abdominal fat. The values are presented both on a whole weight basis and on a lipid adjusted basis for each tissue. While there is a marked difference in the concentration of the 2,3,7,8-dibenzo-p-dioxins in the edible tissues expressed on a whole weight basis, the lipid-adjusted concentrations of the individual dioxins were not statistically different in the various tissues. This validates the use of lipid adjusted concentrations of 2,3,7,8-PCDDs/PCDFs in abdominal fat for the determination of the presence of these compounds in different tissues.

Impact of furan derivatives and phenolic compounds on hydrogen production from organic fraction of municipal solid waste using co-culture of Enterobacter aerogenes and E. coli.

PubMed

Sharma, Preeti; Melkania, Uma

2017-09-01

In the present study, the effect of furan derivatives (furfural and 5-hydroxymethylfurfural) and phenolic compounds (vanillin and syringaldehyde) on hydrogen production from organic fraction of municipal solid waste (OFMSW) was investigated using co-culture of facultative anaerobes Enterobacter aerogenes and E. coli. The inhibitors were applied in the concentration ranges of 0.25, 0.5, 1, 2 and 5g/L each. Inhibition coefficients of phenolic compounds were higher than those of furan derivatives and vanillin exhibited maximum inhibition coefficients correspondingly lowest hydrogen yield among all inhibitors. Furfural and 5-hydroxymethylfurfural addition resulted in an average decrease of 26.99% and 37.16% in hydrogen yield respectively, while vanillin and syringaldehyde resulted in 49.40% and 42.26% average decrease in hydrogen yield respectively. Further analysis revealed that Furfural and 5-hydroxymethylfurfural were completely degraded up to concentrations of 1g/L, while vanillin and syringaldehyde were degraded completely up to the concentration of 0.5g/L. Volatile fatty acid generation decreased with inhibitors addition. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metabolic Profile of Skimmianine in Rats Determined by Ultra-Performance Liquid Chromatography Coupled with Quadrupole Time-of-Flight Tandem Mass Spectrometry.

PubMed

Huang, Aihua; Xu, Hui; Zhan, Ruoting; Chen, Weiwen; Liu, Jiawei; Chi, Yuguang; Chen, Daidi; Ji, Xiaoyu; Luo, Chaoquan

2017-03-23

Skimmianine is a furoquinoline alkaloid present mainly in the Rutaceae family. It has been reported to have analgesic, antispastic, sedative, anti-inflammatory, and other pharmacologic activities. Despite its critical pharmacological function, its metabolite profiling is still unclear. In this study, the in vivo metabolite profiling of skimmianine in rats was investigated using ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UPLC/Q-TOF-MS). The metabolites were predicted using MetabolitePilot TM software. These predicted metabolites were further analyzed by MS² spectra, and compared with the detailed fragmentation pathway of the skimmianine standard and literature data. A total of 16 metabolites were identified for the first time in rat plasma, urine, and feces samples after oral administration of skimmianine. Skimmianine underwent extensive Phase I and Phase II metabolism in rats. The Phase I biotransformations of skimmianine consist of epoxidation of olefin on its furan ring (M1) followed by the hydrolysis of the epoxide ring (M4), hydroxylation (M2, M3), O -demethylation (M5-M7), didemethylation (M14-M16). The Phase II biotransformations include glucuronide conjugation (M8-M10) and sulfate conjugation (M11-M13). The epoxidation of 2,3-olefinic bond followed by the hydrolysis of the epoxide ring and O -demethylation were the major metabolic pathways of skimmianine. The results provide key information for understanding the biotransformation processes of skimmianine and the related furoquinoline alkaloids.

Economic viability of thin-film tandem solar modules in the United States

NASA Astrophysics Data System (ADS)

Sofia, Sarah E.; Mailoa, Jonathan P.; Weiss, Dirk N.; Stanbery, Billy J.; Buonassisi, Tonio; Peters, I. Marius

2018-05-01

Tandem solar cells are more efficient but more expensive per unit area than established single-junction (SJ) solar cells. To understand when specific tandem architectures should be utilized, we evaluate the cost-effectiveness of different II-VI-based thin-film tandem solar cells and compare them to the SJ subcells. Levelized cost of electricity (LCOE) and energy yield are calculated for four technologies: industrial cadmium telluride and copper indium gallium selenide, and their hypothetical two-terminal (series-connected subcells) and four-terminal (electrically independent subcells) tandems, assuming record SJ quality subcells. Different climatic conditions and scales (residential and utility scale) are considered. We show that, for US residential systems with current balance-of-system costs, the four-terminal tandem has the lowest LCOE because of its superior energy yield, even though it has the highest US per watt (US W-1) module cost. For utility-scale systems, the lowest LCOE architecture is the cadmium telluride single junction, the lowest US W-1 module. The two-terminal tandem requires decreased subcell absorber costs to reach competitiveness over the four-terminal one.

Flow Cytometry Enables Multiplexed Measurements of Genetically Encoded Intramolecular FRET Sensors Suitable for Screening.

PubMed

Doucette, Jaimee; Zhao, Ziyan; Geyer, Rory J; Barra, Melanie M; Balunas, Marcy J; Zweifach, Adam

2016-07-01

Genetically encoded sensors based on intramolecular FRET between CFP and YFP are used extensively in cell biology research. Flow cytometry has been shown to offer a means to measure CFP-YFP FRET; we suspected it would provide a unique way to conduct multiplexed measurements from cells expressing different FRET sensors, which is difficult to do with microscopy, and that this could be used for screening. We confirmed that flow cytometry accurately measures FRET signals using cells transiently transfected with an ERK activity reporter, comparing responses measured with imaging and cytometry. We created polyclonal long-term transfectant lines, each expressing a different intramolecular FRET sensor, and devised a way to bar-code four distinct populations of cells. We demonstrated the feasibility of multiplexed measurements and determined that robust multiplexed measurements can be conducted in plate format. To validate the suitability of the method for screening, we measured responses from a plate of bacterial extracts that in unrelated experiments we had determined contained the protein kinase C (PKC)-activating compound teleocidin A-1. The multiplexed assay correctly identifying the teleocidin A-1-containing well. We propose that multiplexed cytometric FRET measurements will be useful for analyzing cellular function and for screening compound collections. © 2016 Society for Laboratory Automation and Screening.

Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals

NASA Astrophysics Data System (ADS)

Cho, Daeheum; Ko, Kyoung Chul; Ikabata, Yasuhiro; Wakayama, Kazufumi; Yoshikawa, Takeshi; Nakai, Hiromi; Lee, Jin Yong

2015-01-01

The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH&HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals.

PubMed

Cho, Daeheum; Ko, Kyoung Chul; Ikabata, Yasuhiro; Wakayama, Kazufumi; Yoshikawa, Takeshi; Nakai, Hiromi; Lee, Jin Yong

2015-01-14

The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH&HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

Intramolecular electron transport in quinoprotein alcohol dehydrogenase of Acetobacter methanolicus: a redox-titration study

PubMed

Frébortova; Matsushita; Arata; Adachi

1998-01-27

Quinohemoprotein-cytochrome c complex alcohol dehydrogenase (ADH) of acetic acid bacteria consists of three subunits, of which subunit I contains pyrroloquinoline quinone (PQQ) and heme c, and subunit II contains three heme c components. The PQQ and heme c components are believed to be involved in the intramolecular electron transfer from ethanol to ubiquinone. To study the intramolecular electron transfer in ADH of Acetobacter methanolicus, the redox potentials of heme c components were determined with ADH complex and the isolated subunits I and II of A. methanolicus, as well as hybrid ADH consisting of the subunit I/III complex of Gluconobacter suboxydans ADH and subunit II of A. methanolicus ADH. The redox potentials of hemes c in ADH complex were -130, 49, 188, and 188 mV at pH 7.0 and 24, 187, 190, and 255 mV at pH 4.5. In hybrid ADH, one of these heme c components was largely changed in the redox potential. Reduced ADH was fully oxidized with potassium ferricyanide, while ubiquinone oxidized the enzyme partially. The results indicate that electrons extracted from ethanol at PQQ site are transferred to ubiquinone via heme c in subunit I and two of the three hemes c in subunit II. Copyright 1998 Elsevier Science B.V.

ALG-2 activates the MVB sorting function of ALIX through relieving its intramolecular interaction

PubMed Central

Sun, Sheng; Zhou, Xi; Corvera, Joe; Gallick, Gary E; Lin, Sue-Hwa; Kuang, Jian

2015-01-01

The modular adaptor protein ALIX is critically involved in endosomal sorting complexes required for transport (ESCRT)-mediated multivesicular body (MVB) sorting of activated epidermal growth factor receptor (EGFR); however, ALIX contains a default intramolecular interaction that renders ALIX unable to perform this ESCRT function. The ALIX partner protein ALG-2 is a calcium-binding protein that belongs to the calmodulin superfamily. Prompted by a defined biological function of calmodulin, we determined the role of ALG-2 in regulating ALIX involvement in MVB sorting of activated EGFR. Our results show that calcium-dependent ALG-2 interaction with ALIX completely relieves the intramolecular interaction of ALIX and promotes CHMP4-dependent ALIX association with the membrane. EGFR activation induces increased ALG-2 interaction with ALIX, and this increased interaction is responsible for increased ALIX association with the membrane. Functionally, inhibition of ALIX activation by ALG-2 inhibits MVB sorting of activated EGFR as effectively as inhibition of ALIX interaction with CHMP4 does; however, inhibition of ALIX activation by ALG-2 does not affect cytokinetic abscission or equine infectious anemia virus (EIAV) budding. These findings indicate that calcium-dependent ALG-2 interaction with ALIX is specifically responsible for generating functional ALIX that supports MVB sorting of ubiquitinated membrane receptors. PMID:27462417

Typing Clostridium difficile strains based on tandem repeat sequences

PubMed Central

2009-01-01

Background Genotyping of epidemic Clostridium difficile strains is necessary to track their emergence and spread. Portability of genotyping data is desirable to facilitate inter-laboratory comparisons and epidemiological studies. Results This report presents results from a systematic screen for variation in repetitive DNA in the genome of C. difficile. We describe two tandem repeat loci, designated 'TR6' and 'TR10', which display extensive sequence variation that may be useful for sequence-based strain typing. Based on an investigation of 154 C. difficile isolates comprising 75 ribotypes, tandem repeat sequencing demonstrated excellent concordance with widely used PCR ribotyping and equal discriminatory power. Moreover, tandem repeat sequences enabled the reconstruction of the isolates' largely clonal population structure and evolutionary history. Conclusion We conclude that sequence analysis of the two repetitive loci introduced here may be highly useful for routine typing of C. difficile. Tandem repeat sequence typing resolves phylogenetic diversity to a level equivalent to PCR ribotypes. DNA sequences may be stored in databases accessible over the internet, obviating the need for the exchange of reference strains. PMID:19133124

Stereoselective Synthesis of Methylene Oxindoles via Palladium(II)-Catalyzed Intramolecular Cross-Coupling of Carbamoyl Chlorides.

PubMed

Le, Christine M; Sperger, Theresa; Fu, Rui; Hou, Xiao; Lim, Yong Hwan; Schoenebeck, Franziska; Lautens, Mark

2016-11-02

We report a highly robust, general and stereoselective method for the synthesis of 3-(chloromethylene)oxindoles from alkyne-tethered carbamoyl chlorides using PdCl 2 (PhCN) 2 as the catalyst. The transformation involves a stereo- and regioselective chloropalladation of an internal alkyne to generate a nucleophilic vinyl Pd II species, which then undergoes an intramolecular cross-coupling with a carbamoyl chloride. The reaction proceeds under mild conditions, is insensitive to the presence of moisture and air, and is readily scalable. The products obtained from this reaction are formed with >95:5 Z:E selectivity in nearly all cases and can be used to access biologically relevant oxindole cores. Through combined experimental and computational studies, we provide insight into stereo- and regioselectivity of the chloropalladation step, as well as the mechanism for the C-C bond forming process. Calculations provide support for a mechanism involving oxidative addition into the carbamoyl chloride bond to generate a high valent Pd IV species, which then undergoes facile C-C reductive elimination to form the final product. Overall, the transformation constitutes a formal Pd II -catalyzed intramolecular alkyne chlorocarbamoylation reaction.

Morbidity study of extruder personnel with potential exposure to brominated dioxins and furans. II. Results of clinical laboratory studies.

PubMed Central

Ott, M G; Zober, A

1996-01-01

OBJECTIVE: To test whether dioxins affect liver and thyroid function, lipid metabolism and glucose or immunological variables, in workers exposed to brominated dioxins and furans. METHODS: 34 male production employees (29 were extruder operators) and eight technical support personnel were studied, all of whom were potentially exposed to polybrominated dibenzo-p-dioxins (PBDDs) and furans (PBDFs) during production of resins containing polybrominated diphenyl ethers (PBDEs). Controls were from a similar resin producing plant that did not use PBDEs. Blood samples were analysed for tetra, penta, and hexabrominated congeners, but 2,3,7,8-TBDD was the only exposure measure used in the regression analyses. Seven liver function indicators, five measures of blood lipids and glucose, four haematology and blood coagulation measures, and three measures of thyroid function were examined. RESULTS: None of the variables was statistically related to concentration of 2,3,7,8-TBDD in the regression analyses. Cigarette smoking was related to several outcomes at the 0.05 level: aspartate aminotransferase, alanine aminotransferase, glutamate dehydrogenase (GLDH), erythrocyte sedimentation rate, and white blood cell count. Body mass index was also related to alanine aminotransferase, gamma-glutamyltranspeptidase, cholinesterase, GLDH, cholesterol, triglycerides, high density lipoprotein, low density lipoprotein, and glucose concentrations. No definitive associations between liver, blood lipid, thyroid, or immunological variables and exposure to brominated dioxins or blood lipid concentration of 2,3,7,8-TBDD were found. CONCLUSIONS: The study population was small and hence the findings must be interpreted with caution. Nevertheless, these results provide a base for interpreting the results of clinical studies in similarly exposed populations. PMID:8994404

Morbidity study of extruder personnel with potential exposure to brominated dioxins and furans. II. Results of clinical laboratory studies.

