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...

Metabolic engineering of Saccharomyces cerevisiae for production of fatty acid short- and branched-chain alkyl esters biodiesel.

PubMed

Teo, Wei Suong; Ling, Hua; Yu, Ai-Qun; Chang, Matthew Wook

2015-01-01

Biodiesel is a mixture of fatty acid short-chain alkyl esters of different fatty acid carbon chain lengths. However, while fatty acid methyl or ethyl esters are useful biodiesel produced commercially, fatty acid esters with branched-chain alcohol moieties have superior fuel properties. Crucially, this includes improved cold flow characteristics, as one of the major problems associated with biodiesel use is poor low-temperature flow properties. Hence, microbial production as a renewable, nontoxic and scalable method to produce fatty acid esters with branched-chain alcohol moieties from biomass is critical. We engineered Saccharomyces cerevisiae to produce fatty acid short- and branched-chain alkyl esters, including ethyl, isobutyl, isoamyl and active amyl esters using endogenously synthesized fatty acids and alcohols. Two wax ester synthase genes (ws2 and Maqu_0168 from Marinobacter sp.) were cloned and expressed. Both enzymes were found to catalyze the formation of fatty acid esters, with different alcohol preferences. To boost the ability of S. cerevisiae to produce the aforementioned esters, negative regulators of the INO1 gene in phospholipid metabolism, Rpd3 and Opi1, were deleted to increase flux towards fatty acyl-CoAs. In addition, five isobutanol pathway enzymes (Ilv2, Ilv5, Ilv3, Aro10, and Adh7) targeted into the mitochondria were overexpressed to enhance production of alcohol precursors. By combining these engineering strategies with high-cell-density fermentation, over 230 mg/L fatty acid short- and branched-chain alkyl esters were produced, which is the highest titer reported in yeast to date. In this work, we engineered the metabolism of S. cerevisiae to produce biodiesels in the form of fatty acid short- and branched-chain alkyl esters, including ethyl, isobutyl, isoamyl and active amyl esters. To our knowledge, this is the first report of the production of fatty acid isobutyl and active amyl esters in S. cerevisiae. Our findings will be useful for engineering S. cerevisiae strains toward high-level and sustainable biodiesel production.

Cytochrome c oxidase inhibition in the rice weevil Sitophilus oryzae (L.) by formate, the toxic metabolite of volatile alkyl formates.

PubMed

Haritos, V S; Dojchinov, G

2003-10-01

Volatile alkyl formates are potential replacements for the ozone-depleting fumigant, methyl bromide, as postharvest insecticides and here we have investigated their mode of insecticidal action. Firstly, a range of alkyl esters, ethanol and formic acid were tested in mortality bioassays with adults of the rice weevil, Sitophilus oryzae (L.) and the grain borer, Rhyzopertha dominica (F.) to determine whether the intact ester or one of its components was the toxic moiety. Volatile alkyl formates and formic acid caused similar levels of mortality (LC(50) 131-165 micromol l(-1)) to S. oryzae and were more potent than non-formate containing alkyl esters and ethanol (LC(50)>275 micromol l(-1)). The order of potency was the same in R. dominica. Ethyl formate was rapidly metabolised in vitro to formic acid when incubated with insect homogenates, presumably through the action of esterases. S. oryzae and R. dominica fumigated with a lethal dose of ethyl formate had eight and 17-fold higher concentrations of formic acid, respectively, in their bodies than untreated controls. When tested against isolated mitochondria from S. oryzae, alkyl esters, alcohols, acetate and propionate salts were not inhibitory towards cytochrome c oxidase (EC 1.9.3.1), but sodium cyanide and sodium formate were inhibitory with IC(50) values of 0.0015 mM and 59 mM, respectively. Volatile formate esters were more toxic than other alkyl esters, and this was found to be due, at least in part, to their hydrolysis to formic acid and its inhibition of cytochrome c oxidase.

Rapid screening of fatty acid alkyl esters in olive oils by time domain reflectometry.

PubMed

Berardinelli, Annachiara; Ragni, Luigi; Bendini, Alessandra; Valli, Enrico; Conte, Lanfranco; Guarnieri, Adriano; Toschi, Tullia Gallina

2013-11-20

The main aim of the present research is to assess the possibility of quickly screening fatty acid alkyl esters (FAAE) in olive oils using time domain reflectometry (TDR) and partial least-squares (PLS) multivariate statistical analysis. Eighteen virgin olive oil samples with fatty acid alkyl ester contents and fatty acid ethyl ester/methyl ester ratios (FAEE/FAME) ranging from 3 to 100 mg kg(-1) and from 0.3 to 2.6, respectively, were submitted to tests with time domain resolution of 1 ps. The results obtained in test set validation demonstrated that this new and fast analytical approach is able to predict FAME, FAEE, and FAME + FAEE contents with R(2) values of 0.905, 0.923, and 0.927, respectively. Further measurements on mixtures between olive oil and FAAE standards confirmed that the prediction is based on a direct influence of fatty acid alkyl esters on the TDR signal. The suggested technique appeared potentially suitable for monitoring one of the most important quality attribute of the olive oil in the extraction process.

Near Infrared Spectroscopic Identification of Alkyl Aromatic Esters and Phenyl Ketones

NASA Astrophysics Data System (ADS)

Nelyubov, D. V.; Vazhenin, D. A.; Kudriavtsev, A. A.; Buzolina, A. Yu.

2018-03-01

Bands characterizing the content of carbon atoms in alkyl (7177-7205 cm-1) and phenyl structural fragments (9175-9192 cm-1) in organic molecules were revealed by studying the near infrared spectra of such compounds. The optical density at the maxima of these absorption bands was shown to depend strongly on the fraction of carbon atoms in the corresponding fragments. The developed models proved to be adequate for determining the fraction of carbon atoms in alkyl aromatic esters and phenyl ketones. The feasibility of modeling the molecular structure of alkyl aromatic esters using regression models was demonstrated for the product of the condensation of oleic acid and benzyl alcohol.

Cu(II)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds.

PubMed

Ma, Ran; He, Liang-Nian; Liu, An-Hua; Song, Qing-Wen

2016-02-04

A novel Cu(II)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.

Synthesis and Reactivity of Alkyl-1,1,1-trisphosphonate Esters

PubMed Central

Smits, Jacqueline P.; Wiemer, David F.

2011-01-01

The α–trisphosphonic acid esters provide a unique spatial arrangement of three phosphonate groups, and may represent an attractive motif for inhibitors of enzymes that utilize di- or triphosphate substrates. To advance studies of this unique functionality, a general route to alkyl derivatives of the parent system (R = H) has been developed. A set of new α-alkyl-1,1,1-trisphosphonate esters has been prepared through phosphinylation and subsequent oxidation of tetraethyl alkylbisphosphonates, and the reactivity of these new compounds has been studied in representative reactions that afford additional examples of this functionality. PMID:21916407

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

PubMed

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

2008-11-04

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

40 CFR 80.1101 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... fuel” includes cellulosic biomass ethanol, waste derived ethanol, biodiesel (mono-alkyl ester), non... the calendar year) does not exceed 75,000 barrels. (h) Biodiesel (mono-alkyl ester) means a motor... Specification for Biodiesel Fuel Blendstock (B100) for Middle Distillate Fuels.” ASTM D-6751-07 is incorporated...

40 CFR 80.1101 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... fuel” includes cellulosic biomass ethanol, waste derived ethanol, biodiesel (mono-alkyl ester), non... the calendar year) does not exceed 75,000 barrels. (h) Biodiesel (mono-alkyl ester) means a motor... Specification for Biodiesel Fuel Blendstock (B100) for Middle Distillate Fuels.” ASTM D-6751-07 is incorporated...

Transesterified tyrosol and hydroxytyrosol alkyl esters from cuphea oil – antioxidant behavior in Liposomes

USDA-ARS?s Scientific Manuscript database

Tyrosol and hydroxytyrosol are the antioxidant molecules abundantly found in olive oil. Transesterification of tyrosol and hydroxytyrosol with cuphea oil results in medium chain alkyl esters with antioxidant properties. Membrane partitioning, antioxidant capacity, and membrane location of these nove...

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

USDA-ARS?s Scientific Manuscript database

Epoxidation of vegetable oils and consecutive epoxide ring-opening reaction is a widely investigated path for producing biobased lubricants and polymers. The reaction mechanism and products are considered well-studied and known. In the current study, the reactions of epoxidized alkyl soyate with fou...

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...

Tuning the nature and stability of self-assemblies formed by ester benzene 1,3,5-tricarboxamides: the crucial role played by the substituents.

PubMed

Desmarchelier, Alaric; Alvarenga, Bruno Giordano; Caumes, Xavier; Dubreucq, Ludovic; Troufflard, Claire; Tessier, Martine; Vanthuyne, Nicolas; Idé, Julien; Maistriaux, Thomas; Beljonne, David; Brocorens, Patrick; Lazzaroni, Roberto; Raynal, Matthieu; Bouteiller, Laurent

2016-09-20

As the benzene 1,3,5-tricarboxamide (BTA) moiety is commonly used as the central assembling unit for the construction of functionalized supramolecular architectures, strategies to tailor the nature and stability of BTA assemblies are needed. The assembly properties of a library of structurally simple BTAs derived from amino dodecyl esters (ester BTAs, 13 members) have been studied, either in the bulk or in cyclohexane solutions, by means of a series of analytical methods (NMR, DSC, POM, FT-IR, UV-Vis, CD, ITC, high-sensitivity DSC, SANS). Two types of hydrogen-bonded species have been identified and characterized: the expected amide-bonded helical rods (or stacks) that are structurally similar to those formed by BTAs with simple alkyl side chains (alkyl BTAs), and ester-bonded dimers in which the BTAs are connected by means of hydrogen bonds linking the amide N-H and the ester C[double bond, length as m-dash]O. MM/MD calculations coupled with simulations of CD spectra allow for the precise determination of the molecular arrangement and of the hydrogen bond pattern of these dimers. Our study points out the crucial influence of the substituent attached on the amino-ester α-carbon on the relative stability of the rod-like versus dimeric assemblies. By varying this substituent, one can precisely tune the nature of the dominant hydrogen-bonded species (stacks or dimers) in the neat compounds and in cyclohexane over a wide range of temperatures and concentrations. In the neat BTAs, stacks are stable up to 213 °C and dimers above 180 °C whilst in cyclohexane stacks form at c* > 3 × 10 -5 M at 20 °C and dimers are stable up to 80 °C at 7 × 10 -6 M. Ester BTAs that assemble into stacks form a liquid-crystalline phase and yield gels or viscous solutions in cyclohexane, demonstrating the importance of controlling the structure of these assemblies. Our systematic study of these structurally similar ester BTAs also allows for a better understanding of how a single atom or moiety can impact the nature and stability of BTA aggregates, which is of importance for the future development of functionalized BTA supramolecular polymers.

Rhodium(III)-Catalyzed ortho-Alkylation of Phenoxy Substrates with Diazo Compounds via C-H Activation: A Case of Decarboxylative Pyrimidine/Pyridine Migratory Cyclization Rather than Removal of Pyrimidine/Pyridine Directing Group.

PubMed

Ravi, Manjula; Allu, Srinivasarao; Swamy, K C Kumara

2017-03-03

An efficient Rh(III)-catalyzed ortho-alkylation of phenoxy substrates with diazo compounds has been achieved for the first time using pyrimidine or pyridine as the directing group. Furthermore, bis-alkylation has also been achieved using para-substituted phenoxypyrimidine and 3 mol equiv of the diazo ester. The ortho-alkylated derivatives of phenoxy products possessing the ester functionality undergo decarboxylative pyrimidine/pyridine migratory cyclization (rather than deprotection of pyrimidine/pyridine group) using 20% NaOEt in EtOH affording a novel class of 3-(pyrimidin-2(1H)-ylidene)benzofuran-2(3H)-ones and 6-methyl-3-(pyridin-2(1H)-ylidene)benzofuran-2(3H)-one. The ortho-alkylated phenoxypyridine possessing ester functionality also undergoes decarboxylative pyridine migratory cyclization using MeOTf/NaOMe in toluene providing 6-methyl-3-(1-methylpyridin-2(1H)-ylidene)benzofuran-2(3H)-one.

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.

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

PubMed

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

2015-04-01

The goal of this work was to quantitate ester formation between alkyl and aryl boronic acids and vicinal-diols or 1,2-diols in aqueous solution. As used here, 1,2-diols includes polyols with one or more 1,2-diol pairs. Multiple techniques were used including apparent pKa shifts of the boronic acids using UV spectrophotometry (for aryl acids) and titration (for aryl and alkyl acids). Isothermal microcalorimetry was also used, with all reactions being enthalpically favored. For all the acids and 1,2-diols and the conditions studied, evidence only supported 1:1 ester formation. All the esters formed were found to be significantly more acidic, as Lewis acids, by 3-3.5 pKa units than the corresponding nonesterified boronic acid. The equilibrium constants for ester formation increased with increasing number of 1,2-diol pairs but stereochemistry may also play a role as sorbitol with five possible 1,2-diol pairs and five isomers (taking into account the stereochemistry of the alcohol groups) was twice as efficient at ester formation compared with mannitol, also with five possible 1,2-diol pairs but only three isomers. Alkyl boronic acids formed esters to a greater extent than aryl acids. Although some quantitative differences were seen between the various techniques used, rank ordering of the structure/reactivity was consistent. Formulation implications of ester formation between boronic acids and 1,2-diols are discussed. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as sulfuric...

Merging Photoredox with 1,2-Metallate Rearrangements: The Photochemical Alkylation of Vinyl Boronate Complexes.

PubMed

Silvi, Mattia; Sandford, Christopher; Aggarwal, Varinder K

2017-04-26

Vinyl boronates react with electron-deficient alkyl iodides in the presence of visible light to give boronic esters in which two new C-C bonds have been created. The reaction occurs by radical addition of an electron-deficient alkyl radical to the vinyl boronate followed by electron transfer with another molecule of alkyl iodide, continuing the chain, and triggering a 1,2-metalate rearrangement. In a number of cases, the use of a photoredox catalyst enhances yields significantly. The scope of the radical precursor includes α-iodo ketones, esters, nitriles, primary amides, α-fluorinated halo-acetates and perfluoroalkyl iodides.

40 CFR 80.1429 - Requirements for separating RINs from volumes of renewable fuel.

Code of Federal Regulations, 2010 CFR

2010-07-01

... transportation fuel. (6) RINs assigned to a volume of biodiesel (mono-alkyl ester) can only be separated from that volume pursuant to paragraph (b)(2) of this section if such biodiesel is blended into diesel fuel at a concentration of 80 volume percent biodiesel (mono-alkyl ester) or less. (i) This paragraph (b...

40 CFR 80.1129 - Requirements for separating RINs from volumes of renewable fuel.

Code of Federal Regulations, 2011 CFR

2011-07-01

... motor vehicle fuel. (5) RINs assigned to a volume of biodiesel (mono-alkyl ester) can only be separated from that volume pursuant to paragraph (b)(2) of this section if such biodiesel is blended into diesel fuel at a concentration of 80 volume percent biodiesel (mono-alkyl ester) or less. (i) This paragraph...

40 CFR 80.1129 - Requirements for separating RINs from volumes of renewable fuel.

Code of Federal Regulations, 2010 CFR

2010-07-01

... motor vehicle fuel. (5) RINs assigned to a volume of biodiesel (mono-alkyl ester) can only be separated from that volume pursuant to paragraph (b)(2) of this section if such biodiesel is blended into diesel fuel at a concentration of 80 volume percent biodiesel (mono-alkyl ester) or less. (i) This paragraph...

40 CFR 80.1129 - Requirements for separating RINs from volumes of renewable fuel.

Code of Federal Regulations, 2013 CFR

2013-07-01

... motor vehicle fuel. (5) RINs assigned to a volume of biodiesel (mono-alkyl ester) can only be separated from that volume pursuant to paragraph (b)(2) of this section if such biodiesel is blended into diesel fuel at a concentration of 80 volume percent biodiesel (mono-alkyl ester) or less. (i) This paragraph...

40 CFR 80.1129 - Requirements for separating RINs from volumes of renewable fuel.

Code of Federal Regulations, 2012 CFR

2012-07-01

... motor vehicle fuel. (5) RINs assigned to a volume of biodiesel (mono-alkyl ester) can only be separated from that volume pursuant to paragraph (b)(2) of this section if such biodiesel is blended into diesel fuel at a concentration of 80 volume percent biodiesel (mono-alkyl ester) or less. (i) This paragraph...

40 CFR 80.1429 - Requirements for separating RINs from volumes of renewable fuel.

Code of Federal Regulations, 2011 CFR

2011-07-01

... transportation fuel. (6) RINs assigned to a volume of biodiesel (mono-alkyl ester) can only be separated from that volume pursuant to paragraph (b)(2) of this section if such biodiesel is blended into diesel fuel at a concentration of 80 volume percent biodiesel (mono-alkyl ester) or less. (i) This paragraph (b...

40 CFR 80.1129 - Requirements for separating RINs from volumes of renewable fuel.

Code of Federal Regulations, 2014 CFR

2014-07-01

... motor vehicle fuel. (5) RINs assigned to a volume of biodiesel (mono-alkyl ester) can only be separated from that volume pursuant to paragraph (b)(2) of this section if such biodiesel is blended into diesel fuel at a concentration of 80 volume percent biodiesel (mono-alkyl ester) or less. (i) This paragraph...

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

Code of Federal Regulations, 2010 CFR

2010-07-01

..., C12-18 alkyl esters (generic). 721.3025 Section 721.3025 Protection of Environment ENVIRONMENTAL... communication program. A significant new use of these substances is any manner or method of manufacture, import, or processing associated with any use of these substances without providing risk notification as...

Safety Assessment of Alkyl Esters as Used in Cosmetics.

PubMed

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

2015-09-01

The Cosmetic Ingredient Review Expert Panel (Panel) assessed the safety of 237 alkyl esters for use in cosmetics. The alkyl esters included in this assessment have a variety of reported functions in cosmetics, with skin-conditioning agent being the most common function. The Panel reviewed available animal and clinical data in making its determination of safety on these ingredients, and where there were data gaps, similarity in structure, properties, functions, and uses of these ingredients allowed for extrapolation of the available toxicological data to assess the safety of the entire group. The Panel concluded that these ingredients are safe in cosmetic formulations in the present practices of use and concentration when formulated to be nonirritating. © The Author(s) 2015.

Molecular structure, supramolecular organization and thermotropic phase behavior of N-acylglycine alkyl esters with matched acyl and alkyl chains.

PubMed

Reddy, S Thirupathi; Swamy, Musti J

2017-11-01

N-Acylglycines (NAGs), the endogenous single-tailed lipids present in rat brain and other mammalian tissues, play significant roles in cell physiology and exhibit interesting pharmacological properties. In the present study, a homologous series of N-acylglycine alkyl esters (NAGEs) with matched chains were synthesized and characterized. Results of differential scanning calorimetric studies revealed that all NAGEs exhibit a single sharp phase transition and that the transition enthalpy and entropy show a linear dependence on the N-acyl and ester alkyl chain length. The structure of N-myristoylglycine myristyl ester (NMGME), solved by single-crystal X-ray diffraction, showed that the molecule adopts a linear geometry and revealed that the structure of N-myristoyl glycyl moiety in NMGME is identical to that in N-myristoylglycine. The molecules are packed in layers with the polar functional groups of the ester and amide functionalities located at the center of the layer. The crystal packing is stabilized by NH⋯O hydrogen bonds between the amide CO and NH groups of adjacent molecules as well as by CH⋯O hydrogen bonds between the amide carbonyl and the methylene CH adjacent to the ester carbonyl of neighboring molecules as well as between ester carbonyl and methylene group of the glycine moiety of adjacent molecules. Powder X-ray diffraction studies showed a linear dependence of the d-spacings on the acyl chain length, suggesting that all NAGEs adopt a structure similar to the packing exhibited in the crystal lattice of NMGME. Copyright © 2017 Elsevier B.V. All rights reserved.

Rigid Dipeptide Mimics: Synthesis of Enantiopure 5- and 7-Benzyl and 5,7-Dibenzyl Indolizidinone Amino Acids via Enolization and Alkylation of delta-Oxo alpha,omega-Di-[N-(9-(9-phenylfluorenyl))amino]azelate Esters.

PubMed

Polyak, Felix; Lubell, William D.

