- Two new glyceroglycolipids from the fruits of Cucurbita moschata
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Aphytochemical study of Cucurbita moschata resulted in the characterisation of two new glyceroglycolipids, 1-O-(9Z, 12Z,15Z-octadecatrienoyl)-3-0-[β- D-galactopyranosyl-(1-6)-0-p-D-galactopyranosyl-(1?6)-O-p-D-galactopyranosyl] glycerol (1) and 1-0-(9Z,12
- Jianga, Zhi-Guo,Dua, Qi-Zhen
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- Large-scale synthesis of methyl cis-9, trans-11-octadecadienoate from methyl ricinoleate
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The conjugated linoleic acid methyl cis-9, trans-11-octadecadienoate has been prepared on a large scale from methyl ricinoleate. Methyl ricinoleate was purified from castor esters by a partition method. It was converted to the mesylate, which was reacted with a base (1,8-diazabicyclo[5.4.0]-undec-7-ene) to give a product that contained 66% of the desired ester. Two urea crystallizations produced a product containing 83% methyl cis-9,trans-11-octadecadienoate, the identity of which was confirmed by gas chromatography linked to mass spectrometry and by Fourier transform infrared spectroscopy. The remaining impurities were methyl cis-9,cis-11- and cis-9-,trans-12-octadecadienoate.
- Berdeaux,Christie,Gunstone,Sebedio
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- Investigating inner-sphere reorganization via secondary kinetic isotope effects in the C-H cleavage reaction catalyzed by soybean lipoxygenase: Tunneling in the substrate backbone as well as the transferred hydrogen
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This work describes the application of NMR to the measurement of secondary deuterium (2° 2H) and carbon-13 (13C) kinetic isotope effects (KIEs) at positions 9-13 within the substrate linoleic acid (LA) of soybean lipoxygenase-1. The KIEs have been measured using LA labeled with either protium (11,11- h2-LA) or deuterium (11,11-d2-LA) at the reactive C11 position, which has been previously shown to yield a primary deuterium isotope effect of ca. 80. The conditions of measurement yield the intrinsic 2° 2H and 13C KIEs on kcat/Km directly for 11,11-d2-LA, whereas the values for the 2° 2H KIEs for 11,11-h2-LA are obtained after correction for a kinetic commitment. The pattern of the resulting 2° 2H and 13C isotope effects reveals values that lie far above those predicted from changes in local force constants. Additionally, many of the experimental values cannot be modeled by electronic effects, torsional strain, or the simple inclusion of a tunneling correction to the rate. Although previous studies have shown the importance of extensive tunneling for cleavage of the primary hydrogen at C11 of LA, the present findings can only be interpreted by extending the conclusion of nonclassical behavior to the secondary hydrogens and carbons that flank the position undergoing C-H bond cleavage. A quantum mechanical method introduced by Buhks et al. [J. Phys. Chem. 1981, 85, 3763] to model the inner-sphere reorganization that accompanies electron transfer has been shown to be able to reproduce the scale of the 2° 2H KIEs.
- Meyer, Matthew P.,Klinman, Judith P.
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- Linoleic acid, α-linolenic acid, and monolinolenins as antibacterial substances in the heat-processed soybean fermented with Rhizopus oligosporus
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Antibacterial activities against Staphylococcus aureus and Bacillus subtilis were found in an ethanol fraction of tempe, an Indonesian fermented soybean produced using Rhizopus oligosporus. The ethanol fraction contained free fatty acids, monoglycerides, and fatty acid ethyl esters. Among these substances, linoleic acid and α-linolenic acid exhibited antibacterial activities against S. aureus and B. subtilis, whereas 1-monolinolenin and 2-monolinolenin exhibited antibacterial activity against B. subtilis. The other free fatty acids, 1-monoolein, monolinoleins, ethyl linoleate, and ethyl linolenate did not exhibit bactericidal activities. These results revealed that R. oligosporus produced the long-chain polyunsaturated fatty acids and monolinolenins as antibacterial substances against the Gram-positive bacteria during the fungal growth and fermentation of heat-processed soybean.
- Kusumah, Dewi,Maeda, Isamu,Murakami, Mai,Wakui, Misaki,Xie, Xiaonan,Yukihito, Kabuyama
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- Synthesis of linoleic acids combinatorially labeled at the vinylic positions as substrates for lipoxygenases
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Mammalian lipoxygenases have been implicated in a number of inflammation-related human diseases. Soybean lipoxygenase-1 is the archetypical example of known lipoxygenases. Here we report the synthesis of linoleic acid and (11,11)-d2-linoleic acid which are combinatorially labeled at the vinylic positions (9, 10, 12, and 13). Combinatorial labeling schemes allow for the simultaneous determination of KIEs in enzymatic reactions using NMR. Substrates are, thus, available as probes of detailed mechanism in kinetic isotope effect (KIE) studies of lipoxygenases.
- Meyer, Matthew P.,Klinman, Judith P.
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- Bioactive tigliane diterpenoids from the latex of Euphorbia fischeriana
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Latex is a type of sticky endogenous fluids derived from diverse plants including Euphorbia fischeriana, and is of great scientific and commercial values. In the current study, it was demonstrated that the latex extracted from E. fischeriana strongly respelled the growth of cotton bollworm, Helicoverpa armigera. Using spectroscopic methods, HPLC, and GC-MS analyses, six aliphatic tigliane diterpenoids were isolated from the latex of E. fischeriana, among which three compounds (2, 3, and 5) were new. Two major compounds (1 and 4) exhibited remarkable antifeedant activity against H. armigera, with EC50 values at 2.59 and 15.32 μg/cm2, respectively. In addition, the quantification analysis of diterpenoids in different organs indicated that 4 was the most abundant constituent and was highly accumulated in the latex. Collectively, the current study highlighted that the diterpenoids in latex of E. fischeriana had a considerable antifeedant function against H. armigera, which might be employed for the future development of natural insecticides for organic farming.