PubMed

Ott, M G; Zober, A

1996-12-01

To test whether dioxins affect liver and thyroid function, lipid metabolism and glucose or immunological variables, in workers exposed to brominated dioxins and furans. 34 male production employees (29 were extruder operators) and eight technical support personnel were studied, all of whom were potentially exposed to polybrominated dibenzo-p-dioxins (PBDDs) and furans (PBDFs) during production of resins containing polybrominated diphenyl ethers (PBDEs). Controls were from a similar resin producing plant that did not use PBDEs. Blood samples were analysed for tetra, penta, and hexabrominated congeners, but 2,3,7,8-TBDD was the only exposure measure used in the regression analyses. Seven liver function indicators, five measures of blood lipids and glucose, four haematology and blood coagulation measures, and three measures of thyroid function were examined. None of the variables was statistically related to concentration of 2,3,7,8-TBDD in the regression analyses. Cigarette smoking was related to several outcomes at the 0.05 level: aspartate aminotransferase, alanine aminotransferase, glutamate dehydrogenase (GLDH), erythrocyte sedimentation rate, and white blood cell count. Body mass index was also related to alanine aminotransferase, gamma-glutamyltranspeptidase, cholinesterase, GLDH, cholesterol, triglycerides, high density lipoprotein, low density lipoprotein, and glucose concentrations. No definitive associations between liver, blood lipid, thyroid, or immunological variables and exposure to brominated dioxins or blood lipid concentration of 2,3,7,8-TBDD were found. The study population was small and hence the findings must be interpreted with caution. Nevertheless, these results provide a base for interpreting the results of clinical studies in similarly exposed populations.

Intramolecular hydrogen bonds: ab initio Car Parrinello simulations of arylamide torsions

NASA Astrophysics Data System (ADS)

Doerksen, Robert J.; Chen, Bin; Klein, Michael L.

2003-10-01

Gas-phase, room temperature Car-Parrinello molecular dynamics simulations using the HCTH density functional are reported for the arylamides acetanilide ( 1) and ortho-methylthioacetanilide ( 2). The simulations show that in 1, rotation around the ring-amide bond is relatively unrestricted. By contrast, in 2 the methylthio side chain encourages the amide to be directed with N-H pointing toward S, not to flip by 360°, and furthermore to remain close to coplanar with the benzene ring. Because of an intramolecular N-H⋯S hydrogen bond, the N-H stretch frequency of 2 is red-shifted by ˜78 cm -1 compared to that of 1.

Direct electrochemistry and intramolecular electron transfer of ascorbate oxidase confined on L-cysteine self-assembled gold electrode.

PubMed

Patil, Bhushan; Kobayashi, Yoshiki; Fujikawa, Shigenori; Okajima, Takeyoshi; Mao, Lanqun; Ohsaka, Takeo

2014-02-01

A direct electrochemistry and intramolecular electron transfer of multicopper oxidases are of a great importance for the fabrication of these enzyme-based bioelectrochemical-devices. Ascorbate oxidase from Acremonium sp. (ASOM) has been successfully immobilized via a chemisorptive interaction on the l-cysteine self-assembled monolayer modified gold electrode (cys-SAM/AuE). Thermodynamics and kinetics of adsorption of ASOM on the cys-SAM/AuE were studied using cyclic voltammetry. A well-defined redox wave centered at 166±3mV (vs. Ag│AgCl│KCl(sat.)) was observed in 5.0mM phosphate buffer solution (pH7.0) at the fabricated ASOM electrode, abbreviated as ASOM/cys-SAM/AuE, confirming a direct electrochemistry, i.e., a direct electron transfer (DET) between ASOM and cys-SAM/AuE. The direct electrochemistry of ASOM was further confirmed by taking into account the chemical oxidation of ascorbic acid (AA) by O2 via an intramolecular electron transfer in the ASOM as well as the electrocatalytic oxidation of AA at the ASOM/cys-SAM/AuE. Thermodynamics and kinetics of the adsorption of ASOM on the cys-SAM/AuE have been elaborated along with its direct electron transfer at the modified electrodes on the basis of its intramolecular electron transfer and electrocatalytic activity towards ascorbic acid oxidation and O2 reduction. ASOM saturated surface area was obtained as 2.41×10(-11)molcm(-2) with the apparent adsorption coefficient of 1.63×10(6)Lmol(-1). The ASOM confined on the cys-SAM/AuE possesses its essential enzymatic function. © 2013.

Solution-processed parallel tandem polymer solar cells using silver nanowires as intermediate electrode.

PubMed

Guo, Fei; Kubis, Peter; Li, Ning; Przybilla, Thomas; Matt, Gebhard; Stubhan, Tobias; Ameri, Tayebeh; Butz, Benjamin; Spiecker, Erdmann; Forberich, Karen; Brabec, Christoph J

2014-12-23

Tandem architecture is the most relevant concept to overcome the efficiency limit of single-junction photovoltaic solar cells. Series-connected tandem polymer solar cells (PSCs) have advanced rapidly during the past decade. In contrast, the development of parallel-connected tandem cells is lagging far behind due to the big challenge in establishing an efficient interlayer with high transparency and high in-plane conductivity. Here, we report all-solution fabrication of parallel tandem PSCs using silver nanowires as intermediate charge collecting electrode. Through a rational interface design, a robust interlayer is established, enabling the efficient extraction and transport of electrons from subcells. The resulting parallel tandem cells exhibit high fill factors of ∼60% and enhanced current densities which are identical to the sum of the current densities of the subcells. These results suggest that solution-processed parallel tandem configuration provides an alternative avenue toward high performance photovoltaic devices.

2,3,5-Substituted tetrahydrofurans: COX-2 inhibitory activities of 5-hydroxymethyl-/carboxyl-2,3-diaryl-tetrahydro-furan-3-ols.

PubMed

Singh, Palwinder; Mittal, Anu; Kaur, Satwinderjeet; Kumar, Subodh

2008-12-01

5-Hydroxymethyl-/carboxyl-2,3-diaryl-tetrahydro-furan-3-ols have been investigated for their COX-1 and COX-2 inhibitory activities. Compounds 17, 18 and 20 have been identified as showing appreciable COX-2 inhibition and selectivity. The group present at C-5 of tetrahydrofuran and the substituents at the two phenyl rings, through their interactions with active site amino acid residues, significantly affect the activities of these molecules. The quantitative structure-activity relationship studies indicate the role of logP, TPSA, molecular connectivity and valence connectivity towards the activities of these molecules.

Bifunctional ferrocene-based squaramide-phosphine as an organocatalyst for highly enantioselective intramolecular Morita-Baylis-Hillman reaction.

PubMed

Zhang, Xiaorui; Ma, Pengfei; Zhang, Dongxu; Lei, Yang; Zhang, Shengyong; Jiang, Ru; Chen, Weiping

2014-04-21

This work demonstrates that, in accord with metal catalysis, ferrocene could be an excellent scaffold for organocatalysts. The simple and easily accessible bifunctional ferrocene-based squaramide-phosphine shows high enantioselectivity in the intramolecular Morita-Baylis-Hillman reaction of 7-aryl-7-oxo-5-heptenals, giving a variety of 2-aroyl-2-cyclohexenols in up to 96% ee.

Tandem Repeated Irritation Test (TRIT) Studies and Clinical Relevance: Post 2006.

PubMed

Reddy, Rasika; Maibach, Howard

2018-06-11

Single or multiple applications of irritants can lead to occupational contact dermatitis, and most commonly irritant contact dermatitis (ICD). Tandem irritation, the sequential application of two irritants to a target skin area, has been studied using the Tandem Repeated Irritation Test (TRIT) to provide a more accurate representation of skin irritation. Here we present an update to Kartono's review on tandem irritation studies since 2006 [1]. We surveyed the literature available on PubMed, Embase, Google Scholar, and the UCSF Dermatology library databases since 2006. The studies included discuss the tandem effects of common chemical irritants, organic solvents, occlusion as well as clinical relevance - and enlarge our ability to discern whether multiple chemical exposures are more or less likely to enhance irritation.

Bacterial Conversion of Hydroxylamino Aromatic Compounds by both Lyase and Mutase Enzymes Involves Intramolecular Transfer of Hydroxyl Groups

PubMed Central

Nadeau, Lloyd J.; He, Zhongqi; Spain, Jim C.

2003-01-01

Hydroxylamino aromatic compounds are converted to either the corresponding aminophenols or protocatechuate during the bacterial degradation of nitroaromatic compounds. The origin of the hydroxyl group of the products could be the substrate itself (intramolecular transfer mechanism) or the solvent water (intermolecular transfer mechanism). The conversion of hydroxylaminobenzene to 2-aminophenol catalyzed by a mutase from Pseudomonas pseudoalcaligenes JS45 proceeds by an intramolecular hydroxyl transfer. The conversions of hydroxylaminobenzene to 2- and 4-aminophenol by a mutase from Ralstonia eutropha JMP134 and to 4-hydroxylaminobenzoate to protocatechuate by a lyase from Comamonas acidovorans NBA-10 and Pseudomonas sp. strain 4NT were proposed, but not experimentally proved, to proceed by the intermolecular transfer mechanism. GC-MS analysis of the reaction products formed in H218O did not indicate any 18O-label incorporation during the conversion of hydroxylaminobenzene to 2- and 4-aminophenols catalyzed by the mutase from R. eutropha JMP134. During the conversion of 4-hydroxylaminobenzoate catalyzed by the hydroxylaminolyase from Pseudomonas sp. strain 4NT, only one of the two hydroxyl groups in the product, protocatechuate, was 18O labeled. The other hydroxyl group in the product must have come from the substrate. The mutase in strain JS45 converted 4-hydroxylaminobenzoate to 4-amino-3-hydroxybenzoate, and the lyase in Pseudomonas strain 4NT converted hydroxylaminobenzene to aniline and 2-aminophenol but not to catechol. The results indicate that all three types of enzyme-catalyzed rearrangements of hydroxylamino aromatic compounds proceed via intramolecular transfer of hydroxyl groups. PMID:12732549

Effect of structural modifications of ganglioside GM2 on intra-molecular carbohydrate-to-carbohydrate interaction and enzymatic susceptibility

PubMed Central

Li, Yu-Teh; Li, Su-Chen; Kiso, Makoto; Ishida, Hideharu; Mauri, Laura; Raimondi, Laura; Bernardi, Anna; Sonnino, Sandro

2008-01-01

Summary The effect of inter-molecular carbohydrate-to-carbohydrate interaction on basic cell biological processes has been well documented and appreciated. In contrast, very little is known about the intra-molecular carbohydrate-to-carbohydrate interaction. The presence of an interaction between the GalNAc and the Neu5Ac in GM2 detected by NMR spectroscopy represents a well-defined intra-molecular carbohydrate-to-carbohydrate interaction. This intriguing interaction is responsible for the GM2-epitope, GalNAcβ1Π4(Neu5Acα2Π3)Gal-, to exhibit a rigid and compact conformation. We hypothesized that this compact conformation may be the cause for both the GalNAc and the Neu5Ac in GM2 to be refractory to enzymatic hydrolysis and the GM2 activator protein is able to interact with the compact trisaccharide GM2-epitope, rendering the GalNAc and the Neu5Ac accessible to β-hexosaminidase A and sialidase. We have used a series of structurally modified GM2 to study the effect of modifications of sugar chains on the conformation and enzymatic susceptibility of this ganglioside. Our hypothesis was borne out by the fact that when the GalNAcβ1Π4Gal linkage in GM2 was converted to the GalNAcβ1Π6Gal, both the GalNAc and the Neu5Ac became susceptible to β-hexosaminidase A and sialidase, respectively, without GM2 activator protein. We hope our work will engender interest in identifying other intra-molecular carbohydrate-to-carbohydrate interactions in glycoconjugates. PMID:17967427

Effect of structural modifications of ganglioside GM2 on intra-molecular carbohydrate-to-carbohydrate interaction and enzymatic susceptibility.

PubMed

Li, Yu-Teh; Li, Su-Chen; Kiso, Makoto; Ishida, Hideharu; Mauri, Laura; Raimondi, Laura; Bernardi, Anna; Sonnino, Sandro

2008-03-01

The effect of inter-molecular carbohydrate-to-carbohydrate interaction on basic cell biological processes has been well documented and appreciated. In contrast, very little is known about the intra-molecular carbohydrate-to-carbohydrate interaction. The presence of an interaction between the GalNAc and the Neu5Ac in GM2 detected by NMR spectroscopy represents a well-defined intra-molecular carbohydrate-to-carbohydrate interaction. This intriguing interaction is responsible for the GM2-epitope, GalNAcbeta1-->4(Neu5Acalpha2-->3)Gal-, to exhibit a rigid and compact conformation. We hypothesized that this compact conformation may be the cause for both the GalNAc and the Neu5Ac in GM2 to be refractory to enzymatic hydrolysis and the GM2 activator protein is able to interact with the compact trisaccharide GM2-epitope, rendering the GalNAc and the Neu5Ac accessible to beta-hexosaminidase A and sialidase. We have used a series of structurally modified GM2 to study the effect of modifications of sugar chains on the conformation and enzymatic susceptibility of this ganglioside. Our hypothesis was borne out by the fact that when the GalNAcbeta1-->4Gal linkage in GM2 was converted to the GalNAcbeta1-->6Gal, both the GalNAc and the Neu5Ac became susceptible to beta-hexosaminidase A and sialidase, respectively, without GM2 activator protein. We hope our work will engender interest in identifying other intra-molecular carbohydrate-to-carbohydrate interactions in glycoconjugates.