1998-08-21

Azabicyclo[X.Y.0]alkane amino acids are tools for constructing mimics of peptide structure and templates for generating combinatorial libraries for drug discovery. Our methodology for synthesizing these conformationally rigid dipeptides has been elaborated such that alkyl groups can be appended onto the heterocycle to generate mimics of peptide backbone and side-chain structure. Inexpensive glutamic acid was employed as chiral educt in a Claisen condensation/ketone alkylation/reductive amination/lactam cyclization sequence that furnished alkyl-branched azabicyclo[4.3.0]alkane amino acid. Enantiopure 5-benzyl-, 7-benzyl-, and 5,7-dibenzylindolizidinone amino acids 2-4 were stereoselectively synthesized via efficient reaction sequences featuring the alkylation of di-tert-butyl alpha,omega-di-[N-(PhF)amino]azelate delta-ketone 5. A variety of alkyl halides were readily added to the enolate of ketone 5 to provide mono- and dialkylated ketones 6 and 7. Hydride additions to 6 and 7, methanesulfonations, and intramolecular S(N)2 displacements by the PhF amine gave 5-alkylprolines that were converted by lactam cyclizations into 7- and 5-benzyl-, as well as 5,7-dibenzyl-2-oxo-3-N-(BOC)amino-1-azabicyclo[4.3.0]nonane-9-carboxylate methyl esters 10, 11, and 14. Epimerization of the alkyl-branched stereocenter via an iminium-enaminium equilibrium proved effective for controlling diastereoselectivity in reductive aminations with 6 and 7 in order to furnish 5-alkylprolines that were similarly converted to 7- benzyl- and 5,7-dibenzylindolizidinone N-(BOC)amino esters 10 and 14. Ester hydrolysis with hydroxide ion and potassium trimethylsilanolate then gave enantiopure indolizidinone amino acids 2-4. Epimerization at C-9 of benzylindolizidinone amino esters was also used to provide alternative diastereomers of 10, 11, and 14. This practical methodology for introducing side-chain groups onto the heterocycle with regioselective and diastereoselective control is designed to enhance the use of alkyl-branched azabicycloalkane amino acids for the exploration of conformation-activity relationships of various biologically active peptides.

Synthesis of an acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

DOEpatents

Moens, L.

1999-05-25

A process is disclosed for preparing an acid addition salt of delta-aminolevulinic acid comprising. The process involves dissolving a lower alkyl 5-bromolevulinate and an alkali metal diformylamide in an organic solvent selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, 2-methyltetrahydrofuran and methylformate or mixtures to form a suspension of an alkyl 5-(N,N-diformylamino) levulinate ester; and hydrolyzing the alkyl 5-(N,N-diformylamino) levulinate with an inorganic acid to form an acid addition salt of delta-amino levulinic acid.

Synthesis of an acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

DOEpatents

Moens, Luc

1999-01-01

A process of preparing an acid addition salt of delta-aminolevulinic acid comprising: dissolving a lower alkyl 5-bromolevulinate and an alkali metal diformylamide in an organic solvent selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, 2-methyltetrahydrofuran and methylformate or mixtures thereof to form a suspension of an alkyl 5-(N,N-diformylamino) levulinate ester; and hydrolyzing said alkyl 5-(N,N-diformylamino) levulinate with an inorganic acid to form an acid addition salt of delta-amino levulinic acid.

Fe(OTf)3-catalysed Friedel–Crafts reaction of benzenoid arenes with α,β-unsaturated carbonyl compounds: easy access to 1,1-diarylalkanes

PubMed Central

Bhattacharya, Aditya; Shukla, Pushpendra Mani

2017-01-01

A simple and efficient method for the synthesis of 1,1-diarylalkanes via the Friedel–Crafts-type alkylation reaction of electron-rich arenes with cinnamic acid ester derivatives or chalcones is reported. Iron triflate has been found to be the best catalyst for the Friedel–Crafts-type alkylation reaction with α,β-unsaturated carbonyl compounds. This reaction afforded β,β-diaryl carbonyl compounds in good yields (65–93%) and with excellent regioselectivities. Remarkably, this method is also compatible with a variety of indoles to provide 3-indolyl-aryl carbonyl compounds in excellent yields. Great efforts have been made to deduce a plausible reaction mechanism based on isotopic labelling experiments. PMID:29134078

40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. 721.2140 Section 721.2140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specifi...

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

S.I. Zherebtsov; A.I. Moiseev

Changes in the group and individual compositions of the wax fractions of bitumen in the course of brown coal methylation were studied. With the use of IR and NMR spectroscopy and chromatography-mass spectrometry, it was found that the esters of methylated coal waxes consisted of the native esters of fatty acids and the methyl esters of these acids formed as a result of an alkylation treatment. Esterification and transesterification were predominant among the reactions of aliphatic fraction components. A positive effect of methanol alkylation on an increase in the yield of the aliphatic fractions was found.

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

Code of Federal Regulations, 2010 CFR

2010-07-01

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

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

Code of Federal Regulations, 2011 CFR

2011-07-01

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

Production of long chain alkyl esters from carbon dioxide and electricity by a two-stage bacterial process.

PubMed

Lehtinen, Tapio; Efimova, Elena; Tremblay, Pier-Luc; Santala, Suvi; Zhang, Tian; Santala, Ville

2017-11-01

Microbial electrosynthesis (MES) is a promising technology for the reduction of carbon dioxide into value-added multicarbon molecules. In order to broaden the product profile of MES processes, we developed a two-stage process for microbial conversion of carbon dioxide and electricity into long chain alkyl esters. In the first stage, the carbon dioxide is reduced to organic compounds, mainly acetate, in a MES process by Sporomusa ovata. In the second stage, the liquid end-products of the MES process are converted to the final product by a second microorganism, Acinetobacter baylyi in an aerobic bioprocess. In this proof-of-principle study, we demonstrate for the first time the bacterial production of long alkyl esters (wax esters) from carbon dioxide and electricity as the sole sources of carbon and energy. The process holds potential for the efficient production of carbon-neutral chemicals or biofuels. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acids C12-18, C18 unsaturated... Significant New Uses for Specific Chemical Substances § 721.3025 Fatty acids C12-18, C18 unsaturated, C12-18... chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (PMNs...

Biodiesel fuels

USDA-ARS?s Scientific Manuscript database

The mono-alkyl esters, most commonly the methyl esters, of vegetable oils, animal fats or other materials consisting mainly of triacylglycerols, often referred to as biodiesel, are an alternative to conventional petrodiesel for use in compression-ignition engines. The fatty acid esters that thus com...

Methods of making alkyl esters

DOEpatents

Elliott, Brian

2010-08-03

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

Synthesis and characterization of a novel long-alkyl-chain ester-substituted benzimidazole gelator and its octan-1-ol solvate.

PubMed

Geiger, H Cristina; Zick, Patricia L; Roberts, William R; Geiger, David K

2017-04-01

The synthesis of a novel benzimidazole derivative with a long-chain-ester substituent, namely methyl 8-[4-(1H-benzimidazol-2-yl)phenoxy]octanoate, (3), is reported. Ester (3) shows evidence of aggregation in solution and weak gelation ability with toluene. The octan-1-ol solvate, methyl 8-[4-(1H-benzimidazol-2-yl)phenoxy]octanoate octan-1-ol monosolvate, C 22 H 26 N 2 O 3 ·C 8 H 18 O, (4), exhibits a four-molecule hydrogen-bonded motif in the solid state, with N-H...O hydrogen bonds between benzimidazole molecules and O-H...N hydrogen bonds between the octan-1-ol solvent molecules and the benzimidazole unit. The alkyl chains of the ester and the octan-1-ol molecules are in unfolded conformations. The phenylene ring is canted by 10.27 (6)° from the plane of the benzimidazole ring system. H...C contacts make up 20.7% of the Hirshfeld surface coverage. Weak C-H...π interactions involving the benzimidazole alkyl chain and three aromatic rings are observed.

Phenol esterase activity of porcine skin

USDA-ARS?s Scientific Manuscript database

The alkyl esters of plant-derived phenols may serve as slow-release sources for cutaneous delivery of antioxidants. The ability of skin esterases to hydrolyze phenolic esters was examined. Esters of tyrosol and hydroxytyrosol were prepared from decanoic and lipoic acids. Ferulic acid was esterified ...

Impact of the corrin framework of vitamin B12 on the electrochemical carbon-skeleton rearrangement in comparison to an imine/oxime planar ligand; tuning selectivity in 1,2-migration of a functional group by controlling electrolysis potential.

PubMed

Tahara, Keishiro; Pan, Ling; Yamaguchi, Ryoko; Shimakoshi, Hisashi; Abe, Masaaki; Hisaeda, Yoshio

2017-10-01

Among the coenzyme B 12 -dependent enzymes, methylmalonyl-CoA mutase (MMCM) catalyzes the carbon-skeleton rearrangement reaction between R-methylmalonyl-CoA and succinyl-CoA. Diethyl 2-bromomethyl-2-phenylmalonate, an alkyl bromide substrate having two different migrating groups (phenyl and carboxylic ester groups) on the β-carbon, was applied to the electrolysis mediated by a hydrophobic vitamin B 12 model complex, heptamethyl cobyrinate perchlorate in this study. The electrolysis of the substrate at -1.0V vs. Ag-AgCl by light irradiation afforded the simple reduced product (diethyl 2-methyl-2-phenylmalonate) and the phenyl migrated product (diethyl 2-benzyl-2-phenylmalonate), as well as the electrolysis of the substrate at -1.5V vs. Ag-AgCl in the dark. The electrolysis of the substrate at -2.0V vs. Ag-AgCl afforded the carboxylic ester migrated product (diethyl phenylsuccinate) as the major product. The selectivity for the migrating group was successfully tuned by controlling the electrolysis potential. We clarified that the cathodic chemistry of the Co(III) alkylated heptamethyl cobyrinate is critical for the selectivity of the migrating group through mechanistic investigations and comparisons to the simple vitamin B 12 model complex, an imine/oxime-type cobalt complex. Copyright © 2017 Elsevier Inc. All rights reserved.

Probing the effects of the ester functional group, alkyl side chain length and anions on the bulk nanostructure of ionic liquids: a computational study.

PubMed

Fakhraee, Mostafa; Gholami, Mohammad Reza

2016-04-14

The effects of ester addition on nanostructural properties of biodegradable ILs composed of 1-alkoxycarbonyl-3-alkyl-imidazolium cations ([C1COOCnC1im](+), n = 1, 2, 4) combined with [Br](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) were explored by using the molecular dynamics (MD) simulations and quantum theory of atoms in molecules (QTAIM) analysis at 400 K. Various thermodynamic properties of these ILs were extensively computed in our earlier work (Ind. Eng. Chem. Res., 2015, 54, 11678-11700). Nano-scale segregation analysis demonstrates the formation of a small spherical island-like hydrocarbon within the continuous ionic domain for ILs with short alkyl side chain ([C1COOC1C1im]), and a sponge-like nanostructure for the compound with long alkyl side chain ([C1COOC4C1im]). Ester-functionalized ILs with ethyl side chain ([C1COOC2C1im]) are the turning point between two different morphologies. Non-polar channels were observed for [C1COOC4C1im] ILs composed of smaller anions such as [Br] and [NO3], whereas clustering organization was found for the other anions. Formation of the spherical micelle-like nanostructure was seen for lengthened cations. Finally, the incorporation of an ester group into the alkyl side chain of the cation leads to stronger segregation between charged and uncharged networks, which consequently increased the possibility of self-assembly and micelle formation.

Monoalkyl sulfates as alkylating agents in water, alkylsulfatase rate enhancements, and the “energy-rich” nature of sulfate half-esters

PubMed Central

Wolfenden, Richard; Yuan, Yang

2007-01-01

Alkyl sulfate monoesters are involved in cell signaling and structure. Alkyl sulfates are also present in many commercial detergents. Here, we show that monomethyl sulfate acts as an efficient alkylating agent in water, reacting spontaneously with oxygen nucleophiles >100-fold more rapidly than do alkylsulfonium ions, the usual methyl donors in living organisms. These reactions of methyl sulfate, which are much more rapid than its hydrolysis, are insensitive to the nature of the attacking nucleophile, with a Brønsted βnuc value of −0.01. Experiments at elevated temperatures indicate a rate constant of 2 × 10−11 s−1 for the uncatalyzed hydrolysis of methyl sulfate at 25°C (t1/2 = 1,100 y), corresponding to a rate enhancement of ≈1011-fold by a human alkylsulfatase. Equilibria of formation of methyl sulfate from methanol and sodium hydrogen sulfate indicate a group transfer potential (ΔG′pH7) of −8.9 kcal/mol for sulfate ester hydrolysis. The magnitude of that value, involving release of the strong acid HSO4−, helps to explain the need for harnessing the free energy of hydrolysis of two ATP molecules in activating sulfate for the biosynthesis of sulfate monoesters. The “energy-rich” nature of monoalkyl sulfate esters, coupled with their marked resistance to hydrolysis, renders them capable of acting as sulfating or alkylating agents under relatively mild conditions. These findings raise the possibility that, under appropriate circumstances, alkyl groups may undergo transfer from alkyl sulfate monoesters to biological target molecules. PMID:17182738

Cu/Mn bimetallic catalysis enables carbonylative Suzuki-Miyaura coupling with unactivated alkyl electrophiles.

PubMed

Pye, Dominic R; Cheng, Li-Jie; Mankad, Neal P

2017-07-01

A bimetallic system consisting of Cu-carbene and Mn-carbonyl co-catalysts was employed for carbonylative C-C coupling of arylboronic esters with alkyl halides, allowing for the convergent synthesis of ketones. The system operates under mild conditions and exhibits complementary reactivity to Pd catalysis. The method is compatible with a wide range of arylboronic ester nucleophiles and proceeds smoothly for both primary and secondary alkyl iodide electrophiles. Preliminary mechanistic experiments corroborate a hypothetical catalytic mechanism consisting of co-dependent cycles wherein the Cu-carbene co-catalyst engages in transmetallation to generate an organocopper nucleophile, while the Mn-carbonyl co-catalyst activates the alkyl halide electrophile by single-electron transfer and then undergoes reversible carbonylation to generate an acylmanganese electrophile. The two cycles then intersect with a heterobimetallic, product-releasing C-C coupling step.

Enantiomerically Pure Acetals in Organic Synthesis: Resolutions and Diastereoselective Alkylations of Alpha-Hydroxy Esters

DTIC Science & Technology

1990-01-01

sensitivity of the alkylating agent to the reaction conditions. In either case , a decision was made to use 5-iodo-2- methyl -l-pentene as the alkylating ...agent, and the reaction conditions. In most cases the diastereomeric products of the alkylation were also separated by column chromatography. This...equatorially substituted product. Oxidation of the alcohol to the ketone followed by treatment with an alkyl Grignard reagent gave only the product which

ESR study of electron reactions with esters and triglycerides

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

Sevilla, M.D.; Morehouse, K.M.; Swarts, S.

1981-04-02

Reactions which occurred after electron attachment at 77K to a number of small carboxylic acid esters and triglycerides in an aqueous glass are reported. Most ester anions are found to decay on warming to form alkyl radicals by ..beta.. scission: RC(O/sup -/)OR' ..-->.. RCO/sub 2//sup -/ + R'.. The alkyl radical (R'.) produced by annealing is found to abstract hydrogen from the parent ester at an ..cap alpha..-carbon site, R'.+ R''CH/sub 2/CO/sub 2/R' ..-->.. R''CHCO/sub 2/R', or in the case of ethyl formate from the formate hydrogen, CH/sub 3/CH/sub 2/.+ HCO/sub 2/C/sub 2/H/sub 5/ ..-->.. C/sub 2/H/sub 6/ +.CO/sub 2/C/submore » 2/H/sub 5/. Results found for the methyl formate anion suggest hydrogen abstraction by the anion itself may compete with alkyl radical formation. The anion of the triglyceride triacetin is found to undergo an analogous mechanism to the ester anions producing the propane diol diester radical, .CH/sub 2/CH(Ac)CH/sub 2/(Ac), Ac = acetate. This species subsequently abstracts hydrogen from the parent compound to produce the ..cap alpha..-carbon radical, .CH/sub 2/CO/sub 2/R. Results found after annealing the tripropionin radical anion give evidence for abstraction from the ..cap alpha.. carbon in the propionate side groups producing CH/sub 3/CHCO/sub 2/R. Studies of a ..gamma..-irradiated ester (ethyl myristate) and two triglycerides (tripalmitin and tristearin) yield results which suggest that the mechanism of ester anion decay found in aqueous glasses applies to ..gamma..-irradiated neat long-chain esters and triglycerides. Results found in this work are compared to the results of product analysis.« less

Biodiesel: Fuel properties, its “Design” and a source of “Designer” fuel

USDA-ARS?s Scientific Manuscript database

The fuel properties of biodiesel, a biogenic alternative to petrodiesel, are largely determined by its component fatty acid alkyl esters, most commonly methyl esters. These esters have vastly different properties. The properties of biodiesel are an aggregate of the properties of its components and t...

Inhibitors of glycogen synthase 3 kinase

DOEpatents

Schultz, Peter; Ring, David B.; Harrison, Stephen D.; Bray, Andrew M.

2000-01-01

Compounds of formula 1: ##STR1## wherein R.sub.1 is alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, or heteroaralkyl, substituted with 0-3 substituents selected from lower alkyl, halo, hydroxy, lower alkoxy, amino, lower alkyl-amino, and nitro; R.sub.2 is hydroxy, amino, or lower alkoxy; R.sub.3 is H, lower alkyl, lower acyl, lower alkoxy-acyl, or amnino-acyl; R.sub.4 is H or lower alkyl; and pharmaceutically acceptable salts and esters thereof; are effective inhibitors of GSK3.

Inhibitors of glycogen synthase 3 kinase

DOEpatents

Schultz, Peter; Ring, David B.; Harrison, Stephen D.; Bray, Andrew M.

2006-05-30

Compounds of formula 1: ##STR00001## wherein R.sub.1 is alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, or heteroaralkyl, substituted with 0 3 substituents selected from lower alkyl, halo, hydroxy, lower alkoxy, amino, lower alkyl-amino, and nitro; R.sub.2 is hydroxy, amino, or lower alkoxy; R.sub.3 is H, lower alkyl, lower acyl, lower alkoxy-acyl, or amino-acyl; R.sub.4 is H or lower alkyl; and pharmaceutically acceptable salts and esters thereof; are effective inhibitors of GSK3.

Epoxy-Based Organogels for Thermally Reversible Light Scattering Films and Form-Stable Phase Change Materials.

PubMed

Puig, Julieta; Dell' Erba, Ignacio E; Schroeder, Walter F; Hoppe, Cristina E; Williams, Roberto J J

2017-03-29

Alkyl chains of β-hydroxyesters synthesized by the capping of terminal epoxy groups of diglycidylether of bisphenol A (DGEBA) with palmitic (C16), stearic (C18), or behenic (C22) fatty acids self-assemble forming a crystalline phase. Above a particular concentration solutions of these esters in a variety of solvents led to supramolecular (physical) gels below the crystallization temperature of alkyl chains. A form-stable phase change material (FS-PCM) was obtained by blending the ester derived from behenic acid with eicosane. A blend containing 20 wt % ester was stable as a gel up to 53 °C and exhibited a heat storage capacity of 161 J/g, absorbed during the melting of eicosane at 37 °C. Thermally reversible light scattering (TRLS) films were obtained by visible-light photopolymerization of poly(ethylene glycol) dimethacrylate-ester blends (50 wt %) in the gel state at room temperature. The reaction was very fast and not inhibited by oxygen. TRLS films consisted of a cross-linked methacrylic network interpenetrated by the supramolecular network formed by the esters. Above the melting temperature of crystallites formed by alkyl chains, the film was transparent due to the matching between refractive indices of the methacrylic network and the amorphous ester. Below the crystallization temperature, the film was opaque because of light dispersion produced by the organic crystallites uniformly dispersed in the material. Of high significance for application was the fact that the contrast ratio did not depend on heating and cooling rates.

Structural and Mechanistic Analysis of the Choline Sulfatase from Sinorhizobium melliloti: A Class I Sulfatase Specific for an Alkyl Sulfate Ester.