- Deng, Yan-Yan,Qu, Bo,Zhan, Zhong-Lang,Wang, An-Qi,Zhou, Wei,Jia, Ming-Yue,Hua, Juan,Luo, Shi-Hong
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- Nickel-Mediated Alkoxycarbonylation for Complete Carbon Isotope Replacement
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Many commercial drugs, as well as upcoming pharmaceutically active compounds in the pipeline, display aliphatic carboxylic acids or derivatives thereof as key structural entities. Synthetic methods for rapidly accessing isotopologues of such compounds are highly relevant for undertaking critical pharmacological studies. In this paper, we disclose a direct synthetic route allowing for full carbon isotope replacement via a nickel-mediated alkoxycarbonylation. Employing a nickelII pincer complex ([(N2N)Ni-Cl]) in combination with carbon-13 labeled CO, alkyl iodide, sodium methoxide, photocatalyst, and blue LED light, it was possible to generate the corresponding isotopically labeled aliphatic carboxylates in good yields. Furthermore, the developed methodology was applied to the carbon isotope substitution of several pharmaceutically active compounds, whereby complete carbon-13 labeling was successfully accomplished. It was initially proposed that the carboxylation step would proceed via the in situ formation of a nickellacarboxylate, generated by CO insertion into the Ni-alkoxide bond. However, preliminary mechanistic investigations suggest an alternative pathway involving attack of an open shell species generated from the alkyl halide to a metal ligated CO to generate an acyl NiIII species. Subsequent reductive elimination involving the alkoxide eventually leads to carboxylate formation. An excess of the alkoxide was essential for obtaining a high yield of the product. In general, the presented methodology provides a simple and convenient setup for the synthesis and carbon isotope labeling of aliphatic carboxylates, while providing new insights about the reactivity of the N2N nickel pincer complex applied.
- Ton, Stephanie J.,Neumann, Karoline T.,N?rby, Peter,Skrydstrup, Troels
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p. 17816 - 17824
(2021/11/04)
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- Branched alkyl sulfonate anionic surfactant and preparation process thereof
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The invention discloses a branched alkyl sulfonate anionic surfactant and a preparation process thereof, and belongs to the field of fine chemical surfactants. The method comprises the steps of (1) conducting a esterification carboxyl-terminated reaction, specifically, catalyzing oleic acid or linoleic acid and fatty alcohol to be subjected to esterification reaction by adopting organic acid as acatalyst to prepare an alkyl oleate or alkyl linoleate compound; and (2) conducting a double bond addition sulfonation reaction, specifically, in the presence of the catalyst, carrying out sulfonationreaction with the alkyl oleate compound or the alkyl linoleate compound obtained in the step (1) by taking low-carbon alcohol and deionized water as solvents and sodium hydrogen sulfite as a sulfonation reagent to prepare the branched alkyl sulfonate anionic surfactant. The synthesized branched alkyl sulfonate anionic surfactant product can effectively reduce the surface tension of an aqueous solution, and is good in solubility, large in initial foaming amount, high in defoaming speed and excellent in surfactant performance. The method has the advantages of simple process operation, few sidereactions, energy saving and environmental protection.
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Paragraph 0090-0091
(2021/02/10)
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- Novel synthesized microporous ionic polymer applications in transesterification of Jatropha curcas seed oil with short Chain alcohol
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New suites of sulfonic acid-functionalized microporous ionic polymers (PIPs) catalysts were synthesized with polymer, alkyl bromides, and 1, 3-propane sultone via a two-step procedure. The synthesized microporous PIP catalysts were characterized using FT-IR, SEM-Mapping, XPS, N2 adsorption–desorption isotherms, solid NMR spectroscopy, and element analysis. Esterification of several fatty acids with ethanol, which was used as a model reaction in the stabilization of Jatropha curcas seed oil, was checked over functionalized PIP. We tested the catalytic performance of PIP-C8 on the synthesis of fatty acid esters via the transesterification of J. curcas seed oil with a mixture of short-chain alcohols such as ethanol, ethanol–to–diethyl carbonate (1;1 molar ratio), and ethanol–to–dimethyl carbonate (1:1 molar ratio) with 170 mg of PIP-C8 at reflux temperature with agitation. The PIP-C8 catalyst was particularly effective, having achieved yields of 85%, 94%, and 70% for J. curcas seed oil with ethanol, J. curcas seed oil with ethanol–to–DEC, and J. curcas seed oil with ethanol–to–DMC, respectively, under the optimized reaction conditions. The catalyst could be recycled more than five times without significant deactivation. Kinetic studies performed at different temperatures revealed that the conversion of oleic acid to an ethyl ester follows a first-order reaction. The best catalysts with microporous structure (average pore diameter: 1.7–1.9 nm, pore volume: 0.23–0.33 cm3 g–1) and –SO3H density (0.70–0.84 mmol/gcat) were obtained by 1, 3-propane sultone of the chemically activated. The results indicate that the site activity of functionalized microporous ionic polymer materials shows promising approach for the development of environmentally friendly technology.
- Chang, Tao,Hao, Yongjing,Jinxi, Jinxi,Kai, Kai,Panchal, Balaji,Qin, Shenjun,Sun, Yuzhuang,Zhao, Cunling,Zhao, Qiaojing,Zhu, Zheng
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- Highly ordered mesoporous functionalized pyridinium protic ionic liquids framework as efficient system in esterification reactions for biofuels production
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Polysiloxane acidic ionic liquids containing pyridinium trifluoroacetate salts (PMO-Py-IL) were synthesized from pyridine containing organosilane precursors. Characterization by SEM, XRD, TGA, and nitrogen porosimetry confirmed that both pyridinium cation and trifluoroacetate anion were successfully incorporated within the organosilica network. The resulting organic-inorganic hybrid nanomaterial (PMO-Py-IL) was studied as nanocatalyst in free fatty acids esterification into biodiesel-like compounds. Remarkably, the synergistic hydrophilic/hydrophobic effect of pyridinium and trifluoroacetate ionic liquid in the well-ordered channels of PMO-Py-IL nanomaterial enhanced the activity toward sustainable biodiesel-like esters production. More importantly, PMO-Py-IL nanocatalyst also exhibited an exceptional activity and stability. The catalyst could be easily separated to reuse at least in ten reactions runs preserving almost intact its catalytic activity under otherwise identical conditions to those employed for the fresh catalysts.