Expression of a heat-stable NADPH-dependent alcohol dehydrogenase in Caldicellulosiruptor bescii results in furan aldehyde detoxification

DOE PAGES

Chung, Daehwan; Verbeke, Tobin J.; Cross, Karissa L.; ...

2015-07-22

Compounds such as furfural and 5-hydroxymethylfurfural (5-HMF) are generated through the dehydration of xylose and glucose, respectively, during dilute-acid pretreatment of lignocellulosic biomass and are also potent microbial growth and fermentation inhibitors. The enzymatic reduction of these furan aldehydes to their corresponding, and less toxic, alcohols is an engineering approach that has been successfully implemented in both Saccharomyces cerevisiae and ethanologenicEscherichia coli, but has not yet been investigated in thermophiles relevant to biofuel production through consolidated bioprocessing (CBP). Developing CBP-relevant biocatalysts that are either naturally resistant to such inhibitors, or are amenable to engineered resistance, is therefore, an important componentmore » in making biofuels production from lignocellulosic biomass feasible.« less

Effect of Reclamation on the Skin Layer of Ductile Iron Cast in Furan Molds

NASA Astrophysics Data System (ADS)

Dańko, R.; Holtzer, M.; Górny, M.; Żymankowska-Kumon, S.

2013-11-01

The paper presents the results of investigations of the influence of the quality of molding sand with furan resin hardened by paratoluenesulfonic acid, on the formation of microstructure and surface quality of ductile iron castings. Within the studies different molding sands were used: molding sand prepared with fresh sand and molding sands prepared with reclaimed sands of a different purification degree, determined by the ignition loss value. Various concentrations of sulfur and nitrogen in the sand molds as a function of the ignition loss were shown in the paper. A series of experimental melts of ductile iron in molds made of molding sand characterized by different levels of surface-active elements (e.g., sulfur) and different gas evolution rates were performed. It was shown that there exists a significant effect of the quality of the sand on the formation of the graphite degeneration layer.

Crystal structure of 1,2,3,5-di-O-methyl­ene-α-d-xylo­furan­ose

PubMed Central

Tiritiris, Ioannis; Tussetschläger, Stefan; Kantlehner, Willi

2015-01-01

The title compound, C7H10O5, was synthesized by reaction of d-xylose with paraformaldehyde. In the crystal, the central part of the mol­ecule consists of a five-membered C4O ring with an envelope conformation, with the methine C atom adjacent to the O atom being the flap. The protected O atoms of both cyclic acetal groups are oriented so that the four chiral C atoms of the furan­ose part show an R configuration. C—H⋯O hydrogen bonds are present between adjacent mol­ecules, generating a three-dimensional network. PMID:26594582

Spectroscopic studies of the intramolecular hydrogen bonding in o-hydroxy Schiff bases, derived from diaminomaleonitrile, and their deprotonation reaction products

NASA Astrophysics Data System (ADS)

Szady-Chełmieniecka, Anna; Kołodziej, Beata; Morawiak, Maja; Kamieński, Bohdan; Schilf, Wojciech

2018-01-01

The structural study of five Schiff bases derived from diaminomaleonitrile (DAMN) and 2-hydroxy carbonyl compounds was performed using 1H, 13C and 15N NMR methods in solution and in the solid state as well. ATR-FTIR and X-Ray spectroscopies were used for confirmation of the results obtained by NMR method. The imine obtained from DAMN and benzaldehyde was synthesized as a model compound which lacks intramolecular hydrogen bond. Deprotonation of all synthesized compounds was done by treating with tetramethylguanidine (TMG). NMR data revealed that salicylidene Schiff bases in DMSO solution exist as OH forms without intramolecular hydrogen bonds and independent on the substituents in aromatic ring. In the case of 2-hydroxy naphthyl derivative, the OH proton is engaged into weak intramolecular hydrogen bond. Two of imines (salDAMN and 5-BrsalDAMN) exist in DMSO solution as equilibrium mixtures of two isomers (A and B). The structures of equilibrium mixture in the solid state have been studied by NMR, ATR-FTIR and X-Ray methods. The deprotonation of three studied compounds (salDAMN, 5-BrsalDAMN, and 5-CH3salDAMN) proceeded in two different ways: deprotonation of oxygen atom (X form) or of nitrogen atom of free primary amine group of DAMN moiety (Y form). For 5-NO2salDAMN and naphDAMN only one form (X) was observed.

Flow field interactions between two tandem cyclists

NASA Astrophysics Data System (ADS)

Barry, Nathan; Burton, David; Sheridan, John; Thompson, Mark; Brown, Nicholas A. T.

2016-12-01

Aerodynamic drag is the primary resistive force acting on cyclists at racing speeds. Many events involve cyclists travelling in very close proximity. Previous studies have shown that interactions result in significant drag reductions for inline cyclists. However, the interaction between cyclist leg position (pedalling) and the vortical flow structures that contribute significantly to the drag on an isolated cyclist has not previously been quantified or described for tandem cyclists of varying separation. To this end, scale model cyclists were constructed for testing in a water channel for inline tandem configurations. Particle image velocimetry was used to capture time-averaged velocity fields around two tandem cyclists. Perhaps surprisingly, the wake of a trailing cyclist maintains strong similarity to the characteristic wake of a single cyclist despite a significant disturbance to the upstream flow. Together with streamwise velocity measurements through the wake and upstream of the trailing cyclist, this work supports previous findings, which showed that the trailing cyclist drag reduction is primarily due to upstream sheltering effects reducing the stagnation pressure on forward-facing surfaces.

Stacking multiple connecting functional materials in tandem organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Zhang, Tao; Wang, Deng-Ke; Jiang, Nan; Lu, Zheng-Hong

2017-02-01

Tandem device is an important architecture in fabricating high performance organic light-emitting diodes and organic photovoltaic cells. The key element in making a high performance tandem device is the connecting materials stack, which plays an important role in electric field distribution, charge generation and charge injection. For a tandem organic light-emitting diode (OLED) with a simple Liq/Al/MoO3 stack, we discovered that there is a significant current lateral spreading causing light emission over an extremely large area outside the OLED pixel when the Al thickness exceeds 2 nm. This spread light emission, caused by an inductive electric field over one of the device unit, limits one’s ability to fabricate high performance tandem devices. To resolve this issue, a new connecting materials stack with a C60 fullerene buffer layer is reported. This new structure permits optimization of the Al metal layer in the connecting stack and thus enables us to fabricate an efficient tandem OLED having a high 155.6 cd/A current efficiency and a low roll-off (or droop) in current efficiency.

Diazo Esters as Dienophiles in Intramolecular (4 + 2) Cycloadditions: Computational Explorations of Mechanism.

PubMed

Duan, Abing; Yu, Peiyuan; Liu, Fang; Qiu, Huang; Gu, Feng Long; Doyle, Michael P; Houk, K N

2017-02-22

The first experimental examples of Diels-Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the M06-2X functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in intermolecular model systems have been analyzed by the distortion/interaction model. The 1,3-dipolar cycloaddition is strongly favored for the intermolecular system. The intramolecular example is unique because the tether strongly favors the (4 + 2) cycloaddition.

[Polymorphic loci and polymorphism analysis of short tandem repeats within XNP gene].

PubMed

Liu, Qi-Ji; Gong, Yao-Qin; Guo, Chen-Hong; Chen, Bing-Xi; Li, Jiang-Xia; Guo, Yi-Shou

2002-01-01

To select polymorphic short tandem repeat markers within X-linked nuclear protein (XNP) gene, genomic clones which contain XNP gene were recognized by homologous analysis with XNP cDNA. By comparing the cDNA with genomic DNA, non-exonic sequences were identified, and short tandem repeats were selected from non-exonic sequences by using BCM search Launcher. Polymorphisms of the short tandem repeats in Chinese population were evaluated by PCR amplification and PAGE. Five short tandem repeats were identified from XNP gene, two of which were polymorphic. Four and 11 alleles were observed in Chinese population for XNPSTR1 and XNPSTR4, respectively. Heterozygosities were 47% for XNPSTR1 and 70% for XNPSTR4. XNPSTR1 and XNPSTR4 localized within 3' end and intron 10, respectively. Two polymorphic short tandem repeats have been identified within XNP gene and will be useful for linkage analysis and gene diagnosis of XNP gene.

Low-Cost CdTe/Silicon Tandem Solar Cells

DOE PAGES

Tamboli, Adele C.; Bobela, David C.; Kanevce, Ana; ...

2017-09-06

Achieving higher photovoltaic efficiency in single-junction devices is becoming increasingly difficult, but tandem modules offer the possibility of significant efficiency improvements. By device modeling we show that four-terminal CdTe/Si tandem solar modules offer the prospect of 25%-30% module efficiency, and technoeconomic analysis predicts that these efficiency gains can be realized at costs per Watt that are competitive with CdTe and Si single junction alternatives. The cost per Watt of the modeled tandems is lower than crystalline silicon, but slightly higher than CdTe alone. But, these higher power modules reduce area-related balance of system costs, providing increased value especially in area-constrainedmore » applications. This avenue for high-efficiency photovoltaics enables improved performance on a near-term timeframe, as well as a path to further reduced levelized cost of electricity as module and cell processes continue to advance.« less

Low-Cost CdTe/Silicon Tandem Solar Cells

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

Tamboli, Adele C.; Bobela, David C.; Kanevce, Ana

Achieving higher photovoltaic efficiency in single-junction devices is becoming increasingly difficult, but tandem modules offer the possibility of significant efficiency improvements. By device modeling we show that four-terminal CdTe/Si tandem solar modules offer the prospect of 25%-30% module efficiency, and technoeconomic analysis predicts that these efficiency gains can be realized at costs per Watt that are competitive with CdTe and Si single junction alternatives. The cost per Watt of the modeled tandems is lower than crystalline silicon, but slightly higher than CdTe alone. But, these higher power modules reduce area-related balance of system costs, providing increased value especially in area-constrainedmore » applications. This avenue for high-efficiency photovoltaics enables improved performance on a near-term timeframe, as well as a path to further reduced levelized cost of electricity as module and cell processes continue to advance.« less

Partners in crime: The role of tandem modules in gene transcription.

PubMed

Sharma, Rajal; Zhou, Ming-Ming

2015-09-01

Histones and their modifications play an important role in the regulation of gene transcription. Numerous modifications, such as acetylation, phosphorylation, methylation, ubiquitination, and SUMOylation, have been described. These modifications almost always co-occur and thereby increase the combinatorial complexity of post-translational modification detection. The domains that recognize these histone modifications often occur in tandem in the context of larger proteins and complexes. The presence of multiple modifications can positively or negatively regulate the binding of these tandem domains, influencing downstream cellular function. Alternatively, these tandem domains can have novel functions from their independent parts. Here we summarize structural and functional information known about major tandem domains and their histone binding properties. An understanding of these interactions is key for the development of epigenetic therapy. © 2015 The Protein Society.

Theoretical studies on the Mo-catalyzed asymmetric intramolecular Pauson-Khand-type [2+2+1] cycloadditions of 3-allyloxy-1-propynylphosphonates.

PubMed

Meng, Qingxi; Li, Ming

2012-08-01

Density functional theory (DFT) was used to investigate the Mo-catalyzed intramolecular Pauson-Khand reaction of 3-allyloxy-1-propynylphosphonates. All intermediates and transition states were optimized completely at the B3LYP/6-31 G(d,p) level [LANL2DZ(f) for Mo]. In the Mo-catalyzed intramolecular Pauson-Khand reaction, the C–C oxidative cyclization reaction was the chirality-determining step, and the reductive elimination reaction was the rate-determining step. The carbonyl insertion reaction into the Mo–C(sp(3)) bondwas easier than into the Mo–C=C bond. And the dominant product predicted theoretically was of (S)-chirality, which agreed with experimental data. This reaction was solventd ependent, and toluene was the best among the three solvents toluene, CH3CN, and THF.

Mitigation strategies of acrylamide, furans, heterocyclic amines and browning during the Maillard reaction in foods.

PubMed

Rannou, Cécile; Laroque, Delphine; Renault, Emilie; Prost, Carole; Sérot, Thierry

2016-12-01

The Maillard reaction (MR) occurs widely during food manufacture and storage, through controlled or uncontrolled pathways. Its consequences are ambiguous depending on the nature and processing of the food products. The MR is often used by food manufacturer to develop appealing aromas, colour or texture in food products (cereal based food, coffee, meat…). However, despite some positive aspects, the MR could decrease the nutritional value of food, generate potentially harmful compounds (e.g. acrylamide, furans, heterocyclic amines) or modify aroma or colour although it is not desired (milk, fruit juice). This paper presents a review of the different solutions available to control or moderate the MR in various food products from preventive to removal methods. A brief reminder of the role and influence of the MR on food quality and safety is also provided. Copyright © 2016 Elsevier Ltd. All rights reserved.