PubMed

van Loo, Bert; Schober, Markus; Valkov, Eugene; Heberlein, Magdalena; Bornberg-Bauer, Erich; Faber, Kurt; Hyvönen, Marko; Hollfelder, Florian

2018-03-30

Hydrolysis of organic sulfate esters proceeds by two distinct mechanisms, water attacking at either sulfur (S-O bond cleavage) or carbon (C-O bond cleavage). In primary and secondary alkyl sulfates, attack at carbon is favored, whereas in aromatic sulfates and sulfated sugars, attack at sulfur is preferred. This mechanistic distinction is mirrored in the classification of enzymes that catalyze sulfate ester hydrolysis: arylsulfatases (ASs) catalyze S-O cleavage in sulfate sugars and arylsulfates, and alkyl sulfatases break the C-O bond of alkyl sulfates. Sinorhizobium meliloti choline sulfatase (SmCS) efficiently catalyzes the hydrolysis of alkyl sulfate choline-O-sulfate (k cat /K M =4.8×10 3 s -1 M -1 ) as well as arylsulfate 4-nitrophenyl sulfate (k cat /K M =12s -1 M -1 ). Its 2.8-Å resolution X-ray structure shows a buried, largely hydrophobic active site in which a conserved glutamate (Glu386) plays a role in recognition of the quaternary ammonium group of the choline substrate. SmCS structurally resembles members of the alkaline phosphatase superfamily, being most closely related to dimeric ASs and tetrameric phosphonate monoester hydrolases. Although >70% of the amino acids between protomers align structurally (RMSDs 1.79-1.99Å), the oligomeric structures show distinctly different packing and protomer-protomer interfaces. The latter also play an important role in active site formation. Mutagenesis of the conserved active site residues typical for ASs, H 2 18 O-labeling studies and the observation of catalytically promiscuous behavior toward phosphoesters confirm the close relation to alkaline phosphatase superfamily members and suggest that SmCS is an AS that catalyzes S-O cleavage in alkyl sulfate esters with extreme catalytic proficiency. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Condensation Reactions and Formation of Amides, Esters, and Nitriles Under Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Rushdi, Ahmed I.; Simoneit, Bernd R. T.

2004-06-01

Hydrothermal pyrolysis experiments were performed to assess condensation (dehydration) reactions to amide, ester, and nitrile functionalities from lipid precursors. Beside product formation, organic compound alteration and stability were also evaluated. Mixtures of nonadecanoic acid, hexadecanedioic acid, or hexadecanamide with water, ammonium bicarbonate, and oxalic acid were heated at 300°C for 72 h. In addition, mixtures of ammonium bicarbonate and oxalic acid solutions were used to test the abiotic formation of organic nitrogen compounds at the same temperature. The resulting products were condensation compounds such as amides, nitriles, and minor quantities of N-methylalkyl amides, alkanols, and esters. Mixtures of alkyl amide in water or oxalic acid yielded mainly hydrolysis and dehydration products, and with ammonium bicarbonate and oxalic acid the yield of condensation products was enhanced. The synthesis experiments with oxalic acid and ammonium bicarbonate solutions yielded homologous series of alkyl amides, alkyl amines, alkanes, and alkanoic acids, all with no carbon number predominances. These organic nitrogen compounds are stable and survive under the elevated temperatures of hydrothermal fluids.

Self-Assembly, Supramolecular Organization, and Phase Behavior of L-Alanine Alkyl Esters (n = 9-18) and Characterization of Equimolar L-Alanine Lauryl Ester/Lauryl Sulfate Catanionic Complex.

PubMed

Sivaramakrishna, D; Swamy, Musti J

2015-09-08

A homologous series of l-alanine alkyl ester hydrochlorides (AEs) bearing 9-18 C atoms in the alkyl chain have been synthesized and characterized with respect to self-assembly, supramolecular structure, and phase transitions. The CMCs of AEs bearing 11-18 C atoms were found to range between 0.1 and 10 mM. Differential scanning calorimetric (DSC) studies showed that the transition temperatures (Tt), enthalpies (ΔHt) and entropies (ΔSt) of AEs in the dry state exhibit odd-even alternation, with the odd-chain-length compounds having higher Tt values, but the even-chain-length homologues showing higher values of ΔHt and ΔSt. In DSC measurements on hydrated samples, carried out at pH 5.0 and pH 10.0 (where they exist in cationic and neutral forms, respectively), compounds with 13-18 C atoms in the alkyl chain showed sharp gel-to-liquid crystalline phase transitions, and odd-even alternation was not seen in the thermodynamic parameters. The molecular structure, packing properties, and intermolecular interactions of AEs with 9 and 10 C atoms in the alkyl chain were determined by single crystal X-ray diffraction, which showed that the alkyl chains are packed in a tilted interdigitated bilayer format. d-Spacings obtained from powder X-ray diffraction studies exhibited a linear dependence on the alkyl chain length, suggesting that the other AEs also adopt an interdigitated bilayer structure. Turbidimetric, fluorescence spectroscopic, and isothermal titration calorimetric (ITC) studies established that in aqueous dispersions l-alanine lauryl ester hydrochloride (ALE·HCl) and sodium dodecyl sulfate (SDS) form an equimolar complex. Transmission electron microscopic and DSC studies indicate that the complex exists as unilamellar liposomes, which exhibit a sharp phase transition at ∼39 °C. The aggregates were disrupted at high pH, suggesting that the catanionic complex would be useful to develop a base-labile drug delivery system. ITC studies indicated that ALE·HCl forms a strong complex with DNA, suggesting that the AEs may find use in DNA therapeutics as well.

β-Keto esters from ketones and ethyl chloroformate: a rapid, general, efficient synthesis of pyrazolones and their antimicrobial, in silico and in vitro cytotoxicity studies

PubMed Central

2013-01-01

Background Pyrazolones are traditionally synthesized by the reaction of β-keto esters with hydrazine and its derivatives. There are methods to synthesize β-keto esters from esters and aldehydes, but these methods have main limitation in varying the substituents. Often, there are a number of methods such as acylation of enolates in which a chelating effect has been employed to lock the enolate anion using lithium and magnesium salts; however, these methods suffer from inconsistent yields in the case of aliphatic acylation. There are methods to synthesize β-keto esters from ketones like caboxylation of ketone enolates using carbon dioxide and carbon monoxide sources in the presence of palladium or transition metal catalysts. Currently, the most general and simple method to synthesize β-keto ester is the reaction of dimethyl or ethyl carbonate with ketone in the presence of strong bases which also requires long reaction time, use of excessive amount of reagent and inconsistent yield. These factors lead us to develop a simple method to synthesize β-keto esters by changing the base and reagent. Results A series of β-keto esters were synthesized from ketones and ethyl chloroformate in the presence of base which in turn are converted to pyrazolones and then subjected to cytotoxicity studies towards various cancer cell lines and antimicrobial activity studies towards various bacterial and fungal strains. Conclusion The β-keto esters from ethyl chloroformate was successfully attempted, and the developed method is simple, fast and applicable to the ketones having the alkyl halogens, protecting groups like Boc and Cbz that were tolerated and proved to be useful in the synthesis of fused bicyclic and tricyclic pyrazolones efficiently using cyclic ketones. Since this method is successful for different ketones, it can be useful for the synthesis of pharmaceutically important pyrazolones also. The synthesized pyrazolones were subjected to antimicrobial, docking and cytotoxicity assay against ACHN (human renal cell carcinoma), Panc-1 (human pancreatic adenocarcinoma) and HCT-116 (human colon cancer) cell line, and lead molecules have been identified. Some of the compounds are found to have promising activity against different bacterial and fungal strains tested. PMID:23870758

Enantiomerically Enriched α-Methyl Amino Acids. Use of an Acyclic, Chiral Alanine-Derived Dianion with a High Diastereofacial Bias.†

PubMed Central

Berkowitz, David B.; Smith, Marianne K.

2018-01-01

Hindered esters derived from N-benzoylalanine and the following chiral alcohols have been synthesized: (1) (−)-isopinocampheol; (2) (−)-trans-2-phenylcyclohexanol and (3) (−)-8-phenylmenthol. Sequential treatment of these esters with LDA (1.2 equiv.) and n-butyllithium (2.4 equiv.) at −78°C in THF generates the corresponding chiral dianions. Alkylation of each of these with benzyl bromide reveals that only the (−)-8-phenylmenthyl auxiliary confers a high diastereofacial bias upon its derivative dianion. In fact, that dianion (6) consistently displays diastereomeric ratios in the range of 89:11 to 94:6 for alkylations with a spectrum of nine alkyl halides. If one recrystallization step is included, a single diastereomeric product may be obtained, as is demonstrated for the benzylation of 6. Of particular note, the alkylation with 3,4-bis(tert-butyldimethylsilyloxy)benzyl bromide (18) (94:6 diast. ratio, 72% yield) constitutes a formal synthesis of the clinically important antihypertensive (S)-α-methyl-DOPA (Aldomet), in enantiomerically enriched from. In all cases studied, yields are markedly improved, yet diastereoselectivities unchanged, by the addition of 10% HMPA to the reaction milieu. The (−)-8-phenylmenthol chiral auxiliary is conveniently recovered via ester cleavage with KO2/18-crown-6, following alkylation. Complete deprotection affords enantiomerically enriched (S)-α-methyl amino acids, in all cases examined, indicating that dianion 6 displays a substantial bias in favor of si face alkylation. This sense of diastereoselection is consistent with a chain-extended, internal chelate model for the reactive conformation of the dianion.

[Characteristics of organic pollutants in the sediments from a typical electronics industrial zone].

PubMed

Liu, Jin; Deng, Dai-Yong; Xu, Mei-Ying; Sun, Guo-Ping

2013-03-01

In order to investigate the contamination status of organic pollutants in a river of a typical electrical equipment industrial area, Ronggui, Foshan, the sediments were sampled for the composition, concentration and occurrence analysis of organic pollutants. The polar and non-polar fractionation methods were employed for the fingerprint establishment of organic pollutants. One hundred and seventy-one of organic chemicals including ten categories of alkanes, alkenes, polycyclic aromatic hydrocarbons, benzene, heterocyclic compounds, phthalate esters, aldehydes, ketones, polar compounds, silicon-containing material as well as alkyl esters were examined. The number of different categories of the detected organic pollutants in a descending order was: alkanes > polar compounds > polycyclic aromatic hydrocarbons > aldehydes and ketones > heterocyclic compounds > benzene homologues, phthalate ester > alkyl esters > silicon material > olefins. The abundance of detected organic pollutants in a descending order was: alkanes > polar compounds > alkyl esters > olefins > polycyclic aromatic hydrocarbons > phthalates > silicon material > aldehydes and ketones > heterocyclic compounds > benzene homologues. Among the 51 kinds of alkanes detected, nonadecane accounted for 14.83%, and the persistent organic pollutants accounted for 2.33% of the total organic matter. Compared to similar studies, there were 51 kinds of alkanes and they accounted for 55.5% of the total organic chemicals, showing high diversity and abundance. In addition, some electronics industry-related organic pollutants such as silicone materials were also detected in high frequency.

Rapid determination of amino acids in neonatal blood samples based on derivatization with isobutyl chloroformate followed by solid-phase microextraction and gas chromatography/mass spectrometry.

PubMed

Deng, Chunhui; Li, Ning; Zhang, Xiangmin

2004-01-01

The purpose of this study was to develop a simple, rapid and sensitive analytical method for determination of amino acids in neonatal blood samples. The developed method involves the employment of derivatization and a solid-phase microextraction (SPME) technique together with gas chromatography/mass spectrometry (GC/MS). Amino acids in blood samples were derivatized by a mixture of isobutyl chloroformate, methanol and pyridine, and the N(O,S)-alkoxycarbonyl alkyl esters thus formed were headspace extracted by a SPME fiber. Finally, the extracted analytes on the fiber were desorbed and detected by GC/MS in electron impact (EI) mode. L-Valine, L-leucine, L-isoleucine, L-phenylanaline and L-tyrosine in blood samples were quantitatively analyzed by measurement of the corresponding N(O,S)-alkoxycarbonyl alkyl esters using an external standard method. SPME conditions were optimized, and the method was validated. The method was applied to diagnosis of neonatal phenylkenuria (PKU) and maple syrup urine disease (MSUD) by the analyses of five amino acids in blood samples. The results showed that the proposed method is a potentially powerful tool for simultaneous screening for neonatal PKU and MSUD. Copyright (c) 2004 John Wiley & Sons, Ltd.

Fundamental Characterization of the Micellar Self-Assembly of Sophorolipid Esters.

PubMed

Koh, Amanda; Todd, Katherine; Sherbourne, Ezekiel; Gross, Richard A

2017-06-13

Surfactants are ubiquitous constituents of commercial and biological systems that function based on complex structure-dependent interactions. Sophorolipid (SL) n-alkyl esters (SL-esters) comprise a group of modified naturally derived glycolipids from Candida bombicola. Herein, micellar self-assembly behavior as a function of SL-ester chain length was studied. Surface tensions as low as 31.2 mN/m and critical micelle concentrations (CMCs) as low as 1.1 μM were attained for diacetylated SL-decyl ester (dASL-DE) and SL-octyl ester, respectively. For deacetylated SL-esters, CMC values reach a lower limit at SL-ester chains above n-butyl (SL-BE, 1-3 μM). This behavior of SL-esters with increasing hydrophobic tail length is unlike other known surfactants. Diffusion-ordered spectroscopy (DOSY) and T 1 relaxation NMR experiments indicate this behavior is due to a change in intramolecular interactions, which impedes the self-assembly of SL-esters with chain lengths above SL-BE. This hypothesis is supported by micellar thermodynamics where a disruption in trends occurs at n-alkyl ester chain lengths above those of SL-BE and SL-hexyl ester (SL-HE). Diacetylated (dA) SL-esters exhibit an even more unusual trend in that CMC increases from 1.75 to 815 μM for SL-ester chain lengths of dASL-BE and dASL-DE, respectively. Foaming studies, performed to reveal the macroscopic implications of SL-ester micellar behavior, show that the observed instability in foams formed using SL-esters are due to coalescence, which highlights the importance of understanding intermicellar interactions. This work reveals that SL-esters are an important new family of green high-performing surfactants with unique structure-property relationships that can be tuned to optimize micellar characteristics.

Composition of the epicuticular waxes coating the adaxial side of Phyllostachys aurea leaves: Identification of very-long-chain primary amides.

PubMed

Racovita, Radu C; Jetter, Reinhard

2016-10-01

The present study presents comprehensive chemical analyses of cuticular wax mixtures of the bamboo Phyllostachys aurea. The epicuticular and intracuticular waxes were sampled selectively from the adaxial side of leaves on young and old plants and investigated by gas chromatography-mass spectrometry and flame ionization detection. The epi- and intracuticular layers on young and old leaves had wax loads ranging from 1.7 μg/cm(2) to 1.9 μg/cm(2). Typical very-long-chain aliphatic wax constituents were found with characteristic chain length patterns, including alkyl esters (primarily C48), alkanes (primarily C29), fatty acids (primarily C28 and C16), primary alcohols (primarily C28) and aldehydes (primarily C30). Alicyclic wax components were identified as tocopherols and triterpenoids, including substantial amounts of triterpenoid esters. Alkyl esters, alkanes, fatty acids and aldehydes were found in greater amounts in the epicuticular layer, while primary alcohols and most terpenoids accumulated more in the intracuticular wax. Alkyl esters occurred as mixtures of metamers, combining C20 alcohol with various acids into shorter ester homologs (C36C40), and a wide range of alcohols with C22 and C24 acids into longer esters (C42C52). Primary amides were identified, with a characteristic chain length profile peaking at C30. The amides were present exclusively in the epicuticular layer and thus at or near the surface, where they may affect plant-herbivore or plant-pathogen interactions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fatty acid alkyl esters as solvents: An evaluation of the kauri-butanol value. Comparison to hydrocarbons, dimethyl diesters and other oxygenates

USDA-ARS?s Scientific Manuscript database

Esters, most commonly methyl esters, of vegetable oils or animal fats or other lipid feedstocks have found increasing use as an alternative diesel fuel known as biodiesel. However, biodiesel also has good solvent properties, a feature rendered additionally attractive by its biodegradability, low tox...

Cu/Mn bimetallic catalysis enables carbonylative Suzuki–Miyaura coupling with unactivated alkyl electrophiles† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc01170a Click here for additional data file.

PubMed Central

Pye, Dominic R.; Cheng, Li-Jie

2017-01-01

A bimetallic system consisting of Cu-carbene and Mn-carbonyl co-catalysts was employed for carbonylative C–C coupling of arylboronic esters with alkyl halides, allowing for the convergent synthesis of ketones. The system operates under mild conditions and exhibits complementary reactivity to Pd catalysis. The method is compatible with a wide range of arylboronic ester nucleophiles and proceeds smoothly for both primary and secondary alkyl iodide electrophiles. Preliminary mechanistic experiments corroborate a hypothetical catalytic mechanism consisting of co-dependent cycles wherein the Cu-carbene co-catalyst engages in transmetallation to generate an organocopper nucleophile, while the Mn-carbonyl co-catalyst activates the alkyl halide electrophile by single-electron transfer and then undergoes reversible carbonylation to generate an acylmanganese electrophile. The two cycles then intersect with a heterobimetallic, product-releasing C–C coupling step. PMID:28966784

Silver-mediated direct trifluoromethoxylation of α-diazo esters via the (-)OCF3 anion.

PubMed

Zha, Gao-Feng; Han, Jia-Bin; Hu, Xiao-Qian; Qin, Hua-Li; Fang, Wan-Yin; Zhang, Cheng-Pan

2016-06-14

Silver-mediated direct trifluoromethoxylation of α-diazo esters and ketosteroid was disclosed. The reactions of alkyl α-diazo arylacetates with AgOCF3 or CF3SO2OCF3/AgF at -30 to 10 °C under a N2 atmosphere provided α-trifluoromethoxyl arylacetates in up to 90% yield, while alkyl α-diazo vinylacetates reacting with CF3SO2OCF3/AgF or AgOCF3 afforded γ-trifluoromethoxyl α,β-unsaturated esters in up to 94% yield. The α-diazo ketosteroid was also trifluoromethoxylated under the standard reaction conditions. This protocol allows for an effective and convenient access to a large number of synthetic building blocks, which are promising in the development of new functional OCF3-molecules.

Lubricating Coolant for Cold Rolling of Aluminum and Its Alloys,

DTIC Science & Technology

The title fluid consists of a mixtures of alkyl esters of high molecular weight acids, an ester of xylitol and a C(subscript 6) or higher fatty acid...molecular weight acids 3-6, an ester of xylitol and a C(subscript 6) or higher fatty acid 1-3, an Al soap 0.3-1, a mineral oil 10-60, a polyoxyethylene

Three approaches to fuels from fatty compounds

USDA-ARS?s Scientific Manuscript database

Biodiesel, the alkyl esters, usually methyl esters, of vegetable oils, animal fats, or other triacylglycerol-containing materials, are the most common approach to producing a fuel from the mentioned materials. This fuel is obtained by transesterifying the oil or fat with an alcohol, usually methanol...

Synthesis and characterization of chitosan alkyl urea.

PubMed

Wang, Jing; Jiang, Ji-Zhou; Chen, Wei; Bai, Zheng-Wu

2016-07-10

Chitosan is a versatile material employed for various purposes in many fields including the development of chiral stationary phases for enantioseparation. Chitosan alkyl urea is a kind of intermediate used to prepare enantioseparation materials. In order to synthesize the intermediates, in the present work, a new way to prepare chitosan alkyl urea has been established: chitosan was first reacted with methyl chloroformate yielding N-methoxyformylated chitosan, which was then converted to chitosan alkyl urea through amine-ester exchange reaction. With a large excess of methyl chloroformate and primary amine of low stereohindrance, the amino group in chitosan could be almost completely converted to ureido group. The as-prepared chitosan alkyl urea derivatives were characterized by IR, (1)H NMR, (13)C NMR,(1)H-(1)H COSY and (1)H-(13)C HSQC NMR spectra. The chemical shifts of hydrogen and carbon atoms of glucose unit were assigned. It was found that the degree of substitution was obviously lower if cyclopropyl amine, aniline, tert-butyl amine and diethyl amine were used as reactants for the amine-ester exchange reaction. The reason was explained with the aid of theoretical calculations. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enantioselective synthesis of chiral oxazolines from unactivated ketones and isocyanoacetate esters by synergistic silver/organocatalysis.