- Luque, Rafael,Rajabi, Fatemeh
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- Second-Generation meta-Phenolsulfonic Acid-Formaldehyde Resin as a Catalyst for Continuous-Flow Esterification
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A second-generation m-phenolsulfonic acid-formaldehyde resin (PAFR II) catalyst was prepared by condensation polymerization of sodium m-phenolsulfonate and paraformaldehyde in an aqueous H2SO4 solution. This reusable, robust acid resin catalyst was improved in both catalytic activity and stability, maintaining the characteristics of the previous generation catalyst (p-phenolsulfonic acid-formaldehyde resin). PAFR II was applied in the batchwise and continuous-flow direct esterification without water removal and provided higher product yields in continuous-flow esterification than any other commercial ion-exchanged acid catalyst tested.
- Hu, Hao,Ota, Hajime,Baek, Heeyoel,Shinohara, Kenta,Mase, Toshiaki,Uozumi, Yasuhiro,Yamada, Yoichi M. A.
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supporting information
p. 160 - 163
(2020/01/02)
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- Identification and α -Glucosidase Inhibitory Activity of Meroterpenoids from Hericium erinaceus
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Hericium erinaceus is a very popular edible and medicinal mushroom used for the treatment of enervation and gastrointestinal diseases in Eastern Asia. Chemical investigation on the fruiting body of Hericium erinaceus led to the isolation of 4 new (1 - 4) and 10 known meroterpenoids (5 - 14). The structures of new compounds were determined via analysis of NMR and MS data in combination with chemical derivatization. The inhibitory activities of 1 - 14 against α -glucosidase were evaluated using p -nitrophenyl- α -D-glucopyranoside, sucrose, or maltose as substrate. Compounds 6, 9, 11 - 13 were demonstrated to show the α -glucosidase inhibitory activities. This work confirms the potential of H. erinaceus in the treatment of diabetes.
- Bao, Li,Chen, Baosong,Han, Junjie,Liu, Hongwei,Ma, Ke,Wang, Wenzhao
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p. 571 - 578
(2020/06/03)
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- Identification of new diterpene esters from green Arabica coffee beans, and their platelet aggregation accelerating activities
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Eight new ent-kaurane diterpene fatty acid esters, namely caffarolides A–H (1–8), were isolated from green beans of Coffea arabica. Their chemical structures were confirmed by extensive spectroscopic analysis including 1D, 2D NMR (HSQC, HMBC, 1
- Wang, Xia,Meng, QianQian,Peng, XingRong,Hu, GuiLin,Qiu, MingHua
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p. 251 - 257
(2018/05/23)
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- Metal-free transesterification catalyzed by tetramethylammonium methyl carbonate
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Environmentally benign metal-free tetramethylammonium methyl carbonate is effective as a catalyst for the chemoselective, scalable, and reusable transesterification of various esters and alcohols in common organic solvents. In situ-generated highly active species, tetramethylammonium alkoxides, can greatly avoid self-decomposition at ≤110 °C, and are reusable. In particular, chelating substrates, such as amino alcohols, diols, triols, sugar derivatives, alkaloids, α-amino acid esters, etc., which deactivate conventional metal salt catalysts, can be used. A 100 gram scale biodiesel production was also demonstrated.
- Hatano, Manabu,Tabata, Yuji,Yoshida, Yurika,Toh, Kohei,Yamashita, Kenji,Ogura, Yoshihiro,Ishihara, Kazuaki
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supporting information
p. 1193 - 1198
(2018/03/27)
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- Metathesis of renewable polyene feedstocks – Indirect evidences of the formation of catalytically active ruthenium allylidene species
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Cross-metathesis (CM) of conjugated polyenes, such as 1,6-diphenyl-1,3,5-hexatriene (1) and α-eleostearic acid methyl ester (2) with several olefins, including 1-hexene, dimethyl maleate and cis-stilbene as model compounds has been carried out using (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)-dichloro(o-isopropoxyphenylmethylene)ruthenium (Hoveyda-Grubbs 2nd generation, HG2) catalyst. The feasibility of these reactions is demonstrated by the observed high conversions and reasonable yields. Thus, regardless of the relatively low electron density, =CH–CH= conjugated units of molecules, including compound 2 as a sustainable, non-foodstuff source, can be utilized as building blocks for the synthesis of various value-added chemicals via olefin metathesis. DFT-studies and the product spectrum of the self-metathesis of 1,6-diphenyl-1,3,5-hexatriene suggest that a Ru η1-allylidene complex is the active species in the reaction.
- Kovács, Ervin,Sághy, Péter,Turczel, Gábor,Tóth, Imre,Lendvay, Gy?rgy,Domján, Attila,Anastas, Paul T.,Tuba, Róbert
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supporting information
p. 213 - 217
(2017/09/12)
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- Heterogeneous esterification of fatty acids with methanol catalyzed by Lewis acidic organozirconium complexes with Keggin-type mono-aluminum-substituted polyoxotungstates
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Two Lewis acidic organozirconium complexes with α-Keggin-type mono-aluminum-substituted polyoxotungstates, [(n-C4H9)4N]6[α-PW11Al(OH)O39ZrCp2]2 (Cp = η5-C5H5?) (TBA-P-Al-Zr) and [(n-C4H9)4N]6[α-SiW11Al(OH)2O38ZrCp2]2·2H2O (TBA-Si-Al-Zr), were used as heterogeneous catalysts for the esterification of various fatty acids with methanol. For the esterification of linoleic acid at 80 ± 2 °C, TBA-P-Al-Zr exhibited 83% conversion after 6 h, approximately six times higher than that of TBA-Si-Al-Zr. TBA-P-Al-Zr also exhibited 69–90% conversion for the esterification of oleic acid, palmitic acid, myristic acid, and lauric acid with methanol at 80 ± 2 °C.
- Kato, Chika Nozaki,Ogasawara, Tsukasa,Kondo, Akari,Kato, Daichi
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- Fatty acid based biocarbonates: Al-mediated stereoselective preparation of mono-, di- and tricarbonates under mild and solvent-less conditions
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A catalytic method for the preparation of a series of fatty acid derived biocarbonates has been developed using a binary Al-complex/PPNCl catalyst. This catalyst system allows conversion of fatty acid derived epoxides under comparatively mild reaction conditions (70-85 °C, 10 bar) while maintaining high levels of diastereospecificity with cis/trans ratios of up to 97:3 in the products. The comparative catalysis data obtained for the reactions catalysed only by the nucleophilic halide based components show that the presence of the Al-complex is crucial for the retention of the original stereochemistry.