The controlled formation and cleavage of an intramolecular d8-d8 Pt-Pt interaction in a dinuclear cycloplatinated molecular "pivot-hinge".

PubMed

Koo, Chi-Kin; Wong, Ka-Leung; Lau, Kai-Cheung; Wong, Wai-Yeung; Lam, Michael Hon-Wah

2009-08-03

The bis(diphenylphosphino)methane (dppm)-bridged dinuclear cycloplatinated complex {[Pt(L)](2)(mu-dppm)}(2+) (Pt(2)dppm; HL: 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine) demonstrates interesting reversible "pivot-hinge"-like intramolecular motions in response to the protonation/deprotonation of L. In its protonated "closed" configuration, the two platinum(II) centers are held in position by intramolecular d(8)-d(8) Pt-Pt interaction. In its deprotonated "open" configuration, such Pt-Pt interaction is cleaved. To further understand the mechanism behind this hingelike motion, an analogous dinuclear cycloplatinated complex, {[Pt(L)](2)(mu-dchpm)}(2+) (Pt(2)dchpm) with bis(dicyclohexylphosphino)methane (dchpm) as the bridging ligand, was synthesized. From its protonation/deprotonation responses, it was revealed that aromatic pi-pi interactions between the phenyl moieties of the mu-dppm and the deprotonated pyrazolyl rings of L was essential to the reversible cleavage of the intramolecular Pt-Pt interaction in Pt(2)dppm. In the case of Pt(2)dchpm, spectroscopic and spectrofluorometric titrations as well as X-ray crystallography indicated that the distance between the two platinum(II) centers shrank upon deprotonation, thus causing a redshift in its room-temperature triplet metal-metal-to-ligand charge-transfer emission from 614 to 625 nm. Ab initio calculations revealed the presence of intramolecular hydrogen bonding between the deprotonated and negatively charged 1-pyrazolyl-N moiety and the methylene CH and phenyl C-H of the mu-dppm. The "open" configuration of the deprotonated Pt(2)dppm was estimated to be 19 kcal mol(-1) more stable than its alternative "closed" configuration. On the other hand, the open configuration of the deprotonated Pt(2)dchpm was 6 kcal mol(-1) less stable than its alternative closed configuration.

A conformationally persistent pseudo-bicyclic guanidinium for anion coordination as stabilized by dual intramolecular hydrogen bonds

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

Seipp, Charles A.; Williams, Neil J.; Bryantsev, Vyacheslav S.

2015-11-30

In this paper, the first example of a pseudo-bicyclic guanidinium ligand is reported. When bound to an anion, the N,N'-bis(2-pyridyl)guanidinium cation persistently adopts the planar α,α conformation featuring intramolecular N···H–N–H···N hydrogen bonds in the solid state, which facilitates crystallization of sulphate from aqueous mixtures of anions.

1,3-Bis[(5-amino-furan-2-yl)meth-yl]-3,4,5,6-tetra-hydro-pyrimidin-1-ium hexa-fluoro-phosphate.

PubMed

Akkurt, Mehmet; Akkoç, Senem; Gök, Yetkin; Tahir, Muhammad Nawaz

2013-01-01

The asymmetric unit of the title salt, C16H21N2O2 (+)·PF6 (-), contains half of the whole ion pair, which has crystallographic mirror symmetry. Two F atoms related by the mirror plane are disordered over two sites of equal occupancy. The dihedral angle between the central ring and the furan ring is 59.3 ()°. In the crystal, the anions and cations are linked through C-H⋯F inter-actions, forming a three-dimensional network.

Biologically active Schiff bases containing thiophene/furan ring and their copper(II) complexes: Synthesis, spectral, nonlinear optical and density functional studies

NASA Astrophysics Data System (ADS)

Gündüzalp, Ayla Balaban; Özsen, İffet; Alyar, Hamit; Alyar, Saliha; Özbek, Neslihan

2016-09-01

Schiff bases; 1,8-bis(thiophene-2-carboxaldimine)-p-menthane (L1) and 1,8-bis(furan-2-carboxaldimine)-p-menthane (L2) have been synthesized and characterized by elemental analysis, 1Hsbnd 13C NMR, UV-vis, FT-IR and LC-MS methods. 1H and 13C shielding tensors for L1 and L2 were calculated with GIAO/DFT/B3LYP/6-311++G(d,p) methods in CDCl3. The vibrational band assignments, nonlinear optical (NLO) activities, frontier molecular orbitals (FMOs) and absorption spectrum have been investigated by the same basis set. Schiff base-copper(II) complexes have been synthesized and structurally characterized with spectroscopic methods, magnetic and conductivity measurements. The spectroscopic data suggest that Schiff base ligands coordinate through azomethine-N and thiophene-S/furan-O donors (as SNNS and ONNO chelating systems) to give a tetragonal geometry around the copper(II) ions. Schiff bases and Cu(II) complexes have been screened for their biological activities on different species of pathogenic bacteria, those are, Gram positive bacteria: Bacillus subtitilus, Yersinia enterotica, Bacillus cereus, Listeria monocytogenes, Micrococcus luteus and Gram negative bacteria: Escherichia coli, Pseudomonas aeroginosa, Shigella dysenteriae, Salmonella typhi, Klebsiella pseudomonas by using microdilution technique (MIC values in mM). Biological activity results show that Cu(II) complexes have higher activities than parent ligands and metal chelation may affect significantly the antibacterial behavior of the organic ligands.

Activation of a Ca(2+)-dependent protein kinase involves intramolecular binding of a calmodulin-like regulatory domain

NASA Technical Reports Server (NTRS)

Huang, J. F.; Teyton, L.; Harper, J. F.; Evans, M. L. (Principal Investigator)

1996-01-01

Ca(2+)-dependent protein kinases (CDPKs) are regulated by a C-terminal calmodulin-like domain (CaM-LD). The CaM-LD is connected to the kinase by a short junction sequence which contains a pseudosubstrate autoinhibitor. To understand how the CaM-LD regulates a CDPK, a recombinant CDPK (isoform CPK-1 from Arabidopsis, accession no. L14771) was made as a fusion protein in Escherichia coli. We show here that a truncated CDPK lacking a CaM-LD (e.g. mutant delta NC-26H) can be activated by exogenous calmodulin or an isolated CaM-LD (Kact approximately 2 microM). We propose that Ca2+ activation of a CDPK normally occurs through intramolecular binding of the CaM-LD to the junction. When the junction and CaM-LD are made as two separate polypeptides, the CaM-LD can bind the junction in a Ca(2+)-dependent fashion with a dissociation constant (KD) of 6 x 10(-6) M, as determined by kinetic binding analyses. When the junction and CaM-LD are tethered in a single polypeptide (e.g. in protein JC-1), their ability to engage in bimolecular binding is suppressed (e.g. the tethered CaM-LD cannot bind a separate junction). A mutation which disrupts the putative CaM-LD binding sequence (e.g. substitution LRV-1444 to DLPG) appears to block intramolecular binding, as indicated by the restored ability of a tethered CaM-LD to engage in bimolecular binding. This mutation, in the context of a full-length enzyme (mutant KJM46H), appears to block Ca2+ activation. Thus, a disruption of intramolecular binding correlates with a disruption of the Ca2+ activation mechanism. CDPKs provide the first example of a member of the calmodulin superfamily where a target binding sequence is located within the same polypeptide.

Perovskite-perovskite tandem photovoltaics with optimized band gaps

NASA Astrophysics Data System (ADS)

Eperon, Giles E.; Leijtens, Tomas; Bush, Kevin A.; Prasanna, Rohit; Green, Thomas; Wang, Jacob Tse-Wei; McMeekin, David P.; Volonakis, George; Milot, Rebecca L.; May, Richard; Palmstrom, Axel; Slotcavage, Daniel J.; Belisle, Rebecca A.; Patel, Jay B.; Parrott, Elizabeth S.; Sutton, Rebecca J.; Ma, Wen; Moghadam, Farhad; Conings, Bert; Babayigit, Aslihan; Boyen, Hans-Gerd; Bent, Stacey; Giustino, Feliciano; Herz, Laura M.; Johnston, Michael B.; McGehee, Michael D.; Snaith, Henry J.

2016-11-01

We demonstrate four- and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, FA0.75Cs0.25Sn0.5Pb0.5I3, that can deliver 14.8% efficiency. By combining this material with a wider-band gap FA0.83Cs0.17Pb(I0.5Br0.5)3 material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with >1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable “all-perovskite” thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs.

Stacking multiple connecting functional materials in tandem organic light-emitting diodes

PubMed Central

Zhang, Tao; Wang, Deng-Ke; Jiang, Nan; Lu, Zheng-Hong

2017-01-01

Tandem device is an important architecture in fabricating high performance organic light-emitting diodes and organic photovoltaic cells. The key element in making a high performance tandem device is the connecting materials stack, which plays an important role in electric field distribution, charge generation and charge injection. For a tandem organic light-emitting diode (OLED) with a simple Liq/Al/MoO3 stack, we discovered that there is a significant current lateral spreading causing light emission over an extremely large area outside the OLED pixel when the Al thickness exceeds 2 nm. This spread light emission, caused by an inductive electric field over one of the device unit, limits one’s ability to fabricate high performance tandem devices. To resolve this issue, a new connecting materials stack with a C60 fullerene buffer layer is reported. This new structure permits optimization of the Al metal layer in the connecting stack and thus enables us to fabricate an efficient tandem OLED having a high 155.6 cd/A current efficiency and a low roll-off (or droop) in current efficiency. PMID:28225028

Electrical and optical analyses of tandem organic light-emitting diodes with organic charge-generation layer

NASA Astrophysics Data System (ADS)

Kim, Bong Sung; Chae, Heeyeop; Chung, Ho Kyoon; Cho, Sung Min

2018-06-01

The electrical and optical properties of tandem organic light-emitting diodes (OLEDs), in which a fluorescent and phosphorescent emitting units are connected by an organic charge-generation layer (CGL), were experimentally analyzed. To investigate the internal properties of the tandem OLEDs, we fabricated and compared two single, two homo-tandem, and two hetero-tandem OLEDs using the fluorescent and phosphorescent units. From the experimental results of the OLEDs obtained at the same current density, the voltage across the CGL as well as the individual emission spectra and luminance of each unit of tandem OLEDs were obtained and compared with the theoretical simulation results. The analysis method proposed in this study can be utilized as a method to verify the accuracy of optical or electrical computer simulation of tandem OLED and it will be useful to understand the overall electrical and optical characteristics of tandem OLEDs.

Structural, photophysical, and theoretical studies of imidazole-based excited-state intramolecular proton transfer molecules

NASA Astrophysics Data System (ADS)

Somasundaram, Sivaraman; Kamaraj, Eswaran; Hwang, Su Jin; Park, Sanghyuk

2018-02-01

Imidazole-based excited state intramolecular proton transfer (ESIPT) blue fluorescent molecules, 2-(1-(4-chlorophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Cl) and 2-(1-(4-bromophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Br) were designed and synthesized by Debus-Radziszewski method through a one-pot multicomponent reaction in high yield. The synthesized compounds were fully characterized by 1H NMR, 13C NMR, FT-IR, FT-Raman, GC-Mass, and elemental analysis. The molecular structures in single crystal lattice were studied by X-ray crystallographic analysis. Because of the intramolecular hydrogen bonding, hydroxyphenyl group is planar to the central imidazole ring, while the other phenyl rings gave distorted conformations to the central heterocyclic ring. BHPI-Cl and BHPI-Br molecules showed intense ESIPT fluorescence at 480 nm, because the two twisted phenyl rings on 4- and 5-positions have reduced intermolecular interaction between adjacent molecules in each crystal through a head-to-tail packing manner. Quantum chemical calculations of energies were carried out by (TD-)DFT using B3LYP/6-31G(d, p) basis set to predict the electronic absorption spectra of the compounds, and they showed good agreement between the computational and the experimental values. The thermal analyses of the synthesized molecules were also carried out by TGA/DSC method.

A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

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

Nguyen, Trong-Nghia; Department of Physical Chemistry, Hanoi University of Science and Technology, Hanoi; Putikam, Raghunath

2015-03-28

We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH{sub 2}OO and anti/syn-CH{sub 3}C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH{sub 2}OO and anti-CH{sub 3}C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH{sub 3}C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C–H bonds. For syn-CH{sub 3}C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH{sub 3} groupmore » by the terminal O atom producing CH{sub 2}C(H)O–OH. At 298 K, the intramolecular insertion process in CH{sub 2}OO was found to be 600 times faster than the commonly assumed ring-closing reaction.« less

Intramolecular transposition by a synthetic IS50 (Tn5) derivative

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

Tomcsanyi, T.; Phadnis, S.H.; Berg, D.E.

1990-11-01

We report the formation of deletions and inversions by intramolecular transposition of Tn5-derived mobile elements. The synthetic transposons used contained the IS50 O and I end segments and the transposase gene, a contraselectable gene encoding sucrose sensitivity (sacB), antibiotic resistance genes, and a plasmid replication origin. Both deletions and inversions were associated with loss of a 300-bp segment that is designated the vector because it is outside of the transposon. Deletions were severalfold more frequent than inversions, perhaps reflecting constraints on DNA twisting or abortive transposition. Restriction and DNA sequence analyses showed that both types of rearrangements extended from onemore » transposon end to many different sites in target DNA. In the case of inversions, transposition generated 9-bp direct repeats of target sequences.« less

Programming Chemical Reaction Networks Using Intramolecular Conformational Motions of DNA.