PubMed

Martínez-Pardo, Pablo; Blay, Gonzalo; Muñoz, M Carmen; Pedro, José R; Sanz-Marco, Amparo; Vila, Carlos

2018-03-15

A multicatalytic approach that combines a bifunctional Brønsted base-squaramide organocatalyst and Ag + as Lewis acid has been applied in the reaction of unactivated ketones with tert-butyl isocyanoacetate to give chiral oxazolines bearing a quaternary stereocenter. The formal [3+2] cycloaddition provided high yields of the corresponding cis-oxazolines with good diastereoselectivity and excellent enantioselectivity, being applied to aryl-alkyl and alkyl-alkyl ketones.

Improved Preparation of Halopropyl Bridged Carboxylic Ortho Esters

USDA-ARS?s Scientific Manuscript database

Protection of a carboxylic acid function as a bridged ortho ester derivative enables the use of strongly basic conditions in the synthetic strategy because the protons, alpha to the previous carbonyl carbon, are less acidic. Protected 3-halopropionic acid can behave like an alkyl halide making them...

40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

Code of Federal Regulations, 2012 CFR

2012-07-01

... subject to reporting. (1) The chemical substance generically identified as carbopolycyclicol azo-al-kyl-a-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting under...

40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

Code of Federal Regulations, 2013 CFR

2013-07-01

... subject to reporting. (1) The chemical substance generically identified as carbopolycyclicol azo-al-kyl-a-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting under...

40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

Code of Federal Regulations, 2014 CFR

2014-07-01

... subject to reporting. (1) The chemical substance generically identified as carbopolycyclicol azo-al-kyl-a-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting under...

40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

Code of Federal Regulations, 2011 CFR

2011-07-01

... subject to reporting. (1) The chemical substance generically identified as carbopolycyclicol azo-al-kyl-a-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting under...

Iron-catalyzed regio- and stereoselective substitution of gamma,delta-epoxy-alpha,beta-unsaturated esters and amides with Grignard reagents.

PubMed

Hata, Takeshi; Bannai, Rie; Otsuki, Mamoru; Urabe, Hirokazu

2010-03-05

When gamma,delta-epoxy-alpha,beta-unsaturated esters or amides were treated with 2 equiv of Grignard reagents in the presence of 10-24 mol % FeCl(2), regio- and stereoselective substitution of the epoxide moiety with the Grignard reagent occurred to give exclusively delta-hydroxy-gamma-alkyl or aryl-alpha,beta-unsaturated esters or amides in good yields.

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

Code of Federal Regulations, 2010 CFR

2010-07-01

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

SEPARATION OF T-MAZ ETHOXYLATED SORBITAN FATTY ACID ESTERS BY REVERSE PHASE CHROMATOGRAPHY

EPA Science Inventory

The method for determination of T-MAZ ethoxylated sorbitan fatty acid esters is described. This work demonstrates that with a less retentive C8 alkyl bonded phase packing, reverse phase chromatography can be used to analyze nonionic polymer mixtures with a molecular weight range ...

Pd-catalyzed allylic alkylation of dienyl carbonates with nitromethane with high C-5 regioselectivity.

PubMed

Yang, Xiao-Fei; Li, Xiao-Hui; Ding, Chang-Hua; Xu, Chao-Fan; Dai, Li-Xin; Hou, Xue-Long

2014-01-14

A highly regioselective palladium-catalyzed allylic alkylation of dienyl esters with nitromethane has been developed, providing selective access to the C-5 attacked products. The structures of the ligands as well as the steric effect of the substrates are important factors in determining the regiochemical outcome of the reaction.

40 CFR 721.10526 - 2-Propenoic acid, 2-methyl-, 2-hydroxyethyl ester, telomers with C18-26-alkyl acrylate, 1...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-dodecanethiol, N-(hydroxymethyl)-2-methyl-2-propenamide, polyfluorooctyl methacrylate and vinylidene chloride, 2...-alkyl acrylate, 1-dodecanethiol, N-(hydroxymethyl)-2-methyl-2-propenamide, polyfluorooctyl methacrylate... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 2-Propenoic acid, 2-methyl-, 2...

40 CFR 721.10526 - 2-Propenoic acid, 2-methyl-, 2-hydroxyethyl ester, telomers with C18-26-alkyl acrylate, 1...

Code of Federal Regulations, 2014 CFR

2014-07-01

...-dodecanethiol, N-(hydroxymethyl)-2-methyl-2-propenamide, polyfluorooctyl methacrylate and vinylidene chloride, 2...-alkyl acrylate, 1-dodecanethiol, N-(hydroxymethyl)-2-methyl-2-propenamide, polyfluorooctyl methacrylate... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 2-Propenoic acid, 2-methyl-, 2...

Effects of Fatty Acid Addition to Oil-in-water Emulsions Stabilized with Sucrose Fatty Acid Ester.

PubMed

Watanabe, Takamasa; Kawai, Takahiro; Nonomura, Yoshimune

2018-03-01

Adding fatty acids to an oil-in-water (O/W) emulsion changes the stability of the emulsion. In this study, we prepared a series of O/W emulsions consisting of oil (triolein/fatty acid mixture), water and a range of surfactants (sucrose fatty acid esters) with varying hydrophilic-lipophilic balance (HLB) in order to determine the effects of alkyl chain length and the degree of unsaturation of the fatty acid molecules on the stability of the emulsions. As a result, sucrose fatty acid esters with HLB = 5-7 were suitable for obtaining O/W emulsions. In addition, the creaming phenomenon was inhibited for 30 days or more when fatty acids having a linear saturated alkyl chain with 14 or more carbon atoms were added. These findings are useful for designing stable O/W emulsions for food and cosmetic products.

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ni-tro-thio-phene-car-boxy-lic acid... Substances § 721.5375 Ni-tro-thio-phene-car-boxy-lic acid, ethyl es-ter, bis-[[[[(sub-sti-tut-ed)] amino... reporting. (1) The chemical substance ni-tro-thio-phene-car-boxy-lic acid, ethyl ester, bis...

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ni-tro-thio-phene-car-boxy-lic acid... Substances § 721.5375 Ni-tro-thio-phene-car-boxy-lic acid, ethyl es-ter, bis-[[[[(sub-sti-tut-ed)] amino... reporting. (1) The chemical substance ni-tro-thio-phene-car-boxy-lic acid, ethyl ester, bis...

Microbial Transformation of Esters of Chlorinated Carboxylic Acids

PubMed Central

Paris, D. F.; Wolfe, N. L.; Steen, W. C.

1984-01-01

Two groups of compounds were selected for microbial transformation studies. In the first group were carboxylic acid esters having a fixed aromatic moiety and an increasing length of the alkyl component. Ethyl esters of chlorine-substituted carboxylic acids were in the second group. Microorganisms from environmental waters and a pure culture of Pseudomonas putida U were used. The bacterial populations were monitored by plate counts, and disappearance of the parent compound was followed by gas-liquid chromatography as a function of time. The products of microbial hydrolysis were the respective carboxylic acids. Octanol-water partition coefficients (Kow) for the compounds were measured. These values spanned three orders of magnitude, whereas microbial transformation rate constants (kb) varied only 50-fold. The microbial rate constants of the carboxylic acid esters with a fixed aromatic moiety increased with an increasing length of alkyl substituents. The regression coefficient for the linear relationships between log kb and log Kow was high for group 1 compounds, indicating that these parameters correlated well. The regression coefficient for the linear relationships for group 2 compounds, however, was low, indicating that these parameters correlated poorly. PMID:16346459

Quantitative analysis of phosphoric acid esters in aqueous samples by isotope dilution stir-bar sorptive extraction combined with direct analysis in real time (DART)-Orbitrap mass spectrometry.

PubMed

Bridoux, Maxime C; Malandain, Hélène; Leprince, Françoise; Progent, Frédéric; Machuron-Mandard, Xavier

2015-04-15

A novel hyphenated technique, namely the combination of stir bar sorptive extraction (SBSE) with isotope dilution direct analysis in real time (DART) Orbitrap™ mass spectrometry (OT-MS) is presented for the extraction of phosphoric acid alkyl esters (tri- (TnBP), di- (HDBP), and mono-butyl phosphate (H2MBP)) from aqueous samples. First, SBSE of phosphate esters was performed using a Twister™ coated with 24 μL of polydimethylsiloxane (PDMS) as the extracting phase. SBSE was optimized for extraction pH, phase ratio (PDMS volume/aqueous phase volume), stirring speed, extraction time and temperature. Then, coupling of SBSE to DART/Orbitrap-MS was achieved by placing the Twister™ in the middle of an open-ended glass tube between the DART and the Orbitrap™. The DART mass spectrometric response of phosphate esters was probed using commercially available and synthesized alkyl phosphate ester standards. The positive ion full scan spectra of alkyl phosphate triesters (TnBP) was characterized by the product of self-protonation [M+H](+) and, during collision-induced dissociation (CID), the major fragmentation ions corresponded to consecutive loss of alkyl chains. Negative ionization gave abundant [M-H](-) ions for both HDnBP and H2MnBP. Twisters™ coated with PDMS successfully extracted phosphate acid esters (tri-, di- and mono-esters) granted that the analytes are present in the aqueous solution in the neutral form. SBSE/DART/Orbitrap-MS results show a good linearity between the concentrations and relative peak areas for the analytes in the concentration range studied (0.1-750 ng mL(-1)). Reproducibility of this SBSE/DART/Orbitrap-MS method was evaluated in terms of %RSD by extracting a sample of water fortified with the analytes. The %RSDs for TnBP, HDnBP and H2MnBP were 4, 3 and 3% (n=5) using the respective perdeuterated internal standards. Matrix effects were investigated by matrix matched calibration standards using underground water samples (UWS) and river water samples (RWS). Matrix effects were effectively compensated by the addition of the perdeuterated internal standards. The application of this new SBSE/DART/Orbitrap-MS method should be very valuable for on-site sampling/monitoring, limiting the transport of large volumes of water samples from the sampling site to the laboratory. Copyright © 2015 Elsevier B.V. All rights reserved.

Chronic toxicity of Pydraul 50E to lake trout

USGS Publications Warehouse

Mayer, Foster L.; Woodward, Daniel F.; Adams, William J.

1993-01-01

Industrial phosphate esters, both triaryl and alkyl aryl phosphate esters, are used as fire resistant hydraulic fluids and as fire retardant plasticizers (Lapp 1976). Hydraulic fluids probably represent the largest contribution of phosphate ester compounds released into the environment. Lapp (1976) estimated that 65 to 70 percent of all phosphate ester hydraulic fluids were utilized in automotive and steel industries. He also estimated that 80 percent of the annual consumption of hydraulic fluids in 1976 was the result of leaks in industrial hydraulic systems. These data suggest phosphate esters are likely to be constituents of industrial effluents and, consequently, could be in point source discharges.

Development of high temperature liquid lubricants for low-heat rejection heavy duty diesel engines

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

Wiczynski, T.A.; Marolewski, T.A.

1993-03-01

Objective was to develop a liquid lubricant that will allow advanced diesel engines to operate at top ring reversal temperatures approaching 500 C and lubricant sump temperatures approaching 250 C. Base stock screening showed that aromatic esters and diesters has the lowest deposit level, compared to polyol esters, poly-alpha-olefins, or refined mineral oil of comparable viscosity. Classical aryl and alkyl ZDP antiwear additives are ineffective in reducing wear with aromatic esters; the phosphate ester was a much better antiwear additive, and polyol esters are more amenable to ZDP treatment. Zeolites and clays were evaluated for filtration.

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

PubMed

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

2007-03-01

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

A systematic resolution of sulfur in reticulated vitreous carbon using X-ray absorption spectroscopy.

PubMed

Frank, Patrick; George, Serena DeBeer; Anxolabéhère-Mallart, Elodie; Hedman, Britt; Hodgson, Keith O

2006-11-27

Sulfur K-edge X-ray absorption spectroscopy (XAS) was used to characterize the approximately 0.1% sulfur found both in native reticulated vitreous carbon (RVC) foam and in RVC oxidatively modified using 0.2 M KMnO4 in 2 M H2SO4. Sulfur valences and functional groups were assessed using K-edge XAS spectral curve-fitting and employing explicit sulfur compounds as models. For native RVC, these were episulfide (approximately 3%), thianthrene (approximately 9%), disulfide (approximately 10%), sulfenate ester (approximately 12%), benzothiophene (approximately 24%), N,N'-thiobisphthalimide (approximately 30%), alkyl sulfonate (approximately 1.2%), alkyl sulfate monoester (approximately 6%), and sulfate dianion (approximately 6%). Permanganate oxidation of RVC diminished sulfenic sulfur to approximately 9%, thianthrenic sulfur to approximately 7%, and sulfate dianion to approximately 1% but increased sulfate monoester to approximately 12%, and newly produced sulfone (approximately 2%) and sulfate diester (approximately 5%). A simple thermodynamic model was derived that allows proportionate functional group comparisons despite differing (approximately +/-15%) total sulfur contents between RVC batches. The limits of accuracy in the XAS curve-fitting analysis are discussed in terms of microenvironments and extended structures in RVC carbon that cannot be exactly modeled by small molecules. Sulfate esters cover approximately 0.15% of the RVC surface, increasing to approximately 0.51% following permanganate/sulfuric acid treatment. The detection of episulfide directly corroborates a proposed mechanism for the migration of elemental sulfur through carbon.

When alcohol is the answer: trapping, identifying and quantifying simple alkylating species in aqueous environments

PubMed Central

Penketh, P. G.; Shyam, K.; Baumann, R. P; Zhu, Rui; Ishiguro, K.; Sartorelli, A. C.; Ratner, E. S.

2016-01-01

Alkylating agents are a significant class of environmental carcinogens as well as commonly used anticancer therapeutics. Traditional alkylating activity assays have utilized the colorimetric reagent 4-(4-nitrobenzyl)pyridine (4NBP). However, 4NBP based assays have a relatively low sensitivity towards harder, more oxophilic alkylating species and are not well suited for the identification of the trapped alkyl moiety due to adduct instability. Herein we describe a method using water as the trapping agent which permits the trapping of simple alkylating electrophiles with a comparatively wide range of softness/hardness and permits the identification of donated simple alkyl moieties. PMID:27188264

Water-soluble polymers and compositions thereof

DOEpatents

Smith, B.F.; Robison, T.W.; Gohdes, J.W.

1999-04-06

Water-soluble polymers including functionalization from the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, aza crown ether groups, oxy crown ethers groups, guanidinium groups, amide groups, ester groups, aminodicarboxylic groups, permethylated polyvinylpyridine groups, permethylated amine groups, mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea groups are disclosed.

Water-soluble polymers and compositions thereof

DOEpatents

Smith, Barbara F.; Robison, Thomas W.; Gohdes, Joel W.

2002-01-01

Water-soluble polymers including functionalization from the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, aza crown ether groups, oxy crown ethers groups, guanidinium groups, amide groups, ester groups, aminodicarboxylic groups, permethylated polvinylpyridine groups, permethylated amine groups, mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea groups are disclosed.

Water-soluble polymers and compositions thereof

DOEpatents

Smith, Barbara F.; Robison, Thomas W.; Gohdes, Joel W.

1999-01-01

Water-soluble polymers including functionalization from the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, aza crown ether groups, oxy crown ethers groups, guanidinium groups, amide groups, ester groups, aminodicarboxylic groups, permethylated polyvinylpyridine groups, permethylated amine groups, mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea groups are disclosed.

Antioxidant properties of ferulic acid and its related compounds.

PubMed

Kikuzaki, Hiroe; Hisamoto, Masashi; Hirose, Kanae; Akiyama, Kayo; Taniguchi, Hisaji

2002-03-27

Antioxidant activity of 24 ferulic acid related compounds together with 6 gallic acid related compounds was evaluated using several different physical systems as well as their radical scavenging activity. The radical scavenging activity on 1,1-diphenyl-2-picrylhydrazyl (DPPH) decreased in the order caffeic acid > sinapic acid > ferulic acid > ferulic acid esters > p-coumaric acid. In bulk methyl linoleate, test hydroxycinnamic acids and ferulic acid esters showed antioxidant activity in parallel with their radical scavenging activity. In an ethanol-buffer solution of linoleic acid, the activity of test compounds was not always associated with their radical scavenging activity. Ferulic acid was most effective among the tested phenolic acids. Esterification of ferulic acid resulted in increasing activity. The activity of alkyl ferulates was somewhat influenced by the chain length of alcohol moiety. When the inhibitory effects of alkyl ferulates against oxidation of liposome induced by AAPH were tested, hexyl, octyl, and 2-ethyl-1-hexyl ferulates were more active than the other alkyl ferulates. Furthermore, lauryl gallate is most effective among the tested alkyl gallates. These results indicated that not only the radical scavenging activity of antioxidants, but also their affinity with lipid substrates, might be important factors in their activity.

Site-directed decapsulation of bolaamphiphilic vesicles with enzymatic cleavable surface groups.

PubMed

Popov, Mary; Grinberg, Sarina; Linder, Charles; Waner, Tal; Levi-Hevroni, Bosmat; Deckelbaum, Richard J; Heldman, Eliahu

2012-06-10

Stable nano-sized vesicles with a monolayer encapsulating membrane were prepared from novel bolaamphiphiles with choline ester head groups. The head groups were covalently bound to the alkyl chain of the bolaamphiphiles either via the nitrogen atom of the choline moiety, or via the choline ester's methyl group. Both types of bolaamphiphiles competed with acetylthiocholine for binding to acetylcholine esterase (AChE), yet, only the choline ester head groups bound to the alkyl chain via the nitrogen atom of the choline moiety were hydrolyzed by the enzyme. Likewise, only vesicles composed of bolaamphiphiles with head groups that were hydrolyzed by AChE released their encapsulated material upon exposure to the enzyme. Injection of carboxyfluorescein (CF)-loaded vesicles with cleavable choline ester head groups into mice resulted in the accumulation of CF in tissues that express high AChE activity, including the brain. By comparison, when vesicles with choline ester head groups that are not hydrolyzed by AChE were injected into mice, there was no accumulation of CF in tissues that highly express the enzyme. These results imply that bolaamphiphilic vesicles with surface groups that are substrates to enzymes which are highly expressed in target organs may potentially be used as a drug delivery system with controlled site-directed drug release. Copyright © 2011 Elsevier B.V. All rights reserved.

When alcohol is the answer: Trapping, identifying and quantifying simple alkylating species in aqueous environments.

PubMed

Penketh, Philip G; Shyam, Krishnamurthy; Baumann, Raymond P; Zhu, Rui; Ishiguro, Kimiko; Sartorelli, Alan C; Ratner, Elena S

2016-09-01

Alkylating agents are a significant class of environmental carcinogens as well as commonly used anticancer therapeutics. Traditional alkylating activity assays have utilized the colorimetric reagent 4-(4-nitrobenzyl)pyridine (4NBP). However, 4NBP based assays have a relatively low sensitivity towards harder, more oxophilic alkylating species and are not well suited for the identification of the trapped alkyl moiety due to adduct instability. Herein we describe a method using water as the trapping agent which permits the trapping of simple alkylating electrophiles with a comparatively wide range of softness/hardness and permits the identification of donated simple alkyl moieties. Copyright © 2016 Elsevier Inc. All rights reserved.

High enantiomeric excess of the flavor relevant 4-alkyl-branched Fatty acids in milk fat and subcutaneous adipose tissue of sheep and goat.

PubMed

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

2015-01-21

Volatile 4-alkyl-branched fatty acids are characteristic flavor compounds of sheep and goat. Due to the methyl branch, the carbon C-4 represents a stereogenic center with the possible presence of one or both enantiomers in the respective samples. In this study, we used enantioselective gas chromatography to study the enantiomeric composition of 4-methyloctanoic acid (4-Me-8:0) and 4-ethyloctanoic acid (4-Et-8:0) in milk and dairy products from sheep and goat as well as in goat subcutaneous tissue. Different columns coated with modified cyclodextrins were tested to resolve racemic 4-alkyl-branched fatty acid methyl ester standards. The best enantiomer resolution was obtained on 25% octakis(2,3,6-tri-O-ethyl)-γ-cyclodextrin (γ-TECD) diluted in OV-1701. For analysis of the food samples, the lipids were extracted and fatty acids in the extracts were converted into fatty acid methyl esters. Non-aqueous reversed-phase high-performance liquid chromatography was used to fractionate the samples in order to gain one solution enriched in 4-Me-8:0 methyl ester and one solution enriched with 4-Et-8:0 methyl ester. Subsequent analysis by enantioselective gas chromatography with mass spectrometry allowed only the detection of one enantiomer of 4-Me-8:0 and 4-Et-8:0 in the samples. By means of a non-racemic standard of 4-Me-8:0, it was found that the predominant enantiomer was (R)-4-Me-8:0.