- Pe?a Carrodeguas,Cristòfol,Fraile,Mayoral,Dorado,Herrerías,Kleij
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supporting information
p. 3535 - 3541
(2017/08/15)
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- Sterols and Fatty Acids of the Harmful Dinoflagellate Cochlodinium polykrikoides
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Sterol and fatty acid compositions were determined for Cochlodinium polykrikoides, a toxic, bloom-forming dinoflagellate of global significance. The major sterols were dinosterol (40% of total sterols), dihydrodinosterol (32%), and the rare 4α-methyl Δ8(14) sterol, amphisterol (23%). A minor sterol, 4α-methylergost-24(28)-enol was also detected (5.0%). The fatty acids had a high proportion of PUFAs (47%), consisting mainly of EPA (20%) and the relatively uncommon octadecapentaenoic acid (18: 5, 22%). While unlikely to be responsible for toxicity to fish, these lipids may contribute to the deleterious effects of this alga to invertebrates.
- Giner, José-Luis,Ceballos, Harriette,Tang, Ying-Zhong,Gobler, Christopher J.
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p. 249 - 252
(2016/02/27)
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- Four new phorbol diesters from Croton tiglium and their cytotoxic activities
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Phytochemical investigation of the seeds of Croton tiglium resulted in the isolation and structure elucidation of four new 4-deoxy-4β-phorbol diesters (1-4) named as 12-O-tiglylphorbol-4-deoxy-4β-phorbol-13-acetate (1), 12-O-tiglylphorbol-4-deoxy-4β-phorbol-13-hexadecanoate (2), 13-O-acetylphorbol-4-deoxy-4β-phorbol-20-oleate (3) and 13-O-acetylphorbol-4-deoxy-4β-phorbol-20-linoleate (4), respectively. The structures of the new compounds were established by 1D, 2D-NMR and HR-ESI-MS spectroscopic data and chemical degradation experiments. The cytotoxic activities of compounds 1-4 were evaluated against hepatic tumor cell lines (SNU387 and SNU398). Among these compounds, compound 4 exhibited the most potent activity against the SNU387 with IC50 value of 0.71 μM.
- Zhang, Xiao-Long,Khan, Ashfaq-Ahmad,Wang, Lun,Yu, Kai,Li, Fu,Wang, Ming-Kui
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- Antiproliferative activity of synthetic fatty acid amides from renewable resources
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In the work, the in vitro antiproliferative activity of a series of synthetic fatty acid amides were investigated in seven cancer cell lines. The study revealed that most of the compounds showed antiproliferative activity against tested tumor cell lines, mainly on human glioma cells (U251) and human ovarian cancer cells with a multiple drug-resistant phenotype (NCI-ADR/RES). In addition, the fatty methyl benzylamide derived from ricinoleic acid (with the fatty acid obtained from castor oil, a renewable resource) showed a high selectivity with potent growth inhibition and cell death for the glioma cell line - the most aggressive CNS cancer.
- Dos Santos, Daiane S.,Piovesan, Luciana A.,D'Oca, Caroline R. Montes,Hack, Carolina R. Lopes,Treptow, Tamara G.M.,Rodrigues, Marieli O.,Vendramini-Costa, Débora B.,Ruiz, Ana Lucia T.G.,De Carvalho, Jo?o Ernesto,D'Oca, Marcelo G. Montes
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p. 340 - 347
(2015/02/02)
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- Design and synthesis of protein kinase C epsilon selective diacylglycerol lactones (DAG-lactones)
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DAG-lactones afford a synthetically accessible, high affinity platform for probing structure activity relationships at the C1 regulatory domain of protein kinase C (PKC). Given the central role of PKC isoforms in cellular signaling, along with their differential biological activities, a critical objective is the design of isoform selective ligands. Here, we report the synthesis of a series of DAG-lactones varying in their side chains, with a particular focus on linoleic acid derivatives. We evaluated their selectivity for PKC epsilon versus PKC alpha both under standard lipid conditions (100% phosphatidylserine, PS) as well as in the presence of a nuclear membrane mimetic lipid mixture (NML). We find that selectivity for PKC epsilon versus PKC alpha tended to be enhanced in the presence of the nuclear membrane mimetic lipid mixture and, for our lead compound, report a selectivity of 32-fold.
- Ann, Jihyae,Yoon, Suyoung,Baek, Jisoo,Kim, Da Hye,Lewin, Nancy E.,Hill, Colin S.,Blumberg, Peter M.,Lee, Jeewoo
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p. 332 - 341
(2015/05/04)
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- Plasticizer and surfactant formation from food-waste- and algal biomass-derived lipids
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The potential of lipids derived from food-waste and algal biomass (produced from food-waste hydrolysate) for the formation of plasticizers and surfactants is investigated herein. Plasticizers were formed by epoxidation of double bonds of methylated unsaturated fatty acids with in situ generated peroxoformic acid. Assuming that all unsaturated fatty acids are convertible, 0.35 and 0.40 g of plasticizer can be obtained from 1 g of crude algae- or food-waste-derived lipids, respectively. Surfactants were formed by transesterification of saturated and epoxidized fatty acid methyl esters (FAMEs) with polyglycerol. The addition of polyglycerol would result in a complete conversion of saturated and epoxidized FAMEs to fatty acid polyglycerol esters. This study successfully demonstrates the conversion of food-waste into value-added chemicals using simple and conventional chemical reactions.
- Pleissner, Daniel,Lau, Kin Yan,Zhang, Chengwu,Lin, Carol Sze Ki
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p. 1686 - 1691
(2015/06/02)
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- Dissociation of proton-bound complexes reveals geometry and arrangement of double bonds in unsaturated lipids
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Double bond position and stereochemistry in unsaturated lipids can have profound impact on biological properties and activities but the assignment of these features by mass spectrometry is frequently challenging. Conventional techniques for lipid identification rely on collision-induced dissociation (CID) and are most often unable to differentiate between lipid isomers, particularly those involving double bond position and geometry (i.e., cis and trans). In this study, CID performed on proton-bound complexes of fatty acid methyl esters and iodoaniline (and related reagents) reveals unusual fragmentation patterns. CID products are shown to result from proton transfer and are associated with specific structures of the unsaturated lipids. Notably, CID of these complexes can not only distinguish cis- and trans-fatty acid methyl esters, but also differentiate conjugated double bond arrangements from non-conjugated analogs. Herein, the mechanisms underpinning this unique CID behavior are investigated by stable isotope labeling and are proposed to involve both carbene and free radical intermediates.