PubMed

Lai, Wei; Ren, Lei; Tang, Qian; Qu, Xiangmeng; Li, Jiang; Wang, Lihua; Li, Li; Fan, Chunhai; Pei, Hao

2018-06-22

The programmable regulation of chemical reaction networks (CRNs) represents a major challenge toward the development of complex molecular devices performing sophisticated motions and functions. Nevertheless, regulation of artificial CRNs is generally energy- and time-intensive as compared to natural regulation. Inspired by allosteric regulation in biological CRNs, we herein develop an intramolecular conformational motion strategy (InCMS) for programmable regulation of DNA CRNs. We design a DNA switch as the regulatory element to program the distance between the toehold and branch migration domain. The presence of multiple conformational transitions leads to wide-range kinetic regulation spanning over 4 orders of magnitude. Furthermore, the process of energy-cost-free strand exchange accompanied by conformational change discriminates single base mismatches. Our strategy thus provides a simple yet effective approach for dynamic programming of complex CRNs.

An excited-state intramolecular photon transfer fluorescence probe for localizable live cell imaging of cysteine

NASA Astrophysics Data System (ADS)

Liu, Wei; Chen, Wen; Liu, Si-Jia; Jiang, Jian-Hui

2017-03-01

Small molecule probes suitable for selective and specific fluorescence imaging of some important but low-concentration intracellular reactive sulfur species such as cysteine (Cys) pose a challenge in chemical biology. We present a readily available, fast-response fluorescence probe CHCQ-Ac, with 2-(5‧-chloro-2-hydroxyl-phenyl)-6-chloro-4(3 H)-quinazolinone (CHCQ) as the fluorophore and acrylate group as the functional moiety, that enables high-selectivity and high-sensitivity for detecting Cys in both solution and biological system. After specifically reacted with Cys, the probe undergoes a seven-membered intramolecular cyclization and released the fluorophore CHCQ with excited-state intramolecular photon transfer effect. A highly fluorescent, insoluble aggregate was then formed to facilitate high-sensitivity and high-resolution imaging. The results showed that probe CHCQ-Ac affords a remarkably large Stokes shift and can detect Cys under physiological pH condition with no interference from other analytes. Moreover, this probe was proved to have excellent chemical stability, low cytotoxicity and good cell permeability. Our design of this probe provides a novel potential tool to visualize and localize cysteine in bioimaging of live cells that would greatly help to explore various Cys-related physiological and pathological cellular processes in cell biology and diagnostics.

The furan microsolvation blind challenge for quantum chemical methods: First steps

NASA Astrophysics Data System (ADS)

Gottschalk, Hannes C.; Poblotzki, Anja; Suhm, Martin A.; Al-Mogren, Muneerah M.; Antony, Jens; Auer, Alexander A.; Baptista, Leonardo; Benoit, David M.; Bistoni, Giovanni; Bohle, Fabian; Dahmani, Rahma; Firaha, Dzmitry; Grimme, Stefan; Hansen, Andreas; Harding, Michael E.; Hochlaf, Majdi; Holzer, Christof; Jansen, Georg; Klopper, Wim; Kopp, Wassja A.; Kröger, Leif C.; Leonhard, Kai; Mouhib, Halima; Neese, Frank; Pereira, Max N.; Ulusoy, Inga S.; Wuttke, Axel; Mata, Ricardo A.

2018-01-01

Herein we present the results of a blind challenge to quantum chemical methods in the calculation of dimerization preferences in the low temperature gas phase. The target of study was the first step of the microsolvation of furan, 2-methylfuran and 2,5-dimethylfuran with methanol. The dimers were investigated through IR spectroscopy of a supersonic jet expansion. From the measured bands, it was possible to identify a persistent hydrogen bonding OH-O motif in the predominant species. From the presence of another band, which can be attributed to an OH-π interaction, we were able to assert that the energy gap between the two types of dimers should be less than or close to 1 kJ/mol across the series. These values served as a first evaluation ruler for the 12 entries featured in the challenge. A tentative stricter evaluation of the challenge results is also carried out, combining theoretical and experimental results in order to define a smaller error bar. The process was carried out in a double-blind fashion, with both theory and experimental groups unaware of the results on the other side, with the exception of the 2,5-dimethylfuran system which was featured in an earlier publication.

TandEM: Titan and Enceladus mission

USGS Publications Warehouse

Coustenis, A.; Atreya, S.K.; Balint, T.; Brown, R.H.; Dougherty, M.K.; Ferri, F.; Fulchignoni, M.; Gautier, D.; Gowen, R.A.; Griffith, C.A.; Gurvits, L.I.; Jaumann, R.; Langevin, Y.; Leese, M.R.; Lunine, J.I.; McKay, C.P.; Moussas, X.; Muller-Wodarg, I.; Neubauer, F.; Owen, T.C.; Raulin, F.; Sittler, E.C.; Sohl, F.; Sotin, Christophe; Tobie, G.; Tokano, T.; Turtle, E.P.; Wahlund, J.-E.; Waite, J.H.; Baines, K.H.; Blamont, J.; Coates, A.J.; Dandouras, I.; Krimigis, T.; Lellouch, E.; Lorenz, R.D.; Morse, A.; Porco, C.C.; Hirtzig, M.; Saur, J.; Spilker, T.; Zarnecki, J.C.; Choi, E.; Achilleos, N.; Amils, R.; Annan, P.; Atkinson, D.H.; Benilan, Y.; Bertucci, C.; Bezard, B.; Bjoraker, G.L.; Blanc, M.; Boireau, L.; Bouman, J.; Cabane, M.; Capria, M.T.; Chassefiere, E.; Coll, P.; Combes, M.; Cooper, J.F.; Coradini, A.; Crary, F.; Cravens, T.; Daglis, I.A.; de Angelis, E.; De Bergh, C.; de Pater, I.; Dunford, C.; Durry, G.; Dutuit, O.; Fairbrother, D.; Flasar, F.M.; Fortes, A.D.; Frampton, R.; Fujimoto, M.; Galand, M.; Grasset, O.; Grott, M.; Haltigin, T.; Herique, A.; Hersant, F.; Hussmann, H.; Ip, W.; Johnson, R.; Kallio, E.; Kempf, S.; Knapmeyer, M.; Kofman, W.; Koop, R.; Kostiuk, T.; Krupp, N.; Kuppers, M.; Lammer, H.; Lara, L.-M.; Lavvas, P.; Le, Mouelic S.; Lebonnois, S.; Ledvina, S.; Li, Ji; Livengood, T.A.; Lopes, R.M.; Lopez-Moreno, J. -J.; Luz, D.; Mahaffy, P.R.; Mall, U.; Martinez-Frias, J.; Marty, B.; McCord, T.; Salvan, C.M.; Milillo, A.; Mitchell, D.G.; Modolo, R.; Mousis, O.; Nakamura, M.; Neish, Catherine D.; Nixon, C.A.; Mvondo, D.N.; Orton, G.; Paetzold, M.; Pitman, J.; Pogrebenko, S.; Pollard, W.; Prieto-Ballesteros, O.; Rannou, P.; Reh, K.; Richter, L.; Robb, F.T.; Rodrigo, R.; Rodriguez, S.; Romani, P.; Bermejo, M.R.; Sarris, E.T.; Schenk, P.; Schmitt, B.; Schmitz, N.; Schulze-Makuch, D.; Schwingenschuh, K.; Selig, A.; Sicardy, B.; Soderblom, L.; Spilker, L.J.; Stam, D.; Steele, A.; Stephan, K.; Strobel, D.F.; Szego, K.; Szopa,

2009-01-01

TandEM was proposed as an L-class (large) mission in response to ESA’s Cosmic Vision 2015–2025 Call, and accepted for further studies, with the goal of exploring Titan and Enceladus. The mission concept is to perform in situ investigations of two worlds tied together by location and properties, whose remarkable natures have been partly revealed by the ongoing Cassini–Huygens mission. These bodies still hold mysteries requiring a complete exploration using a variety of vehicles and instruments. TandEM is an ambitious mission because its targets are two of the most exciting and challenging bodies in the Solar System. It is designed to build on but exceed the scientific and technological accomplishments of the Cassini–Huygens mission, exploring Titan and Enceladus in ways that are not currently possible (full close-up and in situ coverage over long periods of time). In the current mission architecture, TandEM proposes to deliver two medium-sized spacecraft to the Saturnian system. One spacecraft would be an orbiter with a large host of instruments which would perform several Enceladus flybys and deliver penetrators to its surface before going into a dedicated orbit around Titan alone, while the other spacecraft would carry the Titan in situ investigation components, i.e. a hot-air balloon (Montgolfière) and possibly several landing probes to be delivered through the atmosphere.

TandEM: Titan and Enceladus mission

NASA Astrophysics Data System (ADS)

Coustenis, A.; Atreya, S. K.; Balint, T.; Brown, R. H.; Dougherty, M. K.; Ferri, F.; Fulchignoni, M.; Gautier, D.; Gowen, R. A.; Griffith, C. A.; Gurvits, L. I.; Jaumann, R.; Langevin, Y.; Leese, M. R.; Lunine, J. I.; McKay, C. P.; Moussas, X.; Müller-Wodarg, I.; Neubauer, F.; Owen, T. C.; Raulin, F.; Sittler, E. C.; Sohl, F.; Sotin, C.; Tobie, G.; Tokano, T.; Turtle, E. P.; Wahlund, J.-E.; Waite, J. H.; Baines, K. H.; Blamont, J.; Coates, A. J.; Dandouras, I.; Krimigis, T.; Lellouch, E.; Lorenz, R. D.; Morse, A.; Porco, C. C.; Hirtzig, M.; Saur, J.; Spilker, T.; Zarnecki, J. C.; Choi, E.; Achilleos, N.; Amils, R.; Annan, P.; Atkinson, D. H.; Bénilan, Y.; Bertucci, C.; Bézard, B.; Bjoraker, G. L.; Blanc, M.; Boireau, L.; Bouman, J.; Cabane, M.; Capria, M. T.; Chassefière, E.; Coll, P.; Combes, M.; Cooper, J. F.; Coradini, A.; Crary, F.; Cravens, T.; Daglis, I. A.; de Angelis, E.; de Bergh, C.; de Pater, I.; Dunford, C.; Durry, G.; Dutuit, O.; Fairbrother, D.; Flasar, F. M.; Fortes, A. D.; Frampton, R.; Fujimoto, M.; Galand, M.; Grasset, O.; Grott, M.; Haltigin, T.; Herique, A.; Hersant, F.; Hussmann, H.; Ip, W.; Johnson, R.; Kallio, E.; Kempf, S.; Knapmeyer, M.; Kofman, W.; Koop, R.; Kostiuk, T.; Krupp, N.; Küppers, M.; Lammer, H.; Lara, L.-M.; Lavvas, P.; Le Mouélic, S.; Lebonnois, S.; Ledvina, S.; Li, J.; Livengood, T. A.; Lopes, R. M.; Lopez-Moreno, J.-J.; Luz, D.; Mahaffy, P. R.; Mall, U.; Martinez-Frias, J.; Marty, B.; McCord, T.; Menor Salvan, C.; Milillo, A.; Mitchell, D. G.; Modolo, R.; Mousis, O.; Nakamura, M.; Neish, C. D.; Nixon, C. A.; Nna Mvondo, D.; Orton, G.; Paetzold, M.; Pitman, J.; Pogrebenko, S.; Pollard, W.; Prieto-Ballesteros, O.; Rannou, P.; Reh, K.; Richter, L.; Robb, F. T.; Rodrigo, R.; Rodriguez, S.; Romani, P.; Ruiz Bermejo, M.; Sarris, E. T.; Schenk, P.; Schmitt, B.; Schmitz, N.; Schulze-Makuch, D.; Schwingenschuh, K.; Selig, A.; Sicardy, B.; Soderblom, L.; Spilker, L. J.; Stam, D.; Steele, A.; Stephan, K.; Strobel, D. F.; Szego, K.; Szopa, C.; Thissen, R.; Tomasko, M. G.; Toublanc, D.; Vali, H.; Vardavas, I.; Vuitton, V.; West, R. A.; Yelle, R.; Young, E. F.

2009-03-01

TandEM was proposed as an L-class (large) mission in response to ESA’s Cosmic Vision 2015-2025 Call, and accepted for further studies, with the goal of exploring Titan and Enceladus. The mission concept is to perform in situ investigations of two worlds tied together by location and properties, whose remarkable natures have been partly revealed by the ongoing Cassini-Huygens mission. These bodies still hold mysteries requiring a complete exploration using a variety of vehicles and instruments. TandEM is an ambitious mission because its targets are two of the most exciting and challenging bodies in the Solar System. It is designed to build on but exceed the scientific and technological accomplishments of the Cassini-Huygens mission, exploring Titan and Enceladus in ways that are not currently possible (full close-up and in situ coverage over long periods of time). In the current mission architecture, TandEM proposes to deliver two medium-sized spacecraft to the Saturnian system. One spacecraft would be an orbiter with a large host of instruments which would perform several Enceladus flybys and deliver penetrators to its surface before going into a dedicated orbit around Titan alone, while the other spacecraft would carry the Titan in situ investigation components, i.e. a hot-air balloon (Montgolfière) and possibly several landing probes to be delivered through the atmosphere.

Low-energy elastic electron scattering from furan

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

Khakoo, M. A.; Muse, J.; Ralphs, K.