Structure-activity correlations for organophosphorus ester anticholinesterases. Part 2: CNDO/2 calculations applied to ester hydrolysis rates

NASA Technical Reports Server (NTRS)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1984-01-01

Quantitative structure-activity relationships are presented for the hydrolysis of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. CNDO/2 calculations provide values for molecular parameters that correlate with alkaline hydrolysis rates. For each subset of esters with the same leaving group, X, the CNDO-derived net atomic charge at the central phosphorus atom correlates well with the alkaline hydrolysis rate constants. For the whole set of esters with different leaving groups, equations are derived that relate charge, orbital energy and bond order to the hydrolysis rate constants.

Colloidal Properties of Aqueous Fullerenes: Isoelectric Points and Aggregation Kinetics of C60 and C60 Derivatives

EPA Science Inventory

Aqueous colloidal suspensions of C-60 (aqu/C-60) and the C-60 derivatives PCBM ([6,6]-phenyl C-61-butyric acid methyl ester) and the corresponding butyl and octyl esters, PCBB and PCBO (aqu/PCB-R, where R is an alkyl group), were produced by stirring in double deionized water for...

Synergistic cytogenetic and antineoplastic effects by the combined action of esteric steroidal derivatives of nitrogen mustards.

PubMed

Mourelatos, Constantinos; Nikolaropoulos, Sotiris; Fousteris, Manolis; Pairas, Georgios; Argyraki, Maria; Kareli, Dimitra; Dafa, Evaggelia; Mourelatos, Dionisios; Lialiaris, Theodore

2012-06-01

We studied the effect of five newly synthesized steroidal derivatives of nitrogen mustards. These derivatives have as alkylators either P-N, N-bis(2-chloroethyl)aminophenyl-butyrate (CHL) or P-N, N-bis(2-chloroethyl)aminophenyl-acetate (PHE) groups esterified with different modified steroidal nuclei. We examined them alone or in combination, on sister chromatid exchange rates and on human lymphocyte proliferation kinetics. The antitumor activity of these compounds, alone or in combination, was also tested on Leukemia P388-bearing mice. A pronounced cytogenetic and antineoplastic action was demonstrated by the compounds that contain either PHE or CHL as alkylators and are esterified with a steroidal nucleus having added a cholestene group in the 17 position of the D-ring. The exocyclical insertion of an -NHCO- group in the D-ring of the steroidal nucleus esterified with PHE (amide ester of PHE) yielded a compound demonstrating a distinct cytogenetic and antineoplastic effect. In contrast, the ketone group in the D-ring being inserted endocyclically in the steroidal nucleus (androstene) esterified with either CHL or with PHE gave negative cytogenetic and antineoplastic effects. However, the combined action of cholestene esterified with either CHL or with PHE in combination with either the androstene ester of PHE or with the androstene ester of CHL, respectively, gave synergistic cytogenetic and antineoplastic effects. Also the amide ester of PHE in combination with the androstene ester of CHL gave distinct cytogenetic and antineoplastic effects in a synergistic manner.

Stereospecific nickel-catalyzed cross-coupling reactions of benzylic ethers and esters.

PubMed

Tollefson, Emily J; Hanna, Luke E; Jarvo, Elizabeth R

2015-08-18

This Account presents the development of a suite of stereospecific alkyl-alkyl cross-coupling reactions employing nickel catalysts. Our reactions complement related nickel-catalyzed stereoconvergent cross-coupling reactions from a stereochemical and mechanistic perspective. Most reactions of alkyl electrophiles with low-valent nickel complexes proceed through alkyl radicals and thus are stereoablative; the correct enantioselective catalyst can favor the formation of one enantiomer. Our reactions, in contrast, are stereospecific. Enantioenriched ethers and esters are cleanly converted to cross-coupled products with high stereochemical fidelity. While mechanistic details are still to be refined, our results are consistent with a polar, two-electron oxidative addition that avoids the formation of radical intermediates. This reactivity is unusual for a first-row transition metal. The cross-coupling reactions engage a range of benzylic ethers and esters, including methyl ethers, tetrahydropyrans, tetrahydrofurans, esters, and lactones. Coordination of the arene substituent to the nickel catalyst accelerates the reactions. Arenes with low aromatic stabilization energies, such as naphthalene, benzothiophene, and furan, serve as the best ligands and provide the highest reactivity. Traceless directing groups that accelerate reactions of sluggish substrates are described, providing partial compensation for arene coordination. Kumada, Negishi, and Suzuki reactions provide incorporation of a broad range of transmetalating agents. In Kumada coupling reactions, a full complement of Grigard reagents, including methyl, n-alkyl, and aryl Grignard reagents, are employed. In reactions employing methylmagnesium iodide, ligation of the nickel catalyst by rac-BINAP or DPEphos provides the highest yield and stereospecificity. For all other Grignard reagents, Ni(dppe)Cl2 has emerged as the best catalyst. Negishi cross-coupling reactions employing dimethylzinc are reported as a strategy to increase the functional group tolerance of the reaction. We also describe Suzuki reactions using arylboronic esters. These reactions provided the first example in the series of a switch in stereochemical outcome. The reactions maintain stereospecificity, but reactions employing different achiral ligands provide opposite enantiomers of the product. Use of an N-heterocyclic carbene ligand, SIMes, provides inversion, consistent with our prior work in Kumada and Negishi coupling reactions. Use of the electron-rich phosphine PCy3, however, provides retention with stereospecificity, signaling a change in the mechanistic details. Potential applications of the reported cross-coupling reactions include the synthesis of medicinal agents containing the 2-arylalkane and 1,1-diarylalkane moieties, which are pharmacophores in medicinal chemistry. These moieties are found in compounds with activity against a broad range of indications, including cancer, heart disease, diabetes, osteoporosis, smallpox, tuberculosis, and insomnia. We highlight representative examples of bioactive compounds that we have prepared with high enantioselectivity employing our methods, as well as the discovery of a new anti-cancer agent.

The moss Funaria hygrometrica has cuticular wax similar to vascular plants, with distinct composition on leafy gametophyte, calyptra and sporophyte capsule surfaces.

PubMed

Busta, Lucas; Budke, Jessica M; Jetter, Reinhard

2016-09-01

Aerial surfaces of land plants are covered with a waxy cuticle to protect against water loss. The amount and composition of cuticular waxes on moss surfaces had rarely been investigated. Accordingly, the degree of similarity between moss and vascular plant waxes, and between maternal and offspring moss structure waxes is unknown. To resolve these issues, this study aimed at providing a comprehensive analysis of the waxes on the leafy gametophyte, gametophyte calyptra and sporophyte capsule of the moss Funaria hygrometrica Waxes were extracted from the surfaces of leafy gametophytes, gametophyte calyptrae and sporophyte capsules, separated by gas chromatography, identified qualitatively with mass spectrometry, and quantified with flame ionization detection. Diagnostic mass spectral peaks were used to determine the isomer composition of wax esters. The surfaces of the leafy gametophyte, calyptra and sporophyte capsule of F. hygrometrica were covered with 0·94, 2·0 and 0·44 μg cm(-2) wax, respectively. While each wax mixture was composed of mainly fatty acid alkyl esters, the waxes from maternal and offspring structures had unique compositional markers. β-Hydroxy fatty acid alkyl esters were limited to the leafy gametophyte and calyptra, while alkanes, aldehydes and diol esters were restricted to the sporophyte capsule. Ubiquitous fatty acids, alcohols, fatty acid alkyl esters, aldehydes and alkanes were all found on at least one surface. This is the first study to determine wax coverage (μg cm(-2)) on a moss surface, enabling direct comparisons with vascular plants, which were shown to have an equal amount or more wax than F. hygrometrica Wax ester biosynthesis is of particular importance in this species, and the ester-forming enzyme(s) in different parts of the moss may have different substrate preferences. Furthermore, the alkane-forming wax biosynthesis pathway, found widely in vascular plants, is active in the sporophyte capsule, but not in the leafy gametophyte or calyptra. Overall, wax composition and coverage on F. hygrometrica were similar to those reported for some vascular plant species, suggesting that the underlying biosynthetic processes in plants of both lineages were inherited from a common ancestor. © The Author 2016. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

A novel continuous flow biosynthesis of caffeic acid phenethyl ester from alkyl caffeate and phenethanol in a packed bed microreactor.

PubMed

Wang, Jun; Gu, Shuang-Shuang; Cui, Hong-Sheng; Wu, Xiang-Yang; Wu, Fu-An

2014-04-01

Caffeic acid phenethyl ester (CAPE) is a rare natural ingredient with several biological activity, but the industrial production of CAPE using lipase-catalyzed esterification of caffeic acid (CA) and 2-phenylethanol (PE) in ionic liquids is hindered by low substrate concentrations and a long reaction time. To establish a high-efficiency bioprocess for obtaining CAPE, a novel continuous flow biosynthesis of CAPE from alkyl caffeate and PE in [Bmim][Tf2N] using a packed bed microreactor was successfully carried out. Among the tested alkyl caffeates and lipases, methyl caffeate and Novozym 435, respectively, were selected as the suitable substrate and biocatalyst. Under the optimum conditions selected using response surface methodology, a 93.21% CAPE yield was achieved in 2.5h using a packed bed microreactor, compared to 24h using a batch reactor. The reuse of Novozym 435 for 20 cycles and continuous reaction for 9 days did not result in any decrease in activity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Enhanced antiamyloidal activity of hydroxy cinnamic acids by enzymatic esterification with alkyl alcohols.

PubMed

Kondo, Hazuki; Sugiyama, Haruka; Katayama, Shigeru; Nakamura, Soichiro

2014-01-01

Lipophilic derivatives of hydroxyl cinnamic acids (HCAs) including caffeic acid (CA), ferulic acid, sinapic acid (SA), and chlorogenic acid were synthesized by esterification with butanol, octanol, or hexadecanol catalyzed by the lipase from Candida antarctica to investigate the effect of lipophilicity on their antiamyloidal activity assessed by the inhibitory activities toward fibrillization of amyloid β (Aβ) peptide. Among them, CA showed the highest activity at 50 μM, reducing the amyloid fibril formation of Aβ to 34.4 ± 6.8%. The antiamyloidal effects of HCAs were enhanced by esterification with alkyl alcohols, and the longer alkyl chain tended to be more effective except for SA. Aβ fibril formation was suppressed by the hexadecyl ester of CA, which was reduced to 8.8 ± 2.3%. In contrast, those of octyl and butyl esters were 19.3 ± 2.3% and 41.6 ± 6.1%, respectively. These results show that lipophilicity plays an important role in the antiamyloidal activities of esterified phenolic compounds. © 2013 International Union of Biochemistry and Molecular Biology, Inc.

From conventional towards new - natural surfactants in drug delivery systems design: current status and perspectives.

PubMed

Savić, Snezana; Tamburić, Slobodanka; Savić, Miroslav M

2010-03-01

Surfactants play an important role in the development of both conventional and advanced (colloidal) drug delivery systems. There are several commercial surfactants, but a proportionally small group of them is approved as pharmaceutical excipients, recognized in various pharmacopoeias and therefore widely accepted by the pharmaceutical industry. The review covers some of the main categories of natural, sugar-based surfactants (alkyl polyglucosides and sugar esters) as prospective pharmaceutical excipients. It provides analysis of the physicochemical characteristics of sugar-based surfactants and their possible roles in the design of conventional or advanced drug delivery systems for different routes of administration. Summary and analysis of recent data on functionality, applied concentrations and formulation improvements produced by alkyl polyglucosides and sugar esters in different conventional and advanced delivery systems could be of interest to researchers dealing with drug formulation. Recent FDA certification of an alkyl polyglucoside surfactant for topical formulation presents a significant step in the process of recognition of this relatively new group of surfactants. This could trigger further research into the potential benefits of naturally derived materials in both conventional and new drug delivery systems.

40 CFR 80.1101 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) Dedicated energy crops and trees. (ii) Wood and wood residues. (iii) Plants. (iv) Grasses. (v) Agricultural... the calendar year) does not exceed 75,000 barrels. (h) Biodiesel (mono-alkyl ester) means a motor...

40 CFR 80.1101 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) Dedicated energy crops and trees. (ii) Wood and wood residues. (iii) Plants. (iv) Grasses. (v) Agricultural... the calendar year) does not exceed 75,000 barrels. (h) Biodiesel (mono-alkyl ester) means a motor...

Detection of Alkylating Agents using Electrical and Mechanical Means

NASA Astrophysics Data System (ADS)

Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Tal, Shay; Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir; Eichen, Yoav

2011-08-01

Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

Occurrence of fatty acid short-chain-alkyl esters in fruits of Celastraceae plants.

PubMed

Sidorov, Roman A; Zhukov, Anatoly V; Pchelkin, Vasily P; Vereshchagin, Andrei G; Tsydendambaev, Vladimir D

2013-06-01

Small amounts of a mixture of fatty acid short-chain-alkyl esters (FASCAEs) were obtained from the fruits of twelve plant species of Celastraceae family, and in five of them the FASCAEs were present not only in the arils but also in the seeds. These mixtures contained 32 individual FASCAE species, which formed four separate fractions, viz. FA methyl, ethyl, isopropyl, and butyl esters (FAMEs, FAEEs, FAIPEs, and FABEs, resp.). The FASCAE acyl components included the residues of 16 individual C₁₄-C₂₄ saturated, mono-, di-, and trienoic FAs. Linoleic, oleic, and palmitic acids, and, in some cases, also α-linolenic acid predominated in FAMEs and FAEEs, while myristic acid was predominant in FAIPEs. It can be suggested that, in the fruit arils of some plant species, FAMEs and FAEEs were formed at the expense of a same FA pool characteristic of a given species and were strongly different from FAIPEs and FABEs esters regarding the mechanism of their biosynthesis. However, as a whole, the qualitative and quantitative composition of various FASCAE fractions, as well as their FA composition, varied considerably depending on various factors. Therefore, separate FASCAE fractions seem to be synthesized from different FA pools other than those used for triacylglycerol formation. Copyright © 2013 Verlag Helvetica Chimica Acta AG, Zürich.

40 CFR 79.56 - Fuel and fuel additive grouping system.

Code of Federal Regulations, 2012 CFR

2012-07-01

...; mixed alkyl esters of plant and/or animal origin (biodiesel). For each such group, the representative to... following concentration: (A) For biodiesel groups, the representative shall be 100 percent biodiesel fuel...

40 CFR 79.56 - Fuel and fuel additive grouping system.

Code of Federal Regulations, 2013 CFR

2013-07-01

...; mixed alkyl esters of plant and/or animal origin (biodiesel). For each such group, the representative to... following concentration: (A) For biodiesel groups, the representative shall be 100 percent biodiesel fuel...

40 CFR 79.56 - Fuel and fuel additive grouping system.

Code of Federal Regulations, 2011 CFR

2011-07-01

...; mixed alkyl esters of plant and/or animal origin (biodiesel). For each such group, the representative to... following concentration: (A) For biodiesel groups, the representative shall be 100 percent biodiesel fuel...

40 CFR 79.56 - Fuel and fuel additive grouping system.

Code of Federal Regulations, 2014 CFR

2014-07-01

...; mixed alkyl esters of plant and/or animal origin (biodiesel). For each such group, the representative to... following concentration: (A) For biodiesel groups, the representative shall be 100 percent biodiesel fuel...

Palladium-Catalyzed Dynamic Kinetic Asymmetric Transformations of Vinyl Aziridines with Nitrogen Heterocycles: Rapid Access to Biologically Active Pyrroles and Indoles

PubMed Central

Trost, Barry M.; Osipov, Maksim; Dong, Guangbin

2010-01-01

We report that nitrogen heterocycles can serve as competent nucleophiles in the palladium-catalyzed dynamic kinetic asymmetric alkylation of vinyl aziridines. The resulting alkylated products were obtained with high regio-, chemo-, and enantioselectivity. Both substituted 1H-pyrroles and 1H-indoles were successfully employed to give exclusively the branched N-alkylated products. The synthetic utility of this process was demonstrated by applying this method to the preparation of several medicinal chemistry lead compounds and bromopyrrole alkaloids including longamide B, longamide B methyl ester, hanishin, agesamides A and B, and cyclooroidin. PMID:20949972

Gallic acid-based alkyl esters synthesis in a water-free system by celite-bound lipase of Bacillus licheniformis SCD11501.

PubMed

Sharma, Shivika; Kanwar, Shamsher S; Dogra, Priyanka; Chauhan, Ghanshyam S

2015-01-01

Gallic acid (3, 4, 5- trihydroxybenzoic acid) is an important antioxidant, anti-inflammatory, and radical scavenging agent. In the present study, a purified thermo-tolerant extra-cellular lipase of Bacillus licheniformis SCD11501 was successfully immobilized by adsorption on Celite 545 gel matrix followed by treatment with a cross-linking agent, glutaraldehyde. The celite-bound lipase treated with glutaraldehyde showed 94.8% binding/retention of enzyme activity (36 U/g; specific activity 16.8 U/g matrix; relative increase in enzyme activity 64.7%) while untreated matrix resulted in 88.1% binding/retention (28.0 U/g matrix; specific activity 8.5 U/g matrix) of lipase. The celite-bound lipase was successfully used to synthesis methyl gallate (58.2%), ethyl gallate (66.9%), n-propyl gallate (72.1%), and n-butyl gallate (63.8%) at 55(o) C in 10 h under shaking (150 g) in a water-free system by sequentially optimizing various reaction parameters. The low conversion of more polar alcohols such as methanol and ethanol into their respective gallate esters might be due to the ability of these alcohols to severely remove water from the protein hydration shell, leading to enzyme inactivation. Molecular sieves added to the reaction mixture resulted in enhanced yield of the alkyl ester(s). The characterization of synthesised esters was done through fourier transform infrared (FTIR) spectroscopy and (1) H NMR spectrum analysis. © 2015 American Institute of Chemical Engineers.

Aryl sulfonate based anticancer alkylating agents.

PubMed

Sheikh, Hamdullah Khadim; Arshad, Tanzila; Kanwal, Ghazala

2018-05-01

This research work revolves around synthesis of antineoplastic alkylating sulfonate esters with dual alkylating sites for crosslinking of the DNA strands. These molecules were evaluated as potential antineoplastic cross linking alkylating agents by reaction with the nucleoside of Guanine DNA nucleobase at both ends of the synthesized molecule. Synthesis of the alkylating molecules and the crosslinking with the guanosine nucleoside was monitored by MALDITOF mass spectroscopy. The synthesized molecule's crosslinking or adduct forming rate with the nucleoside was compared with that of 1,4 butane disulfonate (busulfan), in form of time taken for the appearance of [M+H] + . It was found that aryl sulfonate leaving group was causing higher rate of nucleophilic attack by the Lewis basic site of the nucleobase. Furthermore, the rate was also found to be a function of electron withdrawing or donating nature of the substituent on the aryl ring. Compound with strong electron withdrawing substituent on the para position of the ring reacted fastest. Hence, new alkylating agents were synthesized with optimized or desired reactivity.

Mycobacterium tuberculosis Rv3406 Is a Type II Alkyl Sulfatase Capable of Sulfate Scavenging

PubMed Central

Sogi, Kimberly M.; Gartner, Zev J.; Breidenbach, Mark A.; Appel, Mason J.; Schelle, Michael W.; Bertozzi, Carolyn R.

2013-01-01

The genome of Mycobacterium tuberculosis (Mtb) encodes nine putative sulfatases, none of which have a known function or substrate. Here, we characterize Mtb’s single putative type II sulfatase, Rv3406, as a non-heme iron (II) and α-ketoglutarate-dependent dioxygenase that catalyzes the oxidation and subsequent cleavage of alkyl sulfate esters. Rv3406 was identified based on its homology to the alkyl sulfatase AtsK from Pseudomonas putida. Using an in vitro biochemical assay, we confirmed that Rv3406 is a sulfatase with a preference for alkyl sulfate substrates similar to those processed by AtsK. We determined the crystal structure of the apo Rv3406 sulfatase at 2.5 Å. The active site residues of Rv3406 and AtsK are essentially superimposable, suggesting that the two sulfatases share the same catalytic mechanism. Finally, we generated an Rv3406 mutant (Δrv3406) in Mtb to study the sulfatase’s role in sulfate scavenging. The Δrv3406 strain did not replicate in minimal media with 2-ethyl hexyl sulfate as the sole sulfur source, in contrast to wild type Mtb or the complemented strain. We conclude that Rv3406 is an iron and α-ketoglutarate-dependent sulfate ester dioxygenase that has unique substrate specificity that is likely distinct from other Mtb sulfatases. PMID:23762287

Abiotic Organic Chemistry in Hydrothermal Systems.