- Pham, Huong T.,Prendergast, Matthew B.,Dunstan, Christopher W.,Trevitt, Adam J.,Mitchell, Todd W.,Julian, Ryan R.,Blanksby, Stephen J.
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p. 170 - 177
(2015/10/20)
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- Selective ethenolysis and oestrogenicity of compounds from cashew nut shell liquid
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The ethenolysis of cardanol (2), a waste product from cashew kernel production, was carried out using a variety of metathesis catalysts. Surprisingly, the best activities and selectivities could be observed with ruthenium based 1st generation type catalysts converting cardanol (2) almost completely to the corresponding 1-octene (6) and 3-non-8-enylphenol (4), a potential detergent precursor. Detailed investigation of the reaction system showed that the high activity and selectivity were due to a combination of ethenolysis and internal self-metathesis of the unsaturated cardanol mixture, 2. Self-metathesis of cardanol (2) containing three double bonds led to the formation of 3-non-8-enylphenol (4) and 1,4-cyclohexadiene (7). The latter was crucial for a high selectivity and activity in the ethenolysis, not only of cardanol (2), but also of other substrates like methyl oleate (10) when using ruthenium based 1st generation catalysts. The endocrine disrupting properties of 3-nonylphenol and related compounds are compared. the Partner Organisations 2014.
- Julis, Jennifer,Bartlett, Stuart A.,Baader, Sabrina,Beresford, Nicola,Routledge, Edwin J.,Cazin, Catherine S.J.,Cole-Hamilton, David J.
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p. 2846 - 2856
(2014/05/06)
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- Biodiesel synthesis from the esterification of free fatty acids and alcohol catalyzed by long-chain Bronsted acid ionic liquid
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A long-chain Bronsted acid ionic liquid (IL), 3-(N,N- dimethyldodecylammonium)propanesulfonic acid p-toluenesulfonate ([DDPA][Tos]), was prepared and characterized by FT-IR, 1H NMR, 13C NMR, UV/vis and TGA. The H0 (Hammett function) value of the IL was also determined. The IL as catalyst was applied to the catalytic synthesis of biodiesel from free fatty acids (FFAs). The influencing factors, such as the type and amount of catalyst, reaction time, molar ratio of fatty acid to methanol and reaction temperature, were investigated. The results indicated that the long-chain Bronsted acid IL showed high catalytic activity and fair reusability. Esterification was accomplished under the following optimized conditions: molar ratio of alcohols to FFA at 1.5:1, mole fraction of ionic liquid at 10%, 60 °C, and 3 h. The products could be separated from the catalyst system by liquid-liquid biphase separation at room temperature with good yields of 92.5% to 96.5%. The catalyst could be reused nine times after the removal of water and alcohol. Therefore, the long-chain Bronsted acid IL has good potential for the synthesis of biodiesel from low-cost feedstocks such as waste oil and woody plant oils.
- He, Leqin,Qin, Shenjun,Chang, Tao,Sun, Yuzhuang,Gao, Xiaorui
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p. 1102 - 1107
(2013/04/24)
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- Sustainable and efficient methodology for CLA synthesis and identification
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Microwave-assisted organic synthesis and continuous-flow techniques have been successfully employed for the preparation of conjugated linoleic acids (CLA), compounds with high health beneficial effects. A good production rate of CLA was obtained. A sustainable methodology for the differentiation of both positional and geometrical CLA isomers (diene), based on the analysis by NMR spectroscopy of the resulting Diels-Alder cycloadducts with an appropriate dienophile, was developed.
- Moreno, Maria,Gomez, M. Victoria,Cebrian, Cristina,Prieto, Pilar,De La Hoz, Antonio,Moreno, Andres
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p. 2584 - 2594
(2013/02/23)
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- Two new aromatic compounds and a new D-arabinitol ester from the mushroom Hericium erinaceum
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Two new aromatic compounds (1, 2), new d-arabinitol ester (3), and two known compounds (4, 5) were isolated from mushroom Hericium erinaceum. The structures of 1-5 were elucidated on the basis of spectral data. Compounds 1, 2, 4, and 5 exhibited α-glucosidasae inhibitory activity.
- Miyazawa, Mitsuo,Takahashi, Toshiyuki,Horibe, Isao,Ishikawa, Ryuuzou
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experimental part
p. 2007 - 2010
(2012/03/26)
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- Echinopsacetylenes A and B, new thiophenes from echinops transiliensis
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Two new polyacetylene thiophenes, echinopsacetylenes A and B (1 and 2), were isolated from the roots of Echinops transiliensis. The structures of 1 and 2 were elucidated on the basis of spectroscopic analyses and chemical transformations. Echinopsacetylenes A (1) is the first natural product possessing an α-terthienyl moiety covalently linked with another thiophene moiety. Echinopsacetylenes B (2) is the first natural thiophene conjugated with a fatty acid moiety. Echinopsacetylene A (1) showed toxicity against the Formosoan subterranean termite (Coptotermes formosanus).
- Nakano, Hiroshi,Cantrell, Charles L.,Mamonov, Leonid K.,Osbrink, Weste L. A.,Ross, Samir A.
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scheme or table
p. 6228 - 6231
(2012/02/05)
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- Catalytic deoxygenation of oleic acid in continuous gas flow for the production of diesel-like hydrocarbons
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Continuous gas phase deoxygenation of oleic acid in the presence of hydrogen employing a granular 2 wt% Pd/C catalyst was investigated under solvent free conditions. Conversion of oleic acid and selectivity to the desired diesel-like C17 hydrocarbons heptadecane and heptadecenes was studied at different reaction conditions such as temperature, gas flow and catalyst amount. The best hydrocarbon yield was achieved with low reaction temperatures, high catalyst amounts and high hydrogen flows. To further decrease the reaction temperature but yet maintain a pure gas phase reaction, reactions were conducted in vacuum. Furthermore, water was added in varying amounts to support desorption and to determine if catalyst deactivation could be overcome. The deoxygenation catalyst was characterized by nitrogen adsorption isotherms (BET; Brunauer-Emmet-Teller method), X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and field emission scanning electron microscopy (FESEM).