We report normalized experimental and theoretical differential cross sections for elastic electron scattering by C{sub 4}H{sub 4}O (furan) molecules from a collaborative project between several Brazilian theoretical groups and an experimental group at California State Fullerton, USA. The measurements are obtained by using the relative flow method with helium as the standard gas and a thin aperture target gas collimating source. The relative flow method is applied without the restriction imposed by the relative flow pressure condition on helium and the unknown gas. The experimental data were taken at incident electron energies of 1, 1.5, 1.73, 2, 2.7, 3, 5,more » 7, 10, 20, 30, and 50 eV and covered the angular range between 10 deg. and 130 deg. The measurements verify observed {pi}* shape resonances at 1.65{+-}0.05eV and 3.10{+-}0.05 eV scattering energies, in good agreement with the transmission electron data of Modelli and Burrow [J. Phys. Chem. A 108, 5721 (2004)]. Furthermore, the present results also indicated both resonances dominantly in the d-wave channel. The differential cross sections are integrated in the standard way to obtain integral elastic cross sections and momentum transfer cross sections. The calculations employed the Schwinger multichannel method with pseudopotentials and were performed in the static-exchange and in the static-exchange plus polarization approximations. The calculated integral and momentum transfer cross sections clearly revealed the presence of two shape resonances located at 1.95 and 3.56 eV and ascribed to the B{sub 1} and A{sub 2} symmetries of the C{sub 2v} point group, respectively, in very good agreement with the experimental findings. Overall agreement between theory and experiment regarding the differential, momentum transfer, and integral cross sections is very good, especially for energies below 10 eV.« less

Spectroscopic studies of the intramolecular hydrogen bonding in o-hydroxy Schiff bases, derived from diaminomaleonitrile, and their deprotonation reaction products.

PubMed

Szady-Chełmieniecka, Anna; Kołodziej, Beata; Morawiak, Maja; Kamieński, Bohdan; Schilf, Wojciech

2018-01-15

The structural study of five Schiff bases derived from diaminomaleonitrile (DAMN) and 2-hydroxy carbonyl compounds was performed using 1 H, 13 C and 15 N NMR methods in solution and in the solid state as well. ATR-FTIR and X-Ray spectroscopies were used for confirmation of the results obtained by NMR method. The imine obtained from DAMN and benzaldehyde was synthesized as a model compound which lacks intramolecular hydrogen bond. Deprotonation of all synthesized compounds was done by treating with tetramethylguanidine (TMG). NMR data revealed that salicylidene Schiff bases in DMSO solution exist as OH forms without intramolecular hydrogen bonds and independent on the substituents in aromatic ring. In the case of 2-hydroxy naphthyl derivative, the OH proton is engaged into weak intramolecular hydrogen bond. Two of imines (salDAMN and 5-BrsalDAMN) exist in DMSO solution as equilibrium mixtures of two isomers (A and B). The structures of equilibrium mixture in the solid state have been studied by NMR, ATR-FTIR and X-Ray methods. The deprotonation of three studied compounds (salDAMN, 5-BrsalDAMN, and 5-CH 3 salDAMN) proceeded in two different ways: deprotonation of oxygen atom (X form) or of nitrogen atom of free primary amine group of DAMN moiety (Y form). For 5-NO 2 salDAMN and naphDAMN only one form (X) was observed. Copyright © 2017 Elsevier B.V. All rights reserved.

An efficient method for the simultaneous determination of furan, 2-methylfuran and 2-pentylfuran in fruit juices by headspace solid phase microextraction and gas chromatography-flame ionisation detector.

PubMed

Hu, Gaofei; Zhu, Yan; Hernandez, Marta; Koutchma, Tatiana; Shao, Suqin

2016-02-01

A headspace solid phase microextraction (HS-SPME) procedure followed by gas chromatography-flame ionisation detector (GC-FID) analysis was developed and validated for the simultaneous analysis of furan, 2-methylfuran and 2-pentylfuran from juice samples. Extraction at 32 °C for 20 min with stirring at 600 rpm and NaCl concentration 15% (W/V) was the optimal HS-SPME condition for all the three compounds by using a carboxen/polydimethylsiloxane fused silica fibre (75 μm). The extracted compounds were base line separated on a SPB-1 GC column within 12 min. The relative standard deviations of all analytes were less than 6.7%. The recovery rates were between 90.2% and 110.1%. The limits of detection and limits of quantification were 0.056-0.23 ng/mL and 0.14-0.76 ng/mL, respectively. The results showed that the developed method was sensitive, precise, accurate and robust for the determination of furan, 2-methylfuran and 2-pentylfuran in complex matrices without interferences from other components. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Tandem microwave waste remediation and decontamination system

DOEpatents

Wicks, George G.; Clark, David E.; Schulz, Rebecca L.

1999-01-01

The invention discloses a tandem microwave system consisting of a primary chamber in which microwave energy is used for the controlled combustion of materials. A second chamber is used to further treat the off-gases from the primary chamber by passage through a susceptor matrix subjected to additional microwave energy. The direct microwave radiation and elevated temperatures provide for significant reductions in the qualitative and quantitative emissions of the treated off gases. The tandem microwave system can be utilized for disinfecting wastes, sterilizing materials, and/or modifying the form of wastes to solidify organic or inorganic materials. The simple design allows on-site treatment of waste by small volume waste generators.

Optimizing a tandem disk model

NASA Astrophysics Data System (ADS)

Healey, J. V.

1983-08-01

The optimum values of the solidity ratio, tip speed ratio (TSR), and the preset angle of attack, the corresponding distribution, and the breakdown mechanism for a tandem disk model for a crosswind machine such as a Darrieus are examined analytically. Equations are formulated for thin blades with zero drag in consideration of two plane rectangular disks, both perpendicular to the wind flow. Power coefficients are obtained for both disks and comparisons are made between a single-disk system and a two-disk system. The power coefficient for the tandem disk model is shown to be a sum of the coefficients of the individual disks, with a maximum value of twice the Betz limit at an angle of attack of -1 deg and the TSR between 4-7. The model, applied to the NACA 0012 profile, gives a maximum power coefficient of 0.967 with a solidity ratio of 0.275 and highly limited ranges for the angle of attack and TSR.

Titanium-Beta Zeolites Catalyze the Stereospecific Isomerization of D-Glucose to L-Sorbose via Intramolecular C5-C1 Hydride Shift

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

Gounder, Rajamani; Davis, Mark E.

Pure-silica zeolite beta containing Lewis acidic framework Ti 4+ centers (Ti-Beta) is shown to catalyze the isomerization of D-glucose to L-sorbose via an intramolecular C5–C1 hydride shift. Glucose–sorbose isomerization occurs in parallel to glucose–fructose isomerization on Ti-Beta in both water and methanol solvents, with fructose formed as the predominant product in water and sorbose as the predominant product in methanol (at 373 K) at initial times and over the course of >10 turnovers. Isotopic tracer studies demonstrate that 13C and D labels placed respectively at the C1 and C2 positions of glucose are retained respectively at the C6 and C5more » positions of sorbose, consistent with its formation via an intramolecular C5–C1 hydride shift isomerization mechanism. This direct Lewis acid-mediated pathway for glucose–sorbose isomerization appears to be unprecedented among heterogeneous or biological catalysts and sharply contrasts indirect base-mediated glucose–sorbose isomerization via 3,4-enediol intermediates or via retro-aldol fragmentation and recombination of sugar fragments. Measured first-order glucose–sorbose isomerization rate constants (per total Ti; 373 K) for Ti-Beta in methanol are similar for glucose and glucose deuterated at the C2 position (within a factor of ~1.1), but are a factor of ~2.3 lower for glucose deuterated at each carbon position, leading to H/D kinetic isotope effects expected for kinetically relevant intramolecular C5–C1 hydride shift steps. Optical rotation measurements show that isomerization of D-(+)-glucose (92% enantiomeric purity) with Ti-Beta in water (373 K) led to the formation of L-(-)-sorbose (73% enantiomeric purity) and D-(-)-fructose (87% enantiomeric purity) as the predominant stereoisomers, indicating that stereochemistry is preserved at carbon centers not directly involved in intramolecular C5–C1 or C2–C1 hydride shift steps, respectively. This new Lewis acid-mediated rearrangement of glucose

Aerobic Oxidation of 5-(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan-2,5-dicarboxylic Acid Formation with CeO2 -Supported Gold Catalyst.

PubMed

Kim, Minjune; Su, Yaqiong; Fukuoka, Atsushi; Hensen, Emiel J M; Nakajima, Kiyotaka

2018-05-14

The utilization of 5-(hydroxymethyl)furfural (HMF) for the large-scale production of essential chemicals has been largely limited by the formation of solid humin as a byproduct, which prevents the operation of stepwise batch-type and continuous flow-type processes. The reaction of HMF with 1,3-propanediol produces an HMF acetal derivative that exhibits excellent thermal stability. Aerobic oxidation of the HMF acetal with a CeO 2 -supported Au catalyst and Na 2 CO 3 in water gives a 90-95 % yield of furan 2,5-dicarboxylic acid, an increasingly important commodity chemical for the biorenewables industry, from concentrated solutions (10-20 wt %) without humin formation. The six-membered acetal ring suppresses thermal decomposition and self-polymerization of HMF in concentrated solutions. Kinetic studies supported by DFT calculations identify two crucial steps in the reaction mechanism, that is, the partial hydrolysis of the acetal into 5-formyl-2-furan carboxylic acid involving OH - and Lewis acid sites on CeO 2 , and subsequent oxidative dehydrogenation of the in situ generated hemiacetal involving Au nanoparticles. These results represent a significant advance over the current state of the art, overcoming an inherent limitation of the oxidation of HMF to an important monomer for biopolymer production. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Far-Infrared Synchrotron-Based Spectroscopy of Furan: Analysis of the ν14-ν11 Perturbation and the ν18 and ν19 Levels

NASA Astrophysics Data System (ADS)

Tokaryk, D. W.; Culligan, S. D.; Billinghurst, B. E.; van Wijngaarden, J. A.

2011-06-01

The ν14 vibrational level of furan lies 603 Cm-1 above the ground vibrational state. It is the lowest lying vibrational level for which a transition from the ground state is allowed. Other groups have conducted rotational analyses on fundamental bands of furan at 745 Cm-1 (ν13), 995 Cm-1 (ν7) and at 1067 Cm-1 (ν6). We have taken the rotationally resolved spectrum of the c-type ν14 band at the Canadian Light Source synchrotron with a Bruker IFS125HR Fourier transform spectrometer operating at 0.00096 Cm-1 resolution, and have found it to be perturbed by the ν11 band at 600 Cm-1, for which transitions from the ground vibrational state are forbidden. By taking the spectra of the b-type ν18 fundamental band and of the very weak c-type ν18- ν11 band we have been able to analyze the ν14- ν11 perturbation. We have also analyzed the spectrum of the b-type ν19 fundamental band. [2]{B. Pankoke, K. M. T. Yamada, G. Winnewisser, Z. Naturforsch. A 48 (1993) 1193-1202. [3]A. Mellouki, M. Herman, J. Demaison, B. Lemoine, L. Margulès, J. Mol. Spectrosc. 198 (1999) 348-357. [4]A. Mellouki, J. Vander Auwera, J. Demaison, M. Herman, J. Mol. Spectrosc. 209 (2001) 136-138.

Dynamics of tandem bubble interaction in a microfluidic channel

PubMed Central

Yuan, Fang; Sankin, Georgy; Zhong, Pei

2011-01-01

The dynamics of tandem bubble interaction in a microfluidic channel (800 × 21 μm, W × H) have been investigated using high-speed photography, with resultant fluid motion characterized by particle imaging velocimetry. A single or tandem bubble is produced reliably via laser absorption by micron-sized gold dots (6 μm in diameter with 40 μm in separation distance) coated on a glass surface of the microfluidic channel. Using two pulsed Nd:YAG lasers at λ = 1064 nm and ∼10 μJ/pulse, the dynamics of tandem bubble interaction (individual maximum bubble diameter of 50 μm with a corresponding collapse time of 5.7 μs) are examined at different phase delays. In close proximity (i.e., interbubble distance = 40 μm or γ = 0.8), the tandem bubbles interact strongly with each other, leading to asymmetric deformation of the bubble walls and jet formation, as well as the production of two pairs of vortices in the surrounding fluid rotating in opposite directions. The direction and speed of the jet (up to 95 m/s), as well as the orientation and strength of the vortices can be varied by adjusting the phase delay. PMID:22088007

Dynamics of tandem bubble interaction in a microfluidic channel.

PubMed

Yuan, Fang; Sankin, Georgy; Zhong, Pei

2011-11-01

The dynamics of tandem bubble interaction in a microfluidic channel (800  ×  21 μm, W × H) have been investigated using high-speed photography, with resultant fluid motion characterized by particle imaging velocimetry. A single or tandem bubble is produced reliably via laser absorption by micron-sized gold dots (6 μm in diameter with 40 μm in separation distance) coated on a glass surface of the microfluidic channel. Using two pulsed Nd:YAG lasers at λ = 1064 nm and ∼10 μJ/pulse, the dynamics of tandem bubble interaction (individual maximum bubble diameter of 50 μm with a corresponding collapse time of 5.7 μs) are examined at different phase delays. In close proximity (i.e., interbubble distance = 40 μm or γ = 0.8), the tandem bubbles interact strongly with each other, leading to asymmetric deformation of the bubble walls and jet formation, as well as the production of two pairs of vortices in the surrounding fluid rotating in opposite directions. The direction and speed of the jet (up to 95 m/s), as well as the orientation and strength of the vortices can be varied by adjusting the phase delay.