NASA Astrophysics Data System (ADS)

Simoneit, B. R.; Rushdi, A. I.

2004-12-01

Abiotic organic chemistry in hydrothermal systems is of interest to biologists, geochemists and oceanographers. This chemistry consists of thermal alteration of organic matter and minor prebiotic synthesis of organic compounds. Thermal alteration has been extensively documented to yield petroleum and heavy bitumen products from contemporary organic detritus. Carbon dioxide, carbon monoxide, ammonia and sulfur species have been used as precursors in prebiotic synthesis experiments to organic compounds. These inorganic species are common components of hot spring gases and marine hydrothermal systems. It is of interest to further test their reactivities in reductive aqueous thermolysis. We have synthesized organic compounds (lipids) in aqueous solutions of oxalic acid, and with carbon disulfide or ammonium bicarbonate at temperatures from 175-400° C. The synthetic lipids from oxalic acid solutions consisted of n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, n-alkenes and n-alkanes, typically to C30 with no carbon number preferences. The products from CS2 in acidic aqueous solutions yielded cyclic thioalkanes, alkyl polysulfides, and thioesters with other numerous minor compounds. The synthesis products from oxalic acid and ammonium bicarbonate solutions were homologous series of n-alkyl amides, n-alkyl amines, n-alkanes and n-alkanoic acids, also to C30 with no carbon number predominance. Condensation (dehydration) reactions also occur under elevated temperatures in aqueous medium as tested by model reactions to form amide, ester and nitrile bonds. It is concluded that the abiotic formation of aliphatic lipids, condensation products (amides, esters, nitriles, and CS2 derivatives (alkyl polysulfides, cyclic polysulfides) is possible under hydrothermal conditions and warrants further studies.

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

NASA Technical Reports Server (NTRS)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1985-01-01

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis. [quantitative structure-activity relationship, complete neglect of differential overlap

NASA Technical Reports Server (NTRS)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1985-01-01

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of cationic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR-primeP(O)X, where R and R-prime are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrolysis rate constant.

Purification and Characterization of an Inverting Stereo- and Enantioselective sec-Alkylsulfatase from the Gram-Positive Bacterium Rhodococcus ruber DSM 44541

PubMed Central

Pogorevc, Mateja; Faber, Kurt

2003-01-01

Whole cells of Rhodococcus ruber DSM 44541 were found to hydrolyze (±)-2-octyl sulfate in a stereo- and enantiospecific fashion. When growing on a complex medium, the cells produced two sec-alkylsulfatases and (at least) one prim-alkylsulfatase in the absence of an inducer, such as a sec-alkyl sulfate or a sec-alcohol. From the crude cell-free lysate, two proteins responsible for sulfate ester hydrolysis (designated RS1 and RS2) were separated from each other based on their different hydrophobicities and were subjected to further chromatographic purification. In contrast to sulfatase RS1, enzyme RS2 proved to be reasonably stable and thus could be purified to homogeneity. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis revealed a single band at a molecular mass of 43 kDa. Maximal enzyme activity was observed at 30°C and at pH 7.5. Sulfatase RS2 showed a clear preference for the hydrolysis of linear secondary alkyl sulfates, such as 2-, 3-, or 4-octyl sulfate, with remarkable enantioselectivity (an enantiomeric ratio of up to 21 [23]). Enzymatic hydrolysis of (R)-2-octyl sulfate furnished (S)-2-octanol without racemization, which revealed that the enzymatic hydrolysis proceeded through inversion of the configuration at the stereogenic carbon atom. Screening of a broad palette of potential substrates showed that the enzyme exhibited limited substrate tolerance; while simple linear sec-alkyl sulfates (C7 to C10) were freely accepted, no activity was found with branched and mixed aryl-alkyl sec-sulfates. Due to the fact that prim-sulfates were not accepted, the enzyme was classified as sec-alkylsulfatase (EC 3.1.6.X). PMID:12732552

Convenient synthesis of 6-nor-9,10-dihydrolysergic acid methyl ester.

PubMed

Crider, A M; Grubb, R; Bachmann, K A; Rawat, A K

1981-12-01

6-Nor-9,10-dihydrolysergic acid methyl ester (IV) was prepared by demethylation of 9,10-dihydrolysergic acid methyl ester (II) with 2,2,2-trichloroethyl chloroformate, followed by reduction of the intermediate carbamate (III) with zinc in acetic acid. The 6-ethyl-V and 6-n-propyl-VI derivatives were prepared by alkylation of IV with the appropriate halide. All of the ergoline derivatives were evaluated for stereotyped behavior in rats, with 6-nor-6-ethyl-9,10-dihydrolysergic acid methyl ester (V) being active but much less potent than apomorphine. Compound VI was evaluated for its effect on blood pressure; at a dose of 30 mg/kg ip, it significantly lowered, diastolic pressure in normotensive rats.

Synthesis of acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

DOEpatents

Moens, Luc

2003-06-24

A process of preparing an acid addition salt of delta-aminolevulinc acid comprising: a) dissolving a lower alkyl 5-bromolevulinate and hexamethylenetetramine in a solvent selected from the group consisting of water, ethyl acetate, chloroform, acetone, ethanol, tetrahydrofuran and acetonitrile, to form a quaternary ammonium salt of the lower alkyl 5-bromolevulinate; and b) hydrolyzing the quaternary ammonium salt with an inorganic acid to form an acid addition salt of delta-aminolevulinic acid.

Biodiesel production from Jatropha oil by catalytic and non-catalytic approaches: an overview.

PubMed

Juan, Joon Ching; Kartika, Damayani Agung; Wu, Ta Yeong; Hin, Taufiq-Yap Yun

2011-01-01

Biodiesel (fatty acids alkyl esters) is a promising alternative fuel to replace petroleum-based diesel that is obtained from renewable sources such as vegetable oil, animal fat and waste cooking oil. Vegetable oils are more suitable source for biodiesel production compared to animal fats and waste cooking since they are renewable in nature. However, there is a concern that biodiesel production from vegetable oil would disturb the food market. Oil from Jatropha curcas is an acceptable choice for biodiesel production because it is non-edible and can be easily grown in a harsh environment. Moreover, alkyl esters of jatropha oil meet the standard of biodiesel in many countries. Thus, the present paper provides a review on the transesterification methods for biodiesel production using jatropha oil as feedstock. Crown Copyright © 2010. Published by Elsevier Ltd. All rights reserved.

Photooxidation of mixed aryl and biarylphosphines.

PubMed

Zhang, Dong; Celaje, Jeff A; Agua, Alon; Doan, Chad; Stewart, Timothy; Bau, Robert; Selke, Matthias

2010-07-02

Arylphosphines and dialkylbiarylphosphines react with singlet oxygen to form phosphine oxides and phosphinate esters. For mixed arylphosphines, the most electron-rich aryl group migrates to form the phosphinate, while for dialkylbiarylphosphines migration of the alkyl group occurs. Dialkylbiarylphosphines also yield arene epoxides, especially in electron-rich systems. Phosphinate ester formation is increased at high temperature, while protic solvents increase the yield of epoxide. The product distribution provides evidence for Buchwald's recent conformational model for the aerobic oxidation of dialkylbiarylphosphines.

Thermochemical Concrete Pavement Scaling Mechanism: Navy F/A-18 Jet Aircraft Parking Apron Problem

DTIC Science & Technology

1998-06-01

boiling and recondensation) in hot, concentrated potassium hydroxide (E): Eqn 11 Alkaline Hydrolysis of Esters with Potassium Hydroxide KOH...RC02R’ -> KC02R + R’OH potassium alkyl ester (B) potassium ethanol(L) hydroxide (E) carboxylate (F) The overall reaction appears to make sense...carbonate (H) water 2. The parallel between calcium hydroxide and potassium hydroxide is not very accurate. Potassium hydroxide is a much stronger alkali

Enantioseparation and optical rotation of flavor-relevant 4-alkyl-branched fatty acids.

PubMed

Eibler, Dorothee; Vetter, Walter

2017-07-07

Short chain 4-alkyl-branched fatty acids are character impact compounds of the flavor of sheep and goat milk and meat. Due to their methyl or ethyl branches these volatile fatty acids are chiral, and both enantiomers are characterized by different aroma intensities. Recently, it was found that 4-methyloctanoic acid (4-Me-8:0), 4-ethyloctanoic acid (4-Et-8:0), and 4-methylnonanoic acid (4-Me-9:0) are enantiopure in goat and sheep samples, if present. Here we generated enantiopure or enantioenriched standards from racemates by means of (R)-selective esterification with lipase B and verified that 4-Me-8:0, 4-Et-8:0 and 4-Me-9:0 were (R)-enantiopure in these tissues. Determination of the optical rotation and [α] D value was carried out to show that (R)-4-Et-8:0 is dextrorotary and to verify the literature values of (R)-4-methyl-branched fatty acids. The elution order of free acids and the methyl and ethyl esters of 4-Me-8:0, 4-Et-8:0, 4-Me-9:0 and 4-methylhexanoic acid (4-Me-6:0) enantiomers was investigated on different chiral columns as well as the (-)-menthyl ester by indirect enantiomer separation on an ionic liquid phase. Different chiral recognition processes were suggested for free acid and esters of 4-Me-8:0 and 4-Me-9:0 on the one hand (decisive: 4-alkyl branch) compared to 4-Me-6:0 on the other hand (decisive: branch on antepenultimate carbon). Copyright © 2017 Elsevier B.V. All rights reserved.

The amphiphilic alkyl ester derivatives of l-ascorbic acid induce reorganization of phospholipid vesicles.

PubMed

Giudice, Francesca; Ambroggio, Ernesto E; Mottola, Milagro; Fanani, Maria Laura

2016-09-01

l-ascorbic acid alkyl esters (ASCn) are lipophilic forms of vitamin C, which maintain some of its antioxidant power. Those properties make this drug family attractive to be used in pharmacological preparations protecting other redox-sensible drugs or designed to reduce possible toxic oxidative processes. In this work, we tested the ability of l-ascorbic acid alkyl esters (ASCn) to modulate the structure, permeability, and rheological properties of phospholipid bilayers. The ASCn studied here (ASC16, ASC14, and ASC12) alter the structural integrity as well as the rheological properties of phospholipid membranes without showing any evident detergent activity. ASC14 appeared as the most efficient drug in destabilize the membrane structure of nano- and micro-size phospholipid liposomes inducing vesicle content leakage and shape elongation on giant unilamellar vesicles. It also was the most potent enhancer of membrane microviscosity and surface water structuring. Only ASC16 induced the formation of drug-enriched condensed domains after its incorporation into the lipid bilayer, while ASC12 appeared as the less membrane-disturbing compound, likely because of its poor, and more superficial, partition into the membrane. We also found that incorporation of ASCn into the lipid bilayers enhanced the reduction of membrane components, compared with soluble vitamin C. Our study shows that ASCn compounds, which vary in the length of the acyl chain, show different effects on phospholipid vesicles used as biomembrane models. Those variances may account for subtly differences in the effectiveness on their pharmacological applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Alternative Fuels Data Center: Renewable Hydrocarbon Biofuels

Science.gov Websites

, biodiesel is a mono-alkyl ester, which has different physical properties and hence different fuel specifications (ASTM D6751 and EN 14214). The two fuels are also produced through very different processes. While

Application of AlkBGT and AlkL from Pseudomonas putida GPo1 for Selective Alkyl Ester ω-Oxyfunctionalization in Escherichia coli

PubMed Central

Eggink, Gerrit; Weusthuis, Ruud A.

2016-01-01

ABSTRACT The enzyme system AlkBGT from Pseudomonas putida GPo1 can efficiently ω-functionalize fatty acid methyl esters. Outer membrane protein AlkL boosts this ω-functionalization. In this report, it is shown that whole cells of Escherichia coli expressing the AlkBGT system can also ω-oxidize ethyl nonanoate (NAEE). Coexpression of AlkBGT and AlkL resulted in 1.7-fold-higher ω-oxidation activity on NAEE. With this strain, initial activity on NAEE was 70 U/g (dry weight) of cells (gcdw), 67% of the initial activity on methyl nonanoate. In time-lapse conversions with 5 mM NAEE the main product was 9-hydroxy NAEE (3.6 mM), but also 9-oxo NAEE (0.1 mM) and 9-carboxy NAEE (0.6 mM) were formed. AlkBGT also ω-oxidized ethyl, propyl, and butyl esters of fatty acids ranging from C6 to C10. Increasing the length of the alkyl chain improved the ω-oxidation activity of AlkBGT on esters of C6 and C7 fatty acids. From these esters, application of butyl hexanoate resulted in the highest ω-oxidation activity, 82 U/gcdw. Coexpression of AlkL only had a positive effect on ω-functionalization of substrates with a total length of C11 or longer. These findings indicate that AlkBGT(L) can be applied as a biocatalyst for ω-functionalization of ethyl, propyl, and butyl esters of medium-chain fatty acids. IMPORTANCE Fatty acid esters are promising renewable starting materials for the production of ω-hydroxy fatty acid esters (ω-HFAEs). ω-HFAEs can be used to produce sustainable polymers. Chemical conversion of the fatty acid esters to ω-HFAEs is challenging, as it generates by-products and needs harsh reaction conditions. Biocatalytic production is a promising alternative. In this study, biocatalytic conversion of fatty acid esters toward ω-HFAEs was investigated using whole cells. This was achieved with recombinant Escherichia coli cells that produce the AlkBGT enzymes. These enzymes can produce ω-HFAEs from a wide variety of fatty acid esters. Medium-chain-length acids (C6 to C10) esterified with ethanol, propanol, or butanol were applied. This is a promising production platform for polymer building blocks that uses renewable substrates and mild reaction conditions. PMID:27084021

Copper-Catalyzed Oxidative Dehydrogenative Carboxylation of Unactivated Alkanes to Allylic Esters via Alkenes

PubMed Central

2015-01-01

We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV–vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C–H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C–H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper–carboxylate, copper–amidate, and copper–imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)–amidate > Cu(II)–imidate > Cu(II)–benzoate. Consistent with this trend, Cu(II)–amidates and Cu(II)–benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products. PMID:25389772

Tandem Carbocupration/Oxygenation of Terminal Alkynes

PubMed Central

Zhang, Donghui; Ready, Joseph M.

2008-01-01

A direct and general synthesis of α-branched aldehydes and their enol derivatives is described. Carbocupration of terminal alkynes and subsequent oxygenation with lithium tert-butyl peroxide generates a metallo-enolate. Trapping with various electrophiles provides α-branched aldehydes or stereo-defined trisubstituted enol esters or silyl ethers. The tandem carbocupration/oxygenation tolerates alkyl and silyl ethers, esters and tertiary amines. The reaction is effective with organocopper complexes derived from primary, secondary and tertiary Grignard reagents and from n-butyllithium. PMID:16321021

Photooxidation of Mixed Aryl and Biarylphosphines

PubMed Central

Zhang, Dong; Celaje, Jeff A.; Agua, Alon; Doan, Chad; Stewart, Timothy; Bau, Robert; Selke, Matthias

2010-01-01

Aryl phosphines and dialkylbiaryl phosphines react with singlet oxygen to form phosphinate esters. For mixed arylphosphines, the most electron-rich aryl group migrates to form the phosphinate, while for dialkylbiaryl phosphines migration of the alkyl group occurs. Dialkylbiaryl phosphines also yield arene epoxides, especially in electron rich systems. Phosphinate ester formation is increased at high temperature while protic solvents increase the yield of epoxide. The product distribution provides evidence for Buchwald’s recent conformational model for the aerobic oxidation of dialkylbiaryl phosphines. PMID:20527907

Steric effects on diffusion into bituminous coals

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

John W. Larsen; Doyoung Lee

2006-02-01

The reactions of maleic anhydride, cis-maleate esters, and acetylenedicarboxylate esters with Pittsburgh No. 8 or Illinois No. 6 coal using o-xylene or o-dichlorobenzene solvent are diffusion controlled. Diffusion is Fickian in all cases. The measured activation energies are between 5.4 and 7.6 kcal/mol. Diffusion rates decrease slowly with increasing alkyl chain length and sharply with branching. Diffusion rates are slightly faster with o-xylene than when o-dichlorobenzene is used. 40 refs., 5 figs., 4 tabs.

Detection and identification of alkylating agents by using a bioinspired "chemical nose".

PubMed

Hertzog-Ronen, Carmit; Borzin, Elena; Gerchikov, Yulia; Tessler, Nir; Eichen, Yoav

2009-10-12

Alkylating agents are simple and reactive molecules that are commonly used in many and diverse fields such as organic synthesis, medicine, and agriculture. Some highly reactive alkylating species are also being used as blister chemical-warfare agents. The detection and identification of alkylating agents is not a trivial issue because of their high reactivity and simple structure. Herein, we report on a new multispot luminescence-based approach to the detection and identification of alkylating agents. In order to demonstrate the potential of the approach, seven pi-conjugated oligomers and polymers bearing nucleophilic pyridine groups, 1-7, were adsorbed onto a solid support and exposed to vapors of alkylators 8-15. The alkylation-induced color-shift patterns of the seven-spot array allow clear discrimination of the different alkylators. The spots are sensitive to minute concentrations of alkylators and, because the detection is based on the formation of new covalent bonds, these spots saturate at about 50 ppb.

Engineering acyclic stereocontrol in the alkylation of vinylglycine-derived dianions: asymmetric synthesis of higher alpha-vinyl amino acids.

PubMed

Berkowitz, D B; McFadden, J M; Sloss, M K

2000-05-19

A generalizable synthesis of higher L-alpha-vinyl amino acids is presented. The strategy pursued here involves the introduction of the amino acid side chain via the alkylation of a chiral, vinylglycine-derived dianionic dienolate, bearing the (-)-8-(beta-naphthyl)menthyl (d'Angelo) auxiliary. A model is presented that postulates a favored "exo-entended" conformation for this dienolate, leading to C(alpha)-alkylation at the si face. The model invokes internal amidate chelation to control ester enolate geometry and soft-soft interactions between the polarizable beta-naphthyl ring of the auxiliary and the extended pi-system of the dienolate to shield the re face. Heats of formation for four conformers of this dianion were calculated for their semiempirical optimized geometries (PM3). The results support the notion that in these vinylglycine-derived dianionic dienolates, "exo" conformations are considerable lower in energy than their "endo" counterparts, with the "exo-entended" conformation being most favorable. In fact, the d'Angelo auxiliary gives a greater degree of acyclic stereocontrol in this system when compared with the (-)-8-phenylmenthyl (Corey) and trans-2-(beta-naphthyl)cyclohexyl auxiliaries, using isobutyl iodide and benzyl bromide as model electrophiles. These dianions are generated from the corresponding dehydrobutyrine esters via sequential deprotonation with LDA and n-BuLi (2 equiv). When alkylations are carried out at -78 degrees C in THF-HMPA, they proceed in 65-81% yields, with both regiocontrol (deconjugative alpha-alkylation is preferred over gamma-alkylation) and a great degree of acyclic stereocontrol [91:9 to >/=98:2 diastereomeric ratios (10 examples)]. The auxiliary may be recovered in high yield (generally 90%) using a modification of Gassman's "anhydrous hydroxide" conditions, in which considerably higher temperatures are employed. Among the side chains introduced directly are those of butyrine, leucine, ornithine, phenylalanine, aspartate, valine, and norvaline. The lysine side chain is elaborated via a 4-step sequence from the alkylation product obtained with 1-chloro-4-iodobutane as electrophile. Importantly, to our knowledge, this work represents the first asymmetric synthesis of L-alpha-vinyl analogues of m-tyrosine, ornithine, and lysine, known time-dependent inhibitors for amino acid decarboxylases.

7 CFR 1424.3 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-01-01

..., Firearms, and Explosives of the United States Department of Justice. Base production means a biodiesel producer's current FY's biodiesel production from eligible commodities that is not an increase over biodiesel production in the previous FY to date. Biodiesel means a mono alkyl ester manufactured in the...