- Arend, Matthias,Nonnen, Thomas,Hoelderich, Wolfgang F.,Fischer, Jürgen,Groos, Jeremie
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experimental part
p. 198 - 204
(2012/02/02)
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- Polymer-mounted N3=P(MeNCH2CH2) 3N: A green, efficient and recyclable catalyst for room-temperature transesterifications and amidations of unactivated esters
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Merrifield resin-supported N3P(MeNCH2CH 2)3N shows excellent activity in the transesterification of higher esters such as glyceryl tribenzoate to methyl esters. The catalyst was successfully cycled 20 times (albeit with an increase in reaction time) without compromising yield up to the 20th cycle. The catalyst also showed good performance in amidation reactions of unactivated esters with amino alcohols.
- Chintareddy, Venkat Reddy,Ho, Hung-An,Sadow, Aaron D.,Verkade, John G.
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experimental part
p. 6523 - 6529
(2011/12/21)
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- Novel H3PW12O40: Catalysed esterification reactions of fatty acids at room temperature for biodiesel production
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The catalytic activity of Bronsted acids on fatty acid (FA) esterification at room temperature has been investigated. Noticeably, the H 3PW12O40 heteropolyacid (HPW) showed a very high activity than other catalysts herein evaluated, i.e. p-toluene sulfonic acid and sulfuric acid. High yields in ethyl esters (ca. 90%) were reached after a 4 h reaction at 25 °C on a HPW catalysed reactions. Despite the fact that HPW catalyst was used in a homogeneous phase, it could be efficiently recovered and reused through out a simple recycling protocol, without any activity loss. The effects of alcohol and the FA nature on yield reaction were also investigated.
- De Godoi Silva, Vinicius Wilker,Laier, Leticia Oliveira,Silva, Marcio Jose Da
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experimental part
p. 207 - 211
(2010/08/03)
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- Efficient conversion of triacylglycerols and fatty acids to biodiesel in a microwave reactor using metal triflate catalysts
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We report that catalytic quantities of the Lewis acidic metal catalysts scandium triflate and bismuth triflate promote conversion of oleic, linoleic, palmitic and myristic acids and their glyceryl triesters to the corresponding methyl esters (biodiesel) in greater than 90% yield upon microwave heating. Additionally, both catalysts could be recovered and reused in esterification reactions at least six times.
- Socha, Aaron M.,Sello, Jason K.
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experimental part
p. 4753 - 4756
(2010/11/19)
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- Lycopersicon esculentum Seeds: An industrial byproduct as an antimicrobial agent
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Lycopersicon esculentum (tomato) fruit is a widely studied matrix. However, only few works focus their attention on its seeds, which constitute a major byproduct of the tomato processing industry. In this study the antimicrobial potential of ten different tomato seed extracts from "Bull s heart" and "Cherry" varieties were analyzed against Gram-positive (Staphylococcus aureus, Staphylococcus epidermidis, Micrococcus luteus, Enterococcus faecalis and Bacillus cereus) and Gram-negative (Proteus mirabilis, Escherichia coli, Pseudomonas aeruginosa and Salmonella typhimurium) bacteria and fungi (Candida albicans, Aspergillus fumigatus and Trichophyton rubrum). Regarding antibacterial capacity, the different extracts were revealed to be active only against Gram-positive bacteria, E. faecalis being the most susceptible one (MIC: 2.5-10 mg/mL). Concerning antifungal activity, "Bull s heart" extracts were the most active. In a general way C. albicans was the most susceptible species (MIC: 5-10 mg/mL). The chemical composition of the extracts was also pursued, concerning organic acids, phenolics and fatty acids, in order to establish a possible relationship with the observed antimicrobial effect.
- Taveira, Marcos,Silva, Luis R.,Vale-Silva, Luis A.,Pinto, Eugenia,Valentao, Patricia,Ferreres, Federico,Guedes De Pinho, Paula,Andrade, Paula B.
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experimental part
p. 9529 - 9536
(2011/05/30)
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- CONTINUOUS METHOD FOR THE HETEROGENICALLY CATALYZED ESTERIFICATION OF FATTY ACIDS
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Continuous method for the esterification of free fatty acids in plant and animal fats with alcohols using a heterogenic acid catalyst.
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Page/Page column 4
(2010/10/19)
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- Method for selective esterification of free fatty acids in triglycerides
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A method for the selective esterification of free fatty acids, alone or in triglycerides, with C1-C8 aliphatic alcohols or diols. The method uses a selective heterogeneous esterification catalyst. The catalyst is contacted with a reaction mixture containing a triglyceride having at least 0.5% free fatty acids, or a reaction mixture containing only free fatty acids, and a C1-C8 aliphatic alcohol or diol under conditions suitable for esterification.
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Page/Page column 3
(2010/04/24)
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- Fatty acid desaturation and elongation reactions of trichoderma sp. 1-OH-2-3
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The fatty acid desaturation and elongation reactions catalyzed by Trichoderma sp. 1-OH-2-3 were investigated. This strain converted palmitic acid (16:0) mainly to stearic acid (18:0), and further to oleic acid (c9-18:1), linoleic acid (c9,c12-18:2), and α-linolenic acid (c9,c12,c15-18:3) through elongation, and Δ9, Δ12, and Δ15 desaturation reactions, respectively. Palmitoleic acid (c9-16:1) and cis-9,cis-12- hexadecadienoic acid were also produced from 16:0 by the strain. This strain converted n-tridecanoic acid (13:0) to cis-9-heptadecenoic acid and further to cis-9,cis-12-heptadecadienoic acid through elongation, and Δ9 and Δ12 desaturation reactions, respectively. trans-Vaccenic acid (t11-18:1) and trans-12-octadecenoic acid (t12-18:1) were desaturated by the strain through Δ9 desaturation. The products derived from t11-18:1 were identified as the conjugated linoleic acids (CLAs) of cis-9,trans-11-octadecadienoic acid and trans-9,trans-11-octadecadienoic acid. The product derived from t12-18:1 was identified as cis-9,trans-12-octadecadienoic acid. cis-6,cis-9-Octadecadienoic acid was desaturated to cis-6,cis-9,cis-12-octadecatrienoic acid by this strain through Δ12 desaturation. The broad substrate specificity of the elongation, and Δ9 and Δ12 desaturation reactions of the strain is useful for fatty acid biotransformation.