On the Relativistic Correction of Particles Trajectory in Tandem Type Electrostatic Accelerator

NASA Astrophysics Data System (ADS)

Minárik, Stanislav

2015-08-01

A constant potential is applied to the acceleration of the ion-beam in the tandem type electrostatic accelerator. However, not just one voltage is applied, but instead a number of applications can be made in succession by means of the tandem arrangement of high voltage tubes. This number of voltage applications, which is the number of so-called "stages" of a tandem accelerator, may be two, three, or four, depending on the chosen design. Electrostatic field with approximately constant intensity acts on ions in any stage. In general, non-relativistic dynamics is used for the description of the ion transport in tandem accelerator. Energies of accelerated ions are too low and relativistic effects cannot be commonly observed by standard experimental technique. Estimation of possible relativistic correction of ion trajectories is therefore only a matter of calculation. In this note, we briefly present such calculation. Our aim is to show how using the relativistic dynamics modifies the particles trajectory in tandem type accelerator and what parameters determine this modification.

Simulation of two dimensional electrophoresis and tandem mass spectrometry for teaching proteomics.

PubMed

Fisher, Amanda; Sekera, Emily; Payne, Jill; Craig, Paul

2012-01-01

In proteomics, complex mixtures of proteins are separated (usually by chromatography or electrophoresis) and identified by mass spectrometry. We have created 2DE Tandem MS, a computer program designed for use in the biochemistry, proteomics, or bioinformatics classroom. It contains two simulations-2D electrophoresis and tandem mass spectrometry. The two simulations are integrated together and are designed to teach the concept of proteome analysis of prokaryotic and eukaryotic organisms. 2DE-Tandem MS can be used as a freestanding simulation, or in conjunction with a wet lab, to introduce proteomics in the undergraduate classroom. 2DE Tandem MS is a free program available on Sourceforge at https://sourceforge.net/projects/jbf/. It was developed using Java Swing and functions in Mac OSX, Windows, and Linux, ensuring that every student sees a consistent and informative graphical user interface no matter the computer platform they choose. Java must be installed on the host computer to run 2DE Tandem MS. Example classroom exercises are provided in the Supporting Information. Copyright © 2012 Wiley Periodicals, Inc.

Intramolecular activation of a Ca(2+)-dependent protein kinase is disrupted by insertions in the tether that connects the calmodulin-like domain to the kinase

NASA Technical Reports Server (NTRS)

Vitart, V.; Christodoulou, J.; Huang, J. F.; Chazin, W. J.; Harper, J. F.; Evans, M. L. (Principal Investigator)

2000-01-01

Ca(2+)-dependent protein kinases (CDPK) have a calmodulin-like domain (CaM-LD) tethered to the C-terminal end of the kinase. Activation is proposed to involve intramolecular binding of the CaM-LD to a junction sequence that connects the CaM-LD to the kinase domain. Consistent with this model, a truncated CDPK (DeltaNC) in which the CaM-LD has been deleted can be activated in a bimolecular interaction with an isolated CaM-LD or calmodulin, similar to the activation of a calmodulin-dependent protein kinase (CaMK) by calmodulin. Here we provide genetic evidence that this bimolecular activation requires a nine-residue binding segment from F436 to I444 (numbers correspond to CPK-1 accession number L14771). Two mutations at either end of this core segment (F436/A and VI444/AA) severely disrupted bimolecular activation, whereas flanking mutations had only minor effects. Intramolecular activation of a full-length kinase was also disrupted by a VI444/AA mutation, but surprisingly not by a F436/A mutation (at the N-terminal end of the binding site). Interestingly, intramolecular but not bimolecular activation was disrupted by insertion mutations placed immediately downstream of I444. To show that mutant enzymes were not misfolded, latent kinase activity was stimulated through binding of an antijunction antibody. Results here support a model of intramolecular activation in which the tether (A445 to G455) that connects the CaM-LD to the kinase provides an important structural constraint and is not just a simple flexible connection.

Intramolecular interactions in polymethylenic chains with polar end groups: The spectroscopic signature

NASA Astrophysics Data System (ADS)

Milani, Alberto; Castiglioni, Chiara; Brambilla, Luigi; Zerbi, Giuseppe

2012-02-01

We present a computational study based on DFT simulations of the infrared spectra of several short alkyl chains carrying polar end groups. The work aims to provide guidelines for the detection of marker bands signalling the occurrence of specific intramolecular interactions between the polar head and CH2 groups at different distances. In particular, the CH stretching region is investigated and new features assigned to normal modes localized on the CH2 groups nearest to the electron-withdrawing atom are identified. The study has been extended also to the rationalization of the experimental IR features shown by a 1-Chloroeicosane (C20H41Cl) sample.

Rotational Isomers, Intramolecular Hydrogen Bond, and IR Spectra of o-Vinylphenol Homologs

NASA Astrophysics Data System (ADS)

Glazunov, V. P.; Berdyshev, D. V.; Balaneva, N. N.; Radchenko, O. S.; Novikov, V. L.

2018-03-01

The ν(OH) stretching-mode bands in solution IR spectra of five o-vinylphenol (o-VPh) homologs in the slightly polar solvents CCl4 and n-hexane were studied. Several rotamers with free OH groups were found in solutions of o-VPh and its methyl-substituted derivatives in n-hexane. The proportion of rotamers in o-VPh homologs with intramolecular hydrogen bonds (IHBs) O-H...π varied from 22 to 97% in the gas and cyclohexane according to B3LYP/cc-pVTZ calculations. The theoretically estimated effective enthalpies -ΔH of their IHBs varied in the range 0.20-2.24 kcal/mol.

Structure and diffusion of furans and other cellulose-derived compounds in solvents via MD simulation

NASA Astrophysics Data System (ADS)

Rabideau, Brooks; Ismail, Ahmed

2011-03-01

There is now a large push towards the development of energy sources that are both environmentally friendly and sustainable; with the conversion of cellulose derived from biomass into biofuels being one promising route. In this conversion, a variety of intermediary compounds have been identified, which appear critical to successful expansion of the process to an industrial scale. Here we examine the structure and diffusion of these furans and acids derived from cellulose within ionic liquids via molecular dynamic simulation. Ionic liquids have shown the ability to dissolve cellulose with certain `green' benefits over existing, conventional solvents. Specifically, we study the solvation properties of these chemicals by examining the pair correlation functions of solute with solvent, and by exploring the agglomeration and separation of these chemicals from the solvent as well as the hydrogen bonding between species. Additionally, we determine the diffusion constant of these compounds in ionic liquid and aqueous solvents.

Development of an advanced spacecraft tandem mass spectrometer

NASA Astrophysics Data System (ADS)

Drew, Russell C.

1992-03-01

The purpose of this research was to apply current advanced technology in electronics and materials to the development of a miniaturized Tandem Mass Spectrometer that would have the potential for future development into a package suitable for spacecraft use. The mass spectrometer to be used as a basis for the tandem instrument would be a magnetic sector instrument, of Nier-Johnson configuration, as used on the Viking Mars Lander mission. This instrument configuration would then be matched with a suitable second stage MS to provide the benefits of tandem MS operation for rapid identification of unknown organic compounds. This tandem instrument is configured with a newly designed GC system to aid in separation of complex mixtures prior to MS analysis. A number of important results were achieved in the course of this project. Among them were the development of a miniaturized GC subsystem, with a unique desorber-injector, fully temperature feedback controlled oven with powered cooling for rapid reset to ambient conditions, a unique combination inlet system to the MS that provides for both membrane sampling and direct capillary column sample transfer, a compact and ruggedized alignment configuration for the MS, an improved ion source design for increased sensitivity, and a simple, rugged tandem MS configuration that is particularly adaptable to spacecraft use because of its low power and low vacuum pumping requirements. The potential applications of this research include use in manned spacecraft like the space station as a real-time detection and warning device for the presence of potentially harmful trace contaminants of the spacecraft atmosphere, use as an analytical device for evaluating samples collected on the Moon or a planetary surface, or even use in connection with monitoring potentially hazardous conditions that may exist in terrestrial locations such as launch pads, environmental test chambers or other sensitive areas. Commercial development of the technology

Development of an advanced spacecraft tandem mass spectrometer

NASA Technical Reports Server (NTRS)

Drew, Russell C.

1992-01-01

The purpose of this research was to apply current advanced technology in electronics and materials to the development of a miniaturized Tandem Mass Spectrometer that would have the potential for future development into a package suitable for spacecraft use. The mass spectrometer to be used as a basis for the tandem instrument would be a magnetic sector instrument, of Nier-Johnson configuration, as used on the Viking Mars Lander mission. This instrument configuration would then be matched with a suitable second stage MS to provide the benefits of tandem MS operation for rapid identification of unknown organic compounds. This tandem instrument is configured with a newly designed GC system to aid in separation of complex mixtures prior to MS analysis. A number of important results were achieved in the course of this project. Among them were the development of a miniaturized GC subsystem, with a unique desorber-injector, fully temperature feedback controlled oven with powered cooling for rapid reset to ambient conditions, a unique combination inlet system to the MS that provides for both membrane sampling and direct capillary column sample transfer, a compact and ruggedized alignment configuration for the MS, an improved ion source design for increased sensitivity, and a simple, rugged tandem MS configuration that is particularly adaptable to spacecraft use because of its low power and low vacuum pumping requirements. The potential applications of this research include use in manned spacecraft like the space station as a real-time detection and warning device for the presence of potentially harmful trace contaminants of the spacecraft atmosphere, use as an analytical device for evaluating samples collected on the Moon or a planetary surface, or even use in connection with monitoring potentially hazardous conditions that may exist in terrestrial locations such as launch pads, environmental test chambers or other sensitive areas. Commercial development of the technology

Intramolecular dynamics within the N-Cap-SH3-SH2 regulatory unit of the c-Abl tyrosine kinase reveal targeting to the cellular membrane.

PubMed

de Oliveira, Guilherme A P; Pereira, Elen G; Ferretti, Giulia D S; Valente, Ana Paula; Cordeiro, Yraima; Silva, Jerson L

2013-09-27

c-Abl is a key regulator of cell signaling and is under strict control via intramolecular interactions. In this study, we address changes in the intramolecular dynamics coupling within the c-Abl regulatory unit by presenting its N-terminal segment (N-Cap) with an alternative function in the cell as c-Abl becomes activated. Using small angle x-ray scattering, nuclear magnetic resonance, and confocal microscopy, we demonstrate that the N-Cap and the Src homology (SH) 3 domain acquire μs-ms motions upon N-Cap association with the SH2-L domain, revealing a stabilizing synergy between these segments. The N-Cap-myristoyl tether likely triggers the protein to anchor to the membrane because of these flip-flop dynamics, which occur in the μs-ms time range. This segment not only presents the myristate during c-Abl inhibition but may also trigger protein localization inside the cell in a functional and stability-dependent mechanism that is lost in Bcr-Abl(+) cells, which underlie chronic myeloid leukemia. This loss of intramolecular dynamics and binding to the cellular membrane is a potential therapeutic target.

Thermal selectivity of intermolecular versus intramolecular reactions on surfaces

PubMed Central

Cirera, Borja; Giménez-Agulló, Nelson; Björk, Jonas; Martínez-Peña, Francisco; Martin-Jimenez, Alberto; Rodriguez-Fernandez, Jonathan; Pizarro, Ana M.; Otero, Roberto; Gallego, José M.; Ballester, Pablo; Galan-Mascaros, José R.; Ecija, David

2016-01-01

On-surface synthesis is a promising strategy for engineering heteroatomic covalent nanoarchitectures with prospects in electronics, optoelectronics and photovoltaics. Here we report the thermal tunability of reaction pathways of a molecular precursor in order to select intramolecular versus intermolecular reactions, yielding monomeric or polymeric phthalocyanine derivatives, respectively. Deposition of tetra-aza-porphyrin species bearing ethyl termini on Au(111) held at room temperature results in a close-packed assembly. Upon annealing from room temperature to 275 °C, the molecular precursors undergo a series of covalent reactions via their ethyl termini, giving rise to phthalocyanine tapes. However, deposition of the tetra-aza-porphyrin derivatives on Au(111) held at 300 °C results in the formation and self-assembly of monomeric phthalocyanines. A systematic scanning tunnelling microscopy study of reaction intermediates, combined with density functional calculations, suggests a [2+2] cycloaddition as responsible for the initial linkage between molecular precursors, whereas the monomeric reaction is rationalized as an electrocyclic ring closure. PMID:26964764

Mechanisms of Intramolecular Communication in a Hyperthermophilic Acylaminoacyl Peptidase: A Molecular Dynamics Investigation

PubMed Central

Papaleo, Elena; Renzetti, Giulia; Tiberti, Matteo

2012-01-01

Protein dynamics and the underlying networks of intramolecular interactions and communicating residues within the three-dimensional (3D) structure are known to influence protein function and stability, as well as to modulate conformational changes and allostery. Acylaminoacyl peptidase (AAP) subfamily of enzymes belongs to a unique class of serine proteases, the prolyl oligopeptidase (POP) family, which has not been thoroughly investigated yet. POPs have a characteristic multidomain three-dimensional architecture with the active site at the interface of the C-terminal catalytic domain and a β-propeller domain, whose N-terminal region acts as a bridge to the hydrolase domain. In the present contribution, protein dynamics signatures of a hyperthermophilic acylaminoacyl peptidase (AAP) of the prolyl oligopeptidase (POP) family, as well as of a deletion variant and alanine mutants (I12A, V13A, V16A, L19A, I20A) are reported. In particular, we aimed at identifying crucial residues for long range communications to the catalytic site or promoting the conformational changes to switch from closed to open ApAAP conformations. Our investigation shows that the N-terminal α1-helix mediates structural intramolecular communication to the catalytic site, concurring to the maintenance of a proper functional architecture of the catalytic triad. Main determinants of the effects induced by α1-helix are a subset of hydrophobic residues (V16, L19 and I20). Moreover, a subset of residues characterized by relevant interaction networks or coupled motions have been identified, which are likely to modulate the conformational properties at the interdomain interface. PMID:22558199

Optimizing removal of arsenic, chromium, copper, pentachlorophenol and polychlorodibenzo-dioxins/furans from the 1-4 mm fraction of polluted soil using an attrition process.