7 CFR 1424.3 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-01-01

..., Firearms, and Explosives of the United States Department of Justice. Base production means a biodiesel producer's current FY's biodiesel production from eligible commodities that is not an increase over biodiesel production in the previous FY to date. Biodiesel means a mono alkyl ester manufactured in the...

7 CFR 1424.3 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-01-01

..., Firearms, and Explosives of the United States Department of Justice. Base production means a biodiesel producer's current FY's biodiesel production from eligible commodities that is not an increase over biodiesel production in the previous FY to date. Biodiesel means a mono alkyl ester manufactured in the...

7 CFR 1424.3 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-01-01

..., Firearms, and Explosives of the United States Department of Justice. Base production means a biodiesel producer's current FY's biodiesel production from eligible commodities that is not an increase over biodiesel production in the previous FY to date. Biodiesel means a mono alkyl ester manufactured in the...

7 CFR 1424.3 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-01-01

..., Firearms, and Explosives of the United States Department of Justice. Base production means a biodiesel producer's current FY's biodiesel production from eligible commodities that is not an increase over biodiesel production in the previous FY to date. Biodiesel means a mono alkyl ester manufactured in the...

Preclinical studies of steroid-linked nitrosoureas in murine pancreatic adenocarcinoma PANO2.

PubMed

Papageorgiou, A; Lialiaris, Th; Stergiou, E; Stergiou, I; Tsigris, C; Kourti, A; Geromichalos, G; Stravoravdi, P; Trafalis, D; Athanassiou, A E; Pitsas, A; Camoutsis, Ch

2008-01-01

In earlier studies, this laboratory carried out research on the synthesis and anticancer evaluation of hybrid compounds, which combine two molecules in one such as homo-aza-steroidal esters (HASE) of carboxylic derivatives of N, N-bis (2-chloroethyl) aniline. In this combination, steroidal hormones are employed as carriers for transporting the alkylating agents to specific targeted tissues. Aiming to continue our research, we used alkylating agents, as nitrosoureas, instead of nitrogen mustards. In this work the N-[N- (2-chloroethyl)-N-nitroso-carbomoyl]-L-alanine (CNC-ala) has been used and was bound to 7 newly synthesized modified steroidal esters (carrier molecule) of nitrosourea and the hybrid molecules were tested for antitumor activity against PANO2 murine pancreatic adenocarcinoma. PANO2 adenocarcinoma was used in this study. C57Bl mice were used for chemotherapy evaluation. The activity was assessed from the inhibition of tumor growth and the oncostatic parameter T/C %. The antitumor activity displayed by 7 hybrid steroidal esters of nitrosourea was quite interesting. It was able to discern 4 of 7 compounds that exhibited considerable antitumor activity, increasing the lifespan of the tumor-bearing mice by inhibiting the tumor growth. The comparative study of 7 newly synthesized hybrid steroidal esters of nitrosourea shows that the antitumor effects of compound 7, which has an enlarged (7 carbon atoms) A-lactamic ring and nitrosourea esterified at the position 17, which seems to be the most appropriate for the connection of a DNA cross-linking amino acid derivative is superior.

Evaluation of nitrate-substituted pseudocholine esters of aspirin as potential nitro-aspirins.

PubMed

Gilmer, John F; Moriarty, Louise M; Clancy, John M

2007-06-01

Herein we explore some designs for nitro-aspirins, compounds potentially capable of releasing both aspirin and nitric oxide in vivo. A series of nitrate-bearing alkyl esters of aspirin were prepared based on the choline ester template preferred by human plasma butyrylcholinesterase. The degradation kinetics of the compounds were followed in human plasma solution. All compounds underwent hydrolysis rapidly (t(1/2) approximately 1min) but generating exclusively the corresponding nitro-salicylate. The one exception, an N-propyl, N-nitroxyethyl aminoethanol ester produced 9.2% aspirin in molar terms indicating that the nitro-aspirin objective is probably achievable if due cognisance can be paid to the demands of the activating enzyme. Even at this low level of aspirin release, this compound is the most successful nitro-aspirin reported to date in the key human plasma model.

Medium-chain alkyl esters of tyrosol and hydroxytyrosol antioxidants by cuphea oil transesterification

USDA-ARS?s Scientific Manuscript database

Effective lipophilic antioxidants were readily prepared by non-aqueous enzymatic transesterification of plant phenols with cuphea oil. Tyrosol (2-(4-hydroxyphenyl)ethanol) and hydroxytyrosol (2-(3,4-dihydroxyphenyl)ethanol), abundantly available phenols from olive oil processing byproduct, were foun...

Polar and aliphatic domains regulate sorption of phthalic acid esters (PAEs) to biochars.

PubMed

Sun, Ke; Jin, Jie; Keiluweit, Marco; Kleber, Markus; Wang, Ziying; Pan, Zezhen; Xing, Baoshan

2012-08-01

Molecular variations among different biochar categories translate into differences in their ability to function as sorbents to three phthalic acid esters (PAEs) representing a gradient in hydrophobicity. The sorption capacity (K(OC)) for all three PAEs was the greatest for amorphous biochars (heat treatment temperature HTT=400 °C), followed by biochars produced at 300 °C, and was best explained by the hydrophobicity of the sorbate. Greater alkyl C content and higher polarity of grass chars versus wood chars prepared at similar temperatures explained both (a) the difference in sorbent strength between feedstocks and (b) the maximum in sorbent strength at relatively low HTTs (300-400 °C). Hydrophobic partitioning into 'soft' alkyl carbon and specific H-bonding involving char-bound O and N groups jointly account for high affinities of PAEs for low-HTT biochars. The results highlight the influence of feedstocks and HTTs on PAEs sorption strength and mechanism. Copyright © 2012 Elsevier Ltd. All rights reserved.

[Comparative assessment of Cladophora, Spirogyra and Oedogonium biomass for the production of fatty acid methyl esters].

PubMed

Haq, I; Muhammad, A; Hameed, U

2014-01-01

The use of alternative fuels for the mitigation of ecological impacts by use of diesel has been focus of intensive research. In the present work, algal oils extracted from cultivated biomass of Cladophora sp., Spirogyra sp. and Oedogonium sp. were evaluated for the lipase-mediated synthesis of fatty acid monoalkyl esters (FAME, biodiesel). To optimize the transesterification of these oils, different parameters such as the alkyl group donor, reaction temperature, stirring time and oil to alcohol ratio were investigated. Four different alcohols i.e. methanol, ethanol, n-propanol and n-butanol were tested as alkyl group donor for the biosynthesis FAME and methanol was found to be the best. Similarly, temperature 50 C and stirring time of 6 h were optimized for the transesterification of oils with methanol. The maximum biodiesel conversions from Cladophora (75.0%), Spirogyra (87.5%) and Oedogonium (92.0%) were obtained when oil to alcohol ratio was 1 : 8.

Synthesis of hydroxyphthioceranic acid using a traceless lithiation-borylation-protodeboronation strategy

NASA Astrophysics Data System (ADS)

Rasappan, Ramesh; Aggarwal, Varinder K.

2014-09-01

In planning organic syntheses, disconnections are most often made adjacent to functional groups, which assist in C-C bond formation. For molecules devoid of obvious functional groups this approach presents a problem, and so functionalities must be installed temporarily and then removed. Here we present a traceless strategy for organic synthesis that uses a boronic ester as such a group in a one-pot lithiation-borylation-protodeboronation sequence. To realize this strategy, we developed a methodology for the protodeboronation of alkyl pinacol boronic esters that involves the formation of a boronate complex with a nucleophile followed by oxidation with Mn(OAc)3 in the presence of the hydrogen-atom donor 4-tert-butylcatechol. Iterative lithiation-borylation-protodeboronation allows the coupling of smaller fragments to build-up long alkyl chains. We employed this strategy in the synthesis of hydroxyphthioceranic acid, a key component of the cell-wall lipid of the virulent Mycobacterium tuberculosis, in just 14 steps (longest linear sequence) with full stereocontrol.

Influence of Sulfur for Oxygen Substitution in the Solvolytic Reactions of Chloroformate Esters and Related Compounds

PubMed Central

D’Souza, Malcolm J.; Kevill, Dennis N.

2014-01-01

The replacement of oxygen within a chloroformate ester (ROCOCl) by sulfur can lead to a chlorothioformate (RSCOCl), a chlorothionoformate (ROCSCl), or a chlorodithioformate (RSCSCl). Phenyl chloroformate (PhOCOCl) reacts over the full range of solvents usually included in Grunwald-Winstein equation studies of solvolysis by an addition-elimination (A-E) pathway. At the other extreme, phenyl chlorodithioformate (PhSCSCl) reacts across the range by an ionization pathway. The phenyl chlorothioformate (PhSCOCl) and phenyl chlorothionoformate (PhOCSCl) react at remarkably similar rates in a given solvent and there is a dichotomy of behavior with the A-E pathway favored in solvents such as ethanol-water and the ionization mechanism favored in aqueous solvents rich in fluoroalcohol. Alkyl esters behave similarly but with increased tendency to ionization as the alkyl group goes from 1° to 2° to 3°. N,N-Disubstituted carbamoyl halides favor the ionization pathway as do also the considerably faster reacting thiocarbamoyl chlorides. The tendency towards ionization increases as, within the three contributing structures of the resonance hybrid for the formed cation, the atoms carrying positive charge (other than the central carbon) change from oxygen to sulfur to nitrogen, consistent with the relative stabilities of species with positive charge on these atoms. PMID:25310653

HPLC method for rapidly following biodiesel fuel transesterification reaction progress using a core-shell column.

PubMed

Allen, Samuel J; Ott, Lisa S

2012-07-01

There are a wide and growing variety of feedstocks for biodiesel fuel. Most commonly, these feedstocks contain triglycerides which are transesterified into the fatty acid alkyl esters (FAAEs) which comprise biodiesel fuel. While the tranesterification reaction itself is simple, monitoring the reaction progress and reaction products is not. Gas chromatography-mass spectrometry is useful for assessing the FAAE products, but does not directly address either the tri-, di-, or monoglycerides present from incomplete transesterification or the free fatty acids which may also be present. Analysis of the biodiesel reaction mixture is complicated by the solubility and physical property differences among the components of the tranesterification reaction mixture. In this contribution, we present a simple, rapid HPLC method which allows for monitoring all of the main components in a biodiesel fuel transesterification reaction, with specific emphasis on the ability to monitor the reaction as a function of time. The utilization of a relatively new, core-shell stationary phase for the HPLC column allows for efficient separation of peaks with short elution times, saving both time and solvent.

New coumarin carboxylates having trifluoromethyl, diethylamino and morpholino terminal groups: Synthesis and mesomorphic characterisations

NASA Astrophysics Data System (ADS)

Srinivasa, Hosapalya Thimmaiah; Harishkumar, Hosanagara Narayana; Palakshamurthy, Bandrehalli Siddagangappa

2017-03-01

New set of trifluromethyl, diethylamino and morpholino derived coumarin compounds were prepared by reacting various coumarin 3-carboxylic acids with various phenyl esters with peripheral alkyl, ester and polar cyano moieties in the presence of EDC.HCl/DMAP as esterification agent. The chemical structures of new coumarin derivatives were confirmed by standard spectroscopic techniques and mesomorphic behaviours were established by polarised optical microscopy (POM) and differential scanning calorimetry (DSC). Trifluoromethane and morpholino derivatives show SmA/Nematic phase, while diethylamino derivatives did not show liquid crystalline property.

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

PubMed

Bouffard, Jean; Itami, Kenichiro

2009-10-01

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

Direct N-alkylation of unprotected amino acids with alcohols

PubMed Central

Yan, Tao; Feringa, Ben L.; Barta, Katalin

2017-01-01

N-alkyl amino acids find widespread application as highly valuable, renewable building blocks. However, traditional synthesis methodologies to obtain these suffer from serious limitations, providing a major challenge to develop sustainable alternatives. We report the first powerful catalytic strategy for the direct N-alkylation of unprotected α-amino acids with alcohols. This method is highly selective, produces water as the only side product leading to a simple purification procedure, and a variety of α-amino acids are mono- or di-N-alkylated, in most cases with excellent retention of optical purity. The hydrophobicity of the products is tunable, and even simple peptides are selectively alkylated. An iron-catalyzed route to mono-N-alkyl amino acids using renewable fatty alcohols is also described that represents an ideal green transformation for obtaining fully bio-based surfactants. PMID:29226249

Biodiesel lubricity and other properties

USDA-ARS?s Scientific Manuscript database

Biodiesel, defined as the mono-alkyl esters of vegetable oils or animal fats, is an “alternative” diesel fuel that is becoming accepted in a steadily growing number of countries worldwide. Since the source of biodiesel varies with the location, and other sources such as recycled oils are continuousl...

Alternative Fuels Data Center

Science.gov Websites

% alcohol, natural gas, propane, coal-derived liquid fuels, hydrogen, electricity, pure biodiesel, renewable . Biodiesel is defined as mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats that meets current ASTM biodiesel standards. (Reference Wyoming Statutes 39-17-301

Synthesis and stereochemical analysis of β-nitromethane substituted γ-amino acids and peptides.

PubMed

Ganesh Kumar, Mothukuri; Mali, Sachitanand M; Gopi, Hosahudya N

2013-02-07

The high diastereoselectivity in the Michael addition of nitromethane to α,β-unsaturated γ-amino esters, crystal conformations of β-nitromethane substituted γ-amino acids and peptides are studied. Results suggest that the N-Boc protected amide NH, conformations of α,β-unsaturated γ-amino esters and alkyl side chains play a crucial role in dictating the high diastereoselectivity of nitromethane addition to E-vinylogous amino esters. Investigation of the crystal conformations of both α,β-unsaturated γ-amino esters and the Michael addition products suggests that an H-C(γ)-C(β)=C(α) eclipsed conformer of the unsaturated amino ester leads to the major (anti) product compared to that of an N-C(γ)-C(β)=C(α) eclipsed conformer. The major diastereomers were separated and subjected to the peptide synthesis. The single crystal analysis of the dipeptide containing β-nitromethane substituted γ-amino acids reveals a helical type of folded conformation with an isolated H-bond involving a nine-atom pseudocycle.

Michael Additions of Highly Basic Enolates to ortho-Quinone Methides

PubMed Central

Lewis, Robert S.; Garza, Christopher J.; Dang, Ann T.; Pedro, Te Kie A.; Chain, William J.

2015-01-01

A protocol by which ketone or ester enolates and ortho-quinone methides (o-QMs) are generated in situ in a single reaction flask from silylated precursors under the action of anhydrous fluoride is reported. The reaction partners are joined to give a variety of β-(2-hydroxyphenyl)-carbonyl compounds in 32–94% yield in a single laboratory operation. The intermediacy of o-QMs is supported by control experiments utilizing enolate precursors and conventional alkyl halides as competitive alkylating agents and the isolation of 1,5-dicarbonyl products resulting from conjugate additions that do not restore the aromatic system. PMID:25906358

Synthesis and biological evaluation of arctigenin ester and ether derivatives as activators of AMPK.

PubMed

Shen, Sida; Zhuang, Jingjing; Chen, Yijia; Lei, Min; Chen, Jing; Shen, Xu; Hu, Lihong

2013-07-01

A series of new arctigenin and 9-deoxy-arctigenin derivatives bearing different ester and ether side chains at the phenolic hydroxyl positions are designed, synthesized, and evaluated for activating AMPK potency in L6 myoblasts. Initial biological evaluation indicates that some alkyl ester and phenethyl ether arctigenin derivatives display potential activities in AMPK phosphorylation improvement. Further structure-activity relationship analysis shows that arctigenin ester derivatives 3a, 3h and 9-deoxy-arctigenin phenethyl ether derivatives 6a, 6c, 6d activate AMPK more potently than arctigenin. Moreover, the 2-(3,4-dimethoxyphenyl)ethyl ether moiety of 6c has been demonstrated as a potential functional group to improve the effect of AMPK phosphorylation. The structural optimization of arctigenin leads to the identification of 6c as a promising lead compound that exhibits excellent activity in AMPK activation. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

Gemini ester quat surfactants and their biological activity.

PubMed

Łuczyński, Jacek; Frąckowiak, Renata; Włoch, Aleksandra; Kleszczyńska, Halina; Witek, Stanisław

2013-03-01

Cationic gemini surfactants are an important class of surface-active compounds that exhibit much higher surface activity than their monomeric counterparts. This type of compound architecture lends itself to the compound being easily adsorbed at interfaces and interacting with the cellular membranes of microorganisms. Conventional cationic surfactants have high chemical stability but poor chemical and biological degradability. One of the main approaches to the design of readily biodegradable and environmentally friendly surfactants involves inserting a bond with limited stability into the surfactant molecule to give a cleavable surfactant. The best-known example of such a compound is the family of ester quats, which are cationic surfactants with a labile ester bond inserted into the molecule. As part of this study, a series of gemini ester quat surfactants were synthesized and assayed for their biological activity. Their hemolytic activity and changes in the fluidity and packing order of the lipid polar heads were used as the measures of their biological activity. A clear correlation between the hemolytic activity of the tested compounds and their alkyl chain length was established. It was found that the compounds with a long hydrocarbon chain showed higher activity. Moreover, the compounds with greater spacing between their alkyl chains were more active. This proves that they incorporate more easily into the lipid bilayer of the erythrocyte membrane and affect its properties to a greater extent. A better understanding of the process of cell lysis by surfactants and of their biological activity may assist in developing surfactants with enhanced selectivity and in widening their range of application.

The potential of biodiesel with improved properties to an alternative energy mix

USDA-ARS?s Scientific Manuscript database

Fuels derived from renewable biological sources (biomass) are prominent among the sustainable energy sources. Biodiesel, the mono-alkyl esters of vegetable oils or animal fats, is one of the significant biomass-derived fuels. It is obtained from vegetable oils or other triacylglycerol feedstocks b...

Effects of monoacylglycerols on kinematic viscosity and cold filter plugging point of methyl soyate

USDA-ARS?s Scientific Manuscript database

Biodiesel is an alternative fuel composed of mono-alkyl fatty acid esters made from the transesterification of plant oils or animal fats with methanol or ethanol. After conversion, biodiesel may contain trace concentrations of unconverted monoacylglycerols (MAG). These MAG have low solubility in bio...

JP-8 and Other Military Fuels (2014 UPDATE)

DTIC Science & Technology

2014-06-17

Biodiesel , Ethanol – Not cost competitive with fossil fuels • 2nd Generation Alternative Fuels – Fischer-Tropsch Synthetic Paraffinic Kerosene (FT-SPK) and...Generation Alternative Fuels Unclassified • Biodiesel – a fuel comprised of mono-alkyl esters of long chain fatty acids derived from Vegetable oils or

40 CFR 180.960 - Polymers; exemptions from the requirement of a tolerance.

Code of Federal Regulations, 2014 CFR

2014-07-01

...-hydroxypoly (oxypropylene) and/or poly (oxyethylene) polymers where the alkyl chain contains a minimum of six...-hydroxypoly(oxyethylene)poly (oxypropylene) poly(oxyethylene) block copolymer; the minimum poly(oxypropylene... weight (in amu), 900,000 62386-95-2 Monophosphate ester of the block copolymer α-hydro-ω-hydroxypoly...

PREPARATION OF ALKYL PYROPHOSPHATE EXTRACTANTS

DOEpatents

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

1960-08-01

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

The presence of functional groups key for biodegradation in ionic liquids: effect on gas solubility.

PubMed

Deng, Yun; Morrissey, Saibh; Gathergood, Nicholas; Delort, Anne-Marie; Husson, Pascale; Costa Gomes, Margarida F

2010-03-22

The effect of the incorporation of either ester or ester and ether functions into the side chain of an 1-alkyl-3-methylimidazolium cation on the physico-chemical properties of ionic liquids containing bis(trifluoromethylsulfonyl)imide or octylsulfate anions is studied. It is believed that the introduction of an ester function into the cation of the ionic liquids greatly increases their biodegradability. The density of three such ionic liquids is measured as a function of temperature, and the solubility of four gases-carbon dioxide, ethane, methane, and hydrogen-is determined between 303 K and 343 K and at pressures close to atmospheric level. Carbon dioxide is the most soluble gas, followed by ethane and methane; the mole fraction solubilities vary from 1.8 x 10(-3) to 3.7 x 10(-2). These solubilities are of the same order of magnitude as those determined for alkylimidazolium-based ionic liquids. The chemical modification of the alkyl side chain does not result in a significant change of the solvation properties of the ionic liquid. All of the solubilities decrease with increasing temperature, corresponding to an exothermal solvation process. From the variation of this property with temperature, the thermodynamic functions of solvation (Gibbs energy, enthalpy, and entropy) are calculated and provide information about the solute-solvent interactions and the molecular structure of the solutions.