- Ando, Akinori,Ogawa, Jun,Kishino, Shigenobu,Ito, Taiyo,Shirasaka, Norifumi,Sakuradani, Eiji,Yokozeki, Kenzo,Shimizu, Sakayu
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experimental part
p. 227 - 233
(2010/06/16)
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- Substrate specificity and regioselectivity of Δ12 and ω3 fatty acid desaturases from Saccharomyces kluyveri
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Δ12 and ω3 fatty acid desaturases are key enzymes in the synthesis of polyunsaturated fatty acids (PUFAs), which are important constituents of membrane glycerolipids and also precursors to signaling molecules in many organisms. In this study, we determined the substrate specificity and regioselectivity of the Δ12 and ω3 fatty acid desaturases from Saccharomyces kluyveri (Sk-FAD2 and Sk-FAD3). Based on heterologous expression in Saccharomyces cerevisiae, it was found that Sk-FAD2 converted C16-20 monounsaturated fatty acids to diunsaturated fatty acids by the introduction of a second double bond at the ν + 3 position, while Sk-FAD3 recognized the ω3 position of C18 and C20. Furthermore, fatty acid analysis of major phospholipids suggested that Sk-FAD2 and Sk-FAD3 have no strong substrate specificity toward the lipid polar head group or the sn-positions of fatty acyl groups in phospholipids.
- Oura, Takahiro,Kajiwara, Susumu
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experimental part
p. 3174 - 3179
(2009/04/07)
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- Glycerogalactolipids from the fruit of Lycium barbarum
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Four glycerogalactolipids (1-4), together with 11 other previously known homologues were isolated from the fruit of Lycium barbarum. Their structures were elucidated by chemical analyses including regio-selective enzymatic, alkaline and acidic hydrolyses and spectroscopic methods involving GCMS, HRESIMS and 1D and 2D NMR, respectively.
- Gao, Zengping,Ali, Zulfiqar,Khan, Ikhlas A.
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experimental part
p. 2856 - 2861
(2009/04/07)
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- DIRECT METHOD AND REAGENT KITS FOR FATTY ACID ESTER SYNTHESIS
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Provided are efficient, cost-effective and water tolerant methods (e.g., single-vial methods) for preparing fatty acid esters from organic matter, comprising: obtaining organic matter comprising at least one fat substituent, contacting the organic matter in a reaction mixture with a basic solution under conditions suitable to provide for hydrolytic release of monomeric fatty acids from the at least one fat substituent to provide a base-treated reaction mixture, and esterifying the monomeric fatty acids of the base-treated reaction mixture by acidification of the reaction mixture and treating in the presence of an organic alcohol to provide fatty acid esters. The methods optionally further comprise, prior to esterifying, neutralizing the base-treated reaction mixture to provide for neutralized fatty acids, separating the neutralized fatty acids from the neutralized reaction mixture, and dissolving the separated fatty acids in the esterification reaction mixture. Also provided are related methods and kits for fat analysis.
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Page/Page column 18; 21-22; 29
(2008/12/07)
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- Novel galactolipids from the leaves of Ipomoea batatas L.: Characterization by liquid chromatography coupled with electrospray ionization-quadrupole time-of-flight tandem mass spectrometry
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Sixteen novel and ten known galactolipids have been isolated and characterized from the leaves of Ipomoea batatas L. (sweet potato) using an analytical method based on high-performance liquid chromatography coupled with electrospray ionization-quadrupole
- Napolitano, Assunta,Carbone, Virginia,Saggese, Paola,Takagaki, Kinya,Pizza, Cosimo
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experimental part
p. 10289 - 10297
(2009/10/02)
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- ADDUCTS OF LEVULINIC DERIVATIVES WITH EPOXIDIZED FATTY ACID ESTERS AND USES THEREOF
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The present disclosure relates to methods of preparation of compounds resulting from the reaction of levulinic esters and epoxidized unsaturated fatty acid esters. The compounds are useful as renewable biomass-based plasticizers for a variety of polymers. Mono-, di- and tri-ketal adducts formed in a reaction between alkyl esters of levulinate and epoxidized unsaturated fatty acid esters derived from vegetable oils are also disclosed.
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Page/Page column 19-20
(2010/11/27)
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- PROCESS FOR PREPARING CONJUGATED LINOLEIC ACID AND DERIVATIVES THEREOF FROM RICINOLEIC ACID
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A process for preparing conjugated linoleic acid (CLA) or derivatives thereof from ricinoleic acid, lower alkyl esters of ricinoleic acid, or salts thereof. The CLA is formed by reacting a carboxylic acid, or anhydride, anhydride equivalent, or ester thereof with the ricinoleic acid or derivative to form an intermediate having a carboxylic ester at the 12-hydroxy position of the ricinoleic acid or derivative, and reacting the intermediate with a base to form a cis-9, trans-11 conjugated linoleic acid.
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Page/Page column 11-12
(2008/06/13)
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- SINGLE-STAGE ESTERIFICATION OF OILS AND FATS
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A process for producing alkyl esters useful as biofuels and/or lubricants. An alkyl ester product produced by the process. The process comprises a single- stage reaction for esterifying a de-watered glyceride-containing feedstock with an anhydrous short chain alcohol in the presence of a basic esterification catalyst to produce a reaction product comprising alkyl esters and a reaction by-product comprising glycerol-containing substances and the catalyst-containing alcohol. The single-stage esterification reaction is conducted within a temperature and negative-pressure controllable vessel. The alkyl ester product is separated from the reaction by-product and may be further de-watered and/or purified. The catalyst-containing alcohol may be separated from the reaction by-product, de- watered and reused. The glycerol-containing substances may be separated from the reaction by-product and further purified. Useful glyceride-containing feedstocks include those prepared from plant or animal or fish materials, particularly those produced from seeds of mustard, canola, soybean, corn, cotton, flax and palm.
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Page/Page column 10-12
(2008/06/13)
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- Process for producing fatty acid alkyl ester composition
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An object of the present invention is to solve a problem of separation and recovery of catalysts present in an alkali metal catalytic method currently often used, a problem of excess consumption of a catalyst by a free fatty acid in a raw material, and other problems, and to solve a problem of the presence of a large excess amount of alcohol in a conventional supercritical methanol method, and to provide a method for producing a fatty acid alkyl ester composition in a reaction system containing water and free fatty acid present. The present invention has attained the above-mentioned object by provided a method for producing a fatty acid alkyl ester composition using fats and oils containing a fatty acid glyceride and/or fatty acid, wherein alcohol and/or water is allowed to co-exist with the above-mentioned fats and oils and the reaction is conducted under conditions of a temperature of 100° C. to 370° C. and a pressure of 1 to 100 MPa.