PubMed

Guemiza, Karima; Coudert, Lucie; Tran, Lan Huong; Metahni, Sabrine; Blais, Jean-François; Besner, Simon; Mercier, Guy

2017-08-01

The objective of this study was to evaluate, at a pilot scale, the performance of an attrition process for removing As, Cr, Cu, pentachlorophenol (PCP) and polychlorodibenzodioxins and furans (PCDDF) from a 1-4 mm soil fraction. A Box-Behnken experimental design was utilized to evaluate the influence of several parameters (temperature, surfactant concentration and pulp density) and to optimize the main operating parameters of this attrition process. According to the results, the concentration of surfactant (cocamidopropylbetaine-BW) was the main parameter influencing both PCP and PCDDF removal from the 1-4 mm soil fraction by attrition. The behavior of each 2,3,7,8-PCDD/F congener during the attrition process was studied. The results indicated that the concentration of surfactant had a significant and positive effect on the removal of almost all of the dioxin and furan. The removal of 56%, 55%, 50%, 67% and 62% of the contaminants were obtained for As, Cr, Cu, PCP and PCDDF, respectively, using the optimized conditions ([BW]= 2% (w.w-1), T = 25°C and PD = 40% (w.w-1)). These results showed that attrition in the presence of a surfactant can be efficiently used to remediate the coarse fractions of soil contaminated by As, Cr, Cu, PCP and PCDDF.

Design and long-term monitoring of DSC/CIGS tandem solar module

NASA Astrophysics Data System (ADS)

Vildanova, M. F.; Nikolskaia, A. B.; Kozlov, S. S.; Shevaleevskiy, O. I.

2015-11-01

This paper describes the design and development of tandem dye-sensitized/Cu(In, Ga)Se (DSC/CIGS) PV modules. The tandem PV module comprised of the top DSC module and a bottom commercial 0,8 m2 CIGS module. The top DSC module was made of 10 DSC mini-modules with the field size of 20 × 20 cm2 each. Tandem DSC/CIGS PV modules were used for providing the long-term monitoring of energy yield and electrical parameters in comparison with standalone CIGS modules under outdoor conditions. The outdoor test facility, containing solar modules of both types and a measurement unit, was located on the roof of the Institute of Biochemical Physics in Moscow. The data obtained during monitoring within the 2014 year period has shown the advantages of the designed tandem DSC/CIGS PV-modules over the conventional CIGS modules, especially for cloudy weather and low-intensity irradiation conditions.

Intramolecular triple helix as a model for regular polyribonucleotide (CAA)(n).

PubMed

Efimov, Alexander V; Spirin, Alexander S

2009-10-09

The regular (CAA)(n) polyribonucleotide, as well as the omega leader sequence containing (CAA)-rich core, have recently been shown to form cooperatively melted and compact structures. In this report, we propose a structural model for the (CAA)(n) sequence in which the polyribonucleotide chain is folded upon itself, so that it forms an intramolecular triple helix. The triple helix is stabilized by hydrogen bonding between bases thus forming coplanar triads, and by stacking interactions between the base triads. A distinctive feature of the proposed triple helix is that it does not contain the canonical double-helix elements. The difference from the known triple helices is that Watson-Crick hydrogen bond pairings do not take place in the interactions between the bases within the base triads.

De novo protein sequencing by combining top-down and bottom-up tandem mass spectra.

PubMed

Liu, Xiaowen; Dekker, Lennard J M; Wu, Si; Vanduijn, Martijn M; Luider, Theo M; Tolić, Nikola; Kou, Qiang; Dvorkin, Mikhail; Alexandrova, Sonya; Vyatkina, Kira; Paša-Tolić, Ljiljana; Pevzner, Pavel A

2014-07-03

There are two approaches for de novo protein sequencing: Edman degradation and mass spectrometry (MS). Existing MS-based methods characterize a novel protein by assembling tandem mass spectra of overlapping peptides generated from multiple proteolytic digestions of the protein. Because each tandem mass spectrum covers only a short peptide of the target protein, the key to high coverage protein sequencing is to find spectral pairs from overlapping peptides in order to assemble tandem mass spectra to long ones. However, overlapping regions of peptides may be too short to be confidently identified. High-resolution mass spectrometers have become accessible to many laboratories. These mass spectrometers are capable of analyzing molecules of large mass values, boosting the development of top-down MS. Top-down tandem mass spectra cover whole proteins. However, top-down tandem mass spectra, even combined, rarely provide full ion fragmentation coverage of a protein. We propose an algorithm, TBNovo, for de novo protein sequencing by combining top-down and bottom-up MS. In TBNovo, a top-down tandem mass spectrum is utilized as a scaffold, and bottom-up tandem mass spectra are aligned to the scaffold to increase sequence coverage. Experiments on data sets of two proteins showed that TBNovo achieved high sequence coverage and high sequence accuracy.

Single P-N junction tandem photovoltaic device

DOEpatents

Walukiewicz, Wladyslaw [Kensington, CA; Ager, III, Joel W.; Yu, Kin Man [Lafayette, CA

2012-03-06

A single P-N junction solar cell is provided having two depletion regions for charge separation while allowing the electrons and holes to recombine such that the voltages associated with both depletion regions of the solar cell will add together. The single p-n junction solar cell includes an alloy of either InGaN or InAlN formed on one side of the P-N junction with Si formed on the other side in order to produce characteristics of a two junction (2J) tandem solar cell through only a single P-N junction. A single P-N junction solar cell having tandem solar cell characteristics will achieve power conversion efficiencies exceeding 30%.

Single P-N junction tandem photovoltaic device

DOEpatents

Walukiewicz, Wladyslaw [Kensington, CA; Ager, III, Joel W.; Yu, Kin Man [Lafayette, CA

2011-10-18

A single P-N junction solar cell is provided having two depletion regions for charge separation while allowing the electrons and holes to recombine such that the voltages associated with both depletion regions of the solar cell will add together. The single p-n junction solar cell includes an alloy of either InGaN or InAlN formed on one side of the P-N junction with Si formed on the other side in order to produce characteristics of a two junction (2J) tandem solar cell through only a single P-N junction. A single P-N junction solar cell having tandem solar cell characteristics will achieve power conversion efficiencies exceeding 30%.

Co2(CO)8-catalyzed intramolecular hetero-Pauson-Khand reaction of alkynecarbodiimide: synthesis of (+/-)-physostigmine.

PubMed

Mukai, Chisato; Yoshida, Tatsunori; Sorimachi, Mao; Odani, Akira

2006-01-05

[reaction: see text] Herein we describe a novel Co(2)(CO)(8)-catalyzed intramolecular aza-Pauson-Khand-type reaction of alkynecarbodiimide derivatives affords pyrrolo[2,3-b]indol-2-one ring systems in reasonable yields. This is the first reported Co(2)(CO)(8) successfully applied in the hetero-Pauson-Khand reaction. Significantly, the transformation of one of our pyrrolo[2,3-b]indol-2-one derivatives into the indole alkaloid, (+/-)-physostigmine, was completed in a highly stereoselective manner.

Enantioselective synthesis of chiral 3-aryl-1-indanones through rhodium-catalyzed asymmetric intramolecular 1,4-addition.

PubMed

Yu, Yue-Na; Xu, Ming-Hua

2013-03-15

Enantioselective synthesis of potentially useful chiral 3-aryl-1-indanones was achieved through a rhodium-catalyzed asymmetric intramolecular 1,4-addition of pinacolborane chalcone derivatives using extraordinary simple MonoPhos as chiral ligand under relatively mild conditions. This novel protocol offers an easy access to a wide variety of enantioenriched 3-aryl-1-indanone derivatives in high yields (up to 95%) with excellent enantioselectivities (up to 95% ee).

Efficient Monolithic Perovskite/Silicon Tandem Solar Cell with Cell Area >1 cm(2).

PubMed

Werner, Jérémie; Weng, Ching-Hsun; Walter, Arnaud; Fesquet, Luc; Seif, Johannes Peter; De Wolf, Stefaan; Niesen, Bjoern; Ballif, Christophe

2016-01-07

Monolithic perovskite/crystalline silicon tandem solar cells hold great promise for further performance improvement of well-established silicon photovoltaics; however, monolithic tandem integration is challenging, evidenced by the modest performances and small-area devices reported so far. Here we present first a low-temperature process for semitransparent perovskite solar cells, yielding efficiencies of up to 14.5%. Then, we implement this process to fabricate monolithic perovskite/silicon heterojunction tandem solar cells yielding efficiencies of up to 21.2 and 19.2% for cell areas of 0.17 and 1.22 cm(2), respectively. Both efficiencies are well above those of the involved subcells. These single-junction perovskite and tandem solar cells are hysteresis-free and demonstrate steady performance under maximum power point tracking for several minutes. Finally, we present the effects of varying the intermediate recombination layer and hole transport layer thicknesses on tandem cell photocurrent generation, experimentally and by transfer matrix simulations.

Palladium-Mediated Catalysis Leads to Intramolecular Narcissistic Self-Sorting on a Cavitand Platform.

PubMed

Nagymihály, Zoltán; Caturello, Naidel A M S; Takátsy, Anikó; Aragay, Gemma; Kollár, László; Albuquerque, Rodrigo Q; Csók, Zsolt

2017-01-06

Palladium-catalyzed aminocarbonylation reactions have been used to directly convert a tetraiodocavitand intermediate into the corresponding carboxamides and 2-ketocarboxamides. When complex mixtures of the amine reactants are employed in competition experiments using polar solvents, such as DMF, no "mixed" products possessing structurally different amide fragments are detected either by 1 H or 13 C NMR. Only highly symmetrical cavitands are sorted out of a large number of potentially feasible products, which represents a rare example of intramolecular, narcissistic self-sorting. Our experimental results along with thermodynamic energy analysis suggest that the observed self-sorting is a symmetry-driven, kinetically controlled process.

Asymmetric intramolecular Pauson-Khand reaction mediated by a remote sulfenyl or sulfinyl group.

PubMed

García Ruano, José Luis; Torrente, Esther; Parra, Alejandro; Alemán, José; Martín-Castro, Ana M

2012-08-03

In this work, we report the use of the asymmetric intramolecular Pauson-Khand reactions of 4-aryl-4-cyano-1,6-enynes for obtaining enantiomerically enriched bicyclo[3.3.0]octenones, and the influence of both the quaternary stereocenter and the sulfur functions located at ortho-position of the aryl group, on their stereoselectivity and reactivity. The sulfenyl derivatives bearing substituted or unsubstituted triple bonds and mono- and disubstituted alkene moieties afford bicyclo[3.3.0]octenones in high yields with complete diastereocontrol. These results are explained by assuming the association of the lone electron pair at sulfur to the Co-alkyne complexes.

An abnormally slow proton transfer reaction in a simple HBO derivative due to ultrafast intramolecular-charge transfer events.

PubMed

Alarcos, Noemí; Gutierrez, Mario; Liras, Marta; Sánchez, Félix; Douhal, Abderrazzak

2015-07-07

We report on the steady-state, picosecond and femtosecond time-resolved studies of a charge and proton transfer dye 6-amino-2-(2'-hydroxyphenyl)benzoxazole (6A-HBO) and its methylated derivative 6-amino-2-(2'-methoxyphenyl)benzoxazole (6A-MBO), in different solvents. With femtosecond resolution and comparison with the photobehaviour of 6A-MBO, we demonstrate for 6A-HBO in solution, the photoproduction of an intramolecular charge-transfer (ICT) process at S1 taking place in ∼140 fs or shorter, followed by solvent relaxation in the charge transferred species. The generated structure (syn-enol charge transfer conformer) experiences an excited-state intramolecular proton-transfer (ESIPT) reaction to produce a keto-type tautomer. This subsequent proton motion occurs in 1.2 ps (n-heptane), 14 ps (DCM) and 35 ps (MeOH). In MeOH, it is assisted by the solvent molecules and occurs through tunneling for which we got a large kinetic isotope effect (KIE) of about 13. For the 6A-DBO (deuterated sample in CD3OD) the global proton-transfer reaction takes place in 200 ps, showing a remarkable slow KIE regime. The slow ESIPT reaction in DCM (14 ps), not through tunnelling as it is not sensitive to OH/OD exchange, has however to overcome an energy barrier using intramolecular as well as solvent coordinates. The rich ESIPT dynamics of 6A-HBO in the used solutions is governed by an ICT reaction, triggered by the amino group, and it is solvent dependent. Thus, the charge injection to a 6A-HBO molecular frame makes the ICT species more stable, and the phenol group less acidic, slowing down the subsequent ESIPT reaction. Our findings bring new insights into the coupling between ICT and ESIPT reactions on the potential-energy surfaces of several barriers.