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Page/Page column 6; 7-8
(2008/06/13)
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- Biodiesel additive and method of preparation thereof
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Fuel oxygenates comprised of fatty acid or fatty acid ester derivatives which have been reacted with ozone; a base; and a lower alkanol (1 to 8 carbon atoms) are described. The oxygenates comprise ester groups at a point of cleavage by the ozone which provide oxygen in the oxygenate.
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Page/Page column 4-5
(2008/06/13)
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- PROCESS FOR EXTRACTION AND CATALYTIC ESTERIFICATION OF FATTY ACIDS FOUND IN SEWAGE SCUM
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The innovation proposed herein describes the process of a fatty acids esterification presents in the sewage scum namely the surface phase of sewage rich in fatty matter, being that this fatty acids are extracted from the scum and esterified by acid catalysts and reagents like as methanol or ethanol.
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- Polymer-supported triazenes as smart reagents for the alkylation of carboxylic acids
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Starting from polystyrene, a simple four-step synthesis of polymer-supported alkyltriazenes (alkyl = Me, Et, benzyl) is described. With this synthesis, a loading capacity of 2.2 mmol g-1 can be reached. The most prominent application of these polymer-supported reagents is the rapid, highly selective and high-yielding esterification of carboxylic acids, which involves a simple mix and filter off procedure at room temperature. If stored in a refrigerator, these reagents are stable for many months and they can be recycled several times.
- Erb, Bernhard,Kucma, Jean-Philippe,Mourey, Sandrine,Struber, Fritz
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p. 2582 - 2588
(2007/10/03)
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- Method for commercial preparation of conjugated linoleic acid using recycled alkali transesterification catalyst
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Conjugated linoleic acid is readily prepared by mixing crude alkaline glycerol solution derived as a byproduct of triglyceride transesterification and a linoleate rich triglyceride, ester, soap, phospholipid, fatty acid, or wax and heating the mixture sufficiently to conjugate the linoleate double bonds. The reaction produces a favorable isomer mixture enriched in 10,12-trans,cis octadecadienoic and 9,11-cis,trans-octadecadienoic acids.
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Page column 4
(2008/06/13)
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- Semi-volatile and particulate emissions from the combustion of alternative diesel fuels
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Motor vehicle emissions are a major anthropogenic source of air pollution and contribute to the deterioration of urban air quality. In this paper, we report results of a laboratory investigation of particle formation from four different alternative diesel fuels, namely, compressed natural gas (CNG), dimethyl ether (DME), biodiesel, and diesel, under fuelrich conditions in the temperature range of 800-1200°C at pressures of approximately 24 atm. A single pulse shock tube was used to simulate compression ignition (CI) combustion conditions. Gaseous fuels (CNG and DME) were exposed premixed in air while liquid fuels (diesel and biodiesel) were injected using a high-pressure liquid injector. The results of surface analysis using a scanning electron microscope showed that the particles formed from combustion of all four of the above-mentioned fuels had a mean diameter less than 0.1 μm. From results of gravimetric analysis and fuel injection size it was found that under the test conditions described above the relative particulate yields from CNG, DME, biodiesel, and diesel were 0.30%, 0.026%, 0.52%, and 0.51%, respectively. Chemical analysis of particles showed that DME combustion particles had the highest soluble organic fraction (SOF) at 71%, followed by biodiesel (66%), CNG (38%) and diesel (20%). This illustrates that in case of both gaseous and liquid fuels, oxygenated fuels have a higher SOF than non-oxygenated fuels. Motor vehicle emissions are a major anthropogenic source of air pollution and contribute to the deterioration of urban air quality. In this paper, we report results of a laboratory investigation of particle formation from four different alternative diesel fuels, namely, compressed natural gas (CNG), dimethyl ether (DME), biodiesel, and diesel, under fuelrich conditions in the temperature range of 800-1200°C at pressures of approximately 24 atm. A single pulse shock tube was used to simulate compression ignition (CI) combustion conditions. Gaseous fuels (CNG and DME) were exposed premixed in air while liquid fuels (diesel and biodiesel) were injected using a high-pressure liquid injector. The results of surface analysis using a scanning electron microscope showed that the particles formed from combustion of all four of the above-mentioned fuels had a mean diameter less than 0.1 μm. From results of gravimetric analysis and fuel injection size it was found that under the test conditions described above the relative particulate yields from CNG, DME, biodiesel, and diesel were 0.30%, 0.026%, 0.52%, and 0.51%, respectively. Chemical analysis of particles showed that DME combustion particles had the highest soluble organic fraction (SOF) at 71%, followed by biodiesel (66%), CNG (38%) and diesel (20%). This illustrates that in case of both gaseous and liquid fuels, oxygenated fuels have a higher SOF than non-oxygenated fuels.
- Sidhu, Sukh,Graham, John,Striebich, Richard
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p. 681 - 690
(2007/10/03)
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- Insecticidal compounds against mosquito larvae from Oscillatoria agardhii strain 27
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It was found that Oscillatoria agardhii strain 27 produced compounds toxic against mosquito larvae (Aedes albopictus), therefore, these compounds were extracted and separated for insecticide development. Structural characterization of the toxic fraction by 1H-NMR and GC-MS showed that these compounds are not the neurotoxins or hepatotoxins conventionally produced by Oscillatoria, but it contained a mixture of unsaturated fatty acids, oleic, linoleic, and γ-linolenic acids, as well as saturated fatty acids, myristic, palmitic, and stearic acids. In a bioassay developed for these hydrophobic compounds using mosquito larvae, authentic unsaturated fatty acids were shown to be toxic, whereas saturated ones were active. The results suggested that it might be possible to use unsaturated fatty acids as environmentally safe and effective insecticides without the side effects of the chemically synthesized insecticides. (C) 2000 by John Wiley and Sons, Inc.
- Harada, Ken-Ichi,Suomalainen, Mette,Uchida, Hideaki,Masui, Hiroaki,Ohmura, Kuniyo,Kiviranta, Jari,Niku-Paavola, Marja-Leena,Ikemoto, Takaya
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p. 114 - 119
(2007/10/03)
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