40 CFR 721.6100 - Phosphoric acid, C6-12-alkyl esters, compounds with 2-(dibutylamino) ethanol.

Code of Federal Regulations, 2013 CFR

2013-07-01

..., compounds with 2-(dibutylamino) ethanol. 721.6100 Section 721.6100 Protection of Environment ENVIRONMENTAL..., compounds with 2-(dibutylamino) ethanol. (a) Chemical substances and significant new uses subject to...-(dibutylamino)ethanol (PMN P-90-384) are subject to reporting under this section for the significant new use...

40 CFR 721.6100 - Phosphoric acid, C6-12-alkyl esters, compounds with 2-(dibutylamino) ethanol.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., compounds with 2-(dibutylamino) ethanol. 721.6100 Section 721.6100 Protection of Environment ENVIRONMENTAL..., compounds with 2-(dibutylamino) ethanol. (a) Chemical substances and significant new uses subject to...-(dibutylamino)ethanol (PMN P-90-384) are subject to reporting under this section for the significant new use...

40 CFR 721.6100 - Phosphoric acid, C6-12-alkyl esters, compounds with 2-(dibutylamino) ethanol.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., compounds with 2-(dibutylamino) ethanol. 721.6100 Section 721.6100 Protection of Environment ENVIRONMENTAL..., compounds with 2-(dibutylamino) ethanol. (a) Chemical substances and significant new uses subject to...-(dibutylamino)ethanol (PMN P-90-384) are subject to reporting under this section for the significant new use...

40 CFR 721.6100 - Phosphoric acid, C6-12-alkyl esters, compounds with 2-(dibutylamino) ethanol.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., compounds with 2-(dibutylamino) ethanol. 721.6100 Section 721.6100 Protection of Environment ENVIRONMENTAL..., compounds with 2-(dibutylamino) ethanol. (a) Chemical substances and significant new uses subject to...-(dibutylamino)ethanol (PMN P-90-384) are subject to reporting under this section for the significant new use...

40 CFR 721.6100 - Phosphoric acid, C6-12-alkyl esters, compounds with 2-(dibutylamino) ethanol.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., compounds with 2-(dibutylamino) ethanol. 721.6100 Section 721.6100 Protection of Environment ENVIRONMENTAL..., compounds with 2-(dibutylamino) ethanol. (a) Chemical substances and significant new uses subject to...-(dibutylamino)ethanol (PMN P-90-384) are subject to reporting under this section for the significant new use...

Effects of monoacylglycerols on low-temperature viscosity and cold filter plugging point of biodiesel

USDA-ARS?s Scientific Manuscript database

Biodiesel is composed of mono-alkyl fatty acid esters made from the transesterification of vegetable oil or animal fat with methanol or ethanol. Biodiesel must meet rigorous standard fuel specifications (ASTM D 6751; CEN EN 14214) to be classified as an alternative fuel. Nevertheless, biodiesel that...

40 CFR 180.960 - Polymers; exemptions from the requirement of a tolerance.

Code of Federal Regulations, 2012 CFR

2012-07-01

...-hydroxypoly (oxypropylene) and/or poly (oxyethylene) polymers where the alkyl chain contains a minimum of six...) block copolymer; the minimum poly(oxypropylene) content is 27 moles and the minimum molecular weight (in... weight (in amu), 900,000 62386-95-2 Monophosphate ester of the block copolymer α-hydro-ω-hydroxypoly...

40 CFR 180.960 - Polymers; exemptions from the requirement of a tolerance.

Code of Federal Regulations, 2013 CFR

2013-07-01

...-hydroxypoly (oxypropylene) and/or poly (oxyethylene) polymers where the alkyl chain contains a minimum of six... (oxypropylene) poly(oxyethylene) block copolymer; the minimum poly(oxypropylene) content is 27 moles and the... number average molecular weight (in amu), 900,000 62386-95-2 Monophosphate ester of the block copolymer α...

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

PubMed

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

2015-02-15

The present paper accounts for the study of the storage of Chemlali olive fruits at two conditions of limited aerobiosis: in closed plastic bags and in open perforated plastic boxes for different periods before oil extraction. The ultimate objective is to investigate the effect of the container type of the postharvest fruit storage on the deterioration of the olive oil quality. The results have shown that the oil quality of Chemlali olives deteriorated more rapidly during fruit storage in closed plastic bags than in perforated plastic boxes. Therefore, the use of perforated plastic boxes is recommended for keeping the olives for longer periods of storage. The repeated measures analysis of variance of all parameters analyzed indicated that the olive oil quality is mainly affected by the olives storage conditions (containers type and storage periods). Finally, blends of extra-virgin olive oil and mildly deodorized low-quality olive oils can be detected by their alkyl esters concentrations. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biodiesel production from triolein and short chain alcohols through biocatalysis.

PubMed

Salis, Andrea; Pinna, Marcella; Monduzzi, Maura; Solinas, Vincenzo

2005-09-29

Oleic acid alkyl esters (biodiesel) were synthesised by biocatalysis in solvent-free conditions. Different commercial immobilised lipases, namely Candida antarctica B, Rizhomucor miehei, and Pseudomonas cepacia, were tested towards the reaction between triolein and butanol to produce butyl oleate. Pseudomonas cepacia lipase resulted to be the most active enzyme reaching 100% of conversion after 6h. Different operative conditions such as reaction temperature, water activity, and reagent stoichiometric ratio were investigated and optimised. These conditions were then used to investigate the effect of linear and branched short chain alcohols. Methanol and 2-butanol were the worst alcohols: the former, probably, due to its low miscibility with the oil and the latter because secondary alcohols usually are less reactive than primary alcohols. Conversely, linear and branched primary alcohols with short alkyl chains (C(2)--C(4)) showed high reaction rate and conversion. A mixture of linear and branched short chain alcohols that mimics the residual of ethanol distillation (fusel oil) was successfully used for oleic acid ester synthesis. These compounds are important in biodiesel mixtures since they improve low temperature properties.

Branched-chain dicationic ionic liquids for fatty acid methyl ester assessment by gas chromatography.

PubMed

Talebi, Mohsen; Patil, Rahul A; Sidisky, Leonard M; Berthod, Alain; Armstrong, Daniel W

2017-12-06

Twelve bis- or dicationic ionic liquids (ILs) including eight based on imidazolium, a single one based on phosphonium, and three based on pyrrolidinium cationic units were prepared with the bis(trifluoromethyl sulfonyl) imide anion. The two identical cationic moieties were attached by different alkyl spacers having three or five carbons and differing alkyl substituents attached to the spacer. The SLB-IL111 column, as the most polar commercial stationary phase known, was included in the study for comparison. Isothermal separations of a rapeseed oil fatty acid methyl ester (FAME) sample were used to study and compare the 12 IL-based column performances and selectivities. The retention times of the most retained methyl esters of lignoceric (C24:0) and erucic (C22:1) acids were used to estimate the IL polarity. The phosphonium dicationic IL column was, by far, the least polar. Imidazolium-based dicationic IL columns were the most polar. Polarity and selectivity for the FAME separation were somewhat related. The separation of a 37-FAME standard mixture allowed the investigation of selectivity variations observed on the 12 IL-based columns under temperature gradients up to 230 °C. The remarkable selectivity of the IL-based columns is demonstrated by the detailed analysis of the cis/trans C18:1 isomers of a partially hydrogenated vegetable oil sample on 30-m columns, separations competing with that done following an "official method" performed on a 100-m column. Graphical abstract Separation of fatty acid methyl esters on a 30-m 3m 2 C 5 (mpy) 2 . 2NTf 2 branched-chain dicationic IL-based column. Branched chain dicationic ILs show great selectivity for separation of cis/trans, ω-3/ω-6, and detailed analysis of cis/trans fats.

Determination of esters in glycerol phase after transesterification of vegetable oil.

PubMed

Hájek, Martin; Skopal, Frantisek; Kwiecien, Jirí; Cernoch, Michal

2010-06-30

In biodiesel production, glycerol is formed as a side product and it is contained in the glycerol phase. This phase contains (besides glycerol): water, soaps, alcohol, traces of catalyst and glycerides and the remaining esters. In this paper, a new method for the determination of esters in the glycerol phase is introduced. The determination enables the minimization of the losses of biodiesel within the production process. It is based on the gradient RP-LC method (water and acetonitrile) with refractometric detection. The analysis is easy and the samples do not need any treatment (only dilution by water) and has a low detection limit. The results of this method were compared with the results of two other published methods: isocratic HPLC and GC. The disadvantage of these two methods is that they need extensive treatment of the sample, which takes many hours, and they are able to determine only the sum of esters. The new method is reliable, much faster and able to differentiate esters of almost each higher fatty acid (e.g. linoleic, linolenic, strearic alkyl ester) in the glycerol phase. Copyright 2010 Elsevier B.V. All rights reserved.

Interfacial self-organization of bolaamphiphiles bearing mesogenic groups: relationships between the molecular structures and their self-organized morphologies.

PubMed

Song, Bo; Liu, Guanqing; Xu, Rui; Yin, Shouchun; Wang, Zhiqiang; Zhang, Xi

2008-04-15

This article discusses the relationship between the molecular structure of bolaamphiphiles bearing mesogenic groups and their interfacial self-organized morphology. On the basis of the molecular structures of bolaamphiphiles, we designed and synthesized a series of molecules with different hydrophobic alkyl chain lengths, hydrophilic headgroups, mesogenic groups, and connectors between the alkyl chains and the mesogenic group. Through investigating their interfacial self-organization behavior, some experiential rules are summarized: (1) An appropriate alkyl chain length is necessary to form stable surface micelles; (2) different categories of headgroups have a great effect on the interfacial self-organized morphology; (3) different types of mesogenic groups have little effect on the structure of the interfacial assembly when it is changed from biphenyl to azobenzene or stilbene; (4) the orientation of the ester linker between the mesogenic group and alkyl chain can greatly influence the interfacial self-organization behavior. It is anticipated that this line of research may be helpful for the molecular engineering of bolaamphiphiles to form tailor-made morphologies.

RELEASE OF IL-8 AND IL-6 BY BEAS-2B CELLS FOLLOWING IN VITRO EXPOSURE TO BIODIESEL PM EXTRACTS

EPA Science Inventory

Abstract Body: Biodiesel, an alkyl ester of plant oils that can be used in an unmodified diesel engine, is a renewable fuel alternative which show signs of becoming a commercially accepted part of our nation¿s energy infrastructure. Biodiesel exhaust has been physicochemically ch...

Mixed alkyl esters from cottonseed oil: Improved biodiesel properties and blends with ultra-low sulfur diesel fuel

USDA-ARS?s Scientific Manuscript database

Transesterification of refined cottonseed oil was carried out with methanol, ethanol, 1-butanol, and various mixtures of these alcohols at constant volume ratio of alcohol to oil (1:2) using KOH (1 wt%) as catalyst to produce biodiesel. In the mixed alcohol transesterifications, the formation of met...

Cuphea Oil as Source of Biodiesel with Improved Fuel Properties Caused by High Content of Methyl Decanoate

USDA-ARS?s Scientific Manuscript database

Biodiesel, defined as the mono-alkyl esters of vegetable oils and animal fats, is an alternative to conventional petroleum-based diesel fuel. Biodiesel has been prepared from numerous common vegetable oils or fats as well as new or less common feedstocks. Major issues facing biodiesel include seve...

PROCESS FOR UTILIZING ORGANIC ORTHOPHOSPHATE EXTRACTANTS

DOEpatents

Grinstead, R.R.

1958-11-11

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

Optimized diazo scaffold for protein esterification.

PubMed

Mix, Kalie A; Raines, Ronald T

2015-05-15

The O-alkylation of carboxylic acids with diazo compounds provides a means to esterify carboxylic acids in aqueous solution. A Hammett analysis of the reactivity of diazo compounds derived from phenylglycinamide revealed that the (p-methylphenyl)glycinamide scaffold has an especially high reaction rate and ester/alcohol product ratio and esterifies protein carboxyl groups more efficiently than any known reagent.

Boron-based dual imaging probes, compositions and methods for rapid aqueous F-18 labeling, and imaging methods using same

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

Li, Zibo; Gabbai, Francois P.; Conti, Peter S.

A composition useful as a PET and/or fluorescence imaging probe a compound a compound of Formula I, including salts, hydrates and solvates thereof: ##STR00001## wherein R.sub.1-R.sub.7 may be independently selected from hydrogen, halogen, hydroxy, alkoxy, nitro, substituted and unsubstituted amino, cycloalkyl, carboxy, carboxylic acids and esters thereof, cyano, haloalkyl, aryl, X is selected from the group consisting of C and N; and A is selected of hydrogen, halogen, hydroxy, alkoxy, nitro, substituted and unsubstituted amino, alkyl, cycloalkyl, carboxy, carboxylic acids and esters thereof, cyano, haloalkyl, aryl, including phenyl and aminophenyl, and heteroaryl.

Expeditious microwave-assisted synthesis of 5-alkoxyoxazoles from α-triflyloxy esters and nitriles.

PubMed

Jouanno, Laurie-Anne; Sabot, Cyrille; Renard, Pierre-Yves

2012-10-05

A rapid and general access to diversely substituted 5-alkoxyoxazoles 2 (i.e., R(1), R(2) = alkyl, phenyl) from easily accessible α-triflyloxy/hydroxy esters 1 and nitriles with good yields (41-76%) is reported. The versatility of the cyclization is shown for a range of substrates with high selectivity toward triflates over mesylates and proved to be compatible with sensitive functional groups. As an illustration of this transformation, the first synthesis of the recently isolated hydroxypyridine methyl multijuguinate 4 was achieved in four steps through a hetero Diels-Alder reaction of the 5-alkoxyoxazole and acrylic acid, followed by a protodecarboxylation reaction.

Syntheses of nicotinamide riboside and derivatives: effective agents for increasing nicotinamide adenine dinucleotide concentrations in mammalian cells.

PubMed

Yang, Tianle; Chan, Noel Yan-Ki; Sauve, Anthony A

2007-12-27

A new two-step methodology achieves stereoselective synthesis of beta-nicotinamide riboside and a series of related amide, ester, and acid nucleosides. Compounds were prepared through a triacetylated-nicotinate ester nucleoside, via coupling of either ethylnicotinate or phenylnicotinate with 1,2,3,5-tetra-O-acetyl-beta-D-ribofuranose. Nicotinamide riboside, nicotinic acid riboside, O-ethylnicotinate riboside, O-methylnicotinate riboside, and several N-alkyl derivatives increased NAD+ concentrations from 1.2-2.7-fold in several mammalian cell lines. These findings establish bioavailability and potent effects of these nucleosides in stimulating the increase of NAD+ concentrations in mammalian cells.

Synthesis and photochemical properties of a novel iron-sulfur-nitrosyl cluster derivatized with the pendant chromophore protoporphyrin IX.

PubMed

Conrado, Christa L; Wecksler, Stephen; Egler, Christian; Magde, Douglas; Ford, Peter C

2004-09-06

The novel Roussin red-salt ester (PPIX-RSE) with a pendant porphyrin chromophore was prepared and investigated as a precursor for the photochemical generation of nitric oxide. PPIX-RSE has the general formula Fe(2)(NO)(4)[(mu-S,mu-S')P] (where (S,S')P is the bis(2-thiolatoethyl) diester of protoporphyrin IX. The photoexcitation of PPIX-RSE with 436- or 546-nm light in an aerated chloroform solution led to the photodecomposition of the cluster with the respective quantum yields (5.2 +/- 0.7) x 10(-4) and (2.5 +/- 0.5 x 10(-4)) and the concomitant release of NO. PPIX-RSE is a significantly more effective NO generator at longer wavelength excitation than are other Fe(2)(mu-SR)(2)(NO)(4) esters for which R is a simple alkyl group such as CH(3)CH(2)- because of the much higher absorptivity of the pendant PPIX chromophore at these wavelengths and a modestly higher quantum yield. Fluorescence intensity and lifetime data indicate that the photoexcited porphyrin of PPIX-RSE is largely quenched by the energy transfer to the Fe(2)S(2)(NO)(4) cluster's core. However, a small fraction of this emission is not quenched, and it is proposed that PPIX-RSE may exist in solution as two conformers.

In vitro induction of micronuclei by monofunctional methanesulphonic acid esters: possible role of alkylation mechanisms.

PubMed

Eder, Erwin; Kütt, Wolfgang; Deininger, Christoph

2006-12-01

Six monofunctional alkylating methanesulphonates of widely varying structures were investigated in the in vitro micronucleus assay with Syrian hamster embryo fibroblast cells. The results were compared with the alkylating activities measured in the 4-(nitrobenzyl)pyridine test (NBP-test) and the N-methyl mercaptoimidazole (MMI-test) as measures for S(N)2 reactivity as well as in the triflouoroacetic acid (TFA) solvolysis and the hydrolysis reaction as measures for S(N)1 reactivity in order to provide insights into the role of alkylation mechanisms on induction of micronuclei. Moreover we compared the results of micronucleus assay with those of the Ames tests in strain TA 100 and TA1535 and with those of the SOS chromotest with the strains PQ37, PQ243, PM21 and GC 4798. The potency of methanesulphonates to induce micronuclei depended only to a certain degree, on the total alkylating activity (S(N)1 and S(N)2 reactivity). An inverse, significant correlation between the Ames test and the micronucleus assay was observed and an inverse correlation between the micronucleus assay and the SOS chromotest with the different strains. The results indicate that the primary mechanism leading to induction of micronuclei is not O-alkylation in DNA as it is the case in the Ames test with the hisG46 strains TA1535 and TA100 and not N-alkylation as with the SOS chromotest. There is evidence that protein alkylation, e.g. in the spindle apparatus in mitosis is decisive for induction of micronuclei by alkylating compounds. The structurally voluminous methanesulphonates 2-phenyl ethyl methanesulphonate and 1-phenyl-2-propyl methanesulphonate show a clear higher micronuclei inducing potency than the other tested though the bulky methanesulphonates possess a lower total alkylating activity than the others. This effect can be explained by a higher disturbance during mitosis after alkylation of the spindle apparatus with the structurally more bulky methanesulphonates.

Mixed-Salt/Ester Electrolytes for Low-Temperature Li+ Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar

2006-01-01

Electrolytes comprising, variously, LiPF6 or LiPF6 plus LiBF4 dissolved at various concentrations in mixtures of alkyl carbonates and alkyl esters have been found to afford improved low-temperature performance in rechargeable lithium-ion electrochemical cells. These and other electrolytes have been investigated in a continuing effort to extend the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles, the most recent being Ester-Based Electrolytes for Low-Temperature Li-Ion Cells (NPO-41097), NASA Tech Briefs, Vol. 29, No. 12 (December 2005), page 59. The ingredients of the solvent mixtures include ethylene carbonate (EC), ethyl methyl carbonate (EMC), methyl butyrate (MB), and methyl propionate (MP). The electrolytes were placed in Li-ion cells containing carbon anodes and LiNi0.8Co0.2O2 cathodes, and the electrical performances of the cells were measured over a range of temperatures down to 60 C. The electrolytes that yielded the best low-temperature performances were found to consist, variously, of 1.0 M LiPF6 + 0.4 M LiBF4 or 1.4 LiPF6 in 1EC + 1EMC + 8MP or 1EC + 1EMC + 8MB, where the concentrations of the salts are given in molar units and the proportions of the solvents are by relative volume.

Comparison of Antioxidant Evaluation Assays for Investigating Antioxidative Activity of Gallic Acid and Its Alkyl Esters in Different Food Matrices.

PubMed

Phonsatta, Natthaporn; Deetae, Pawinee; Luangpituksa, Pairoj; Grajeda-Iglesias, Claudia; Figueroa-Espinoza, Maria Cruz; Le Comte, Jérôme; Villeneuve, Pierre; Decker, Eric A; Visessanguan, Wonnop; Panya, Atikorn

2017-08-30

The addition of antioxidants is one of the strategies to inhibit lipid oxidation, a major cause of lipid deterioration in foods leading to rancidity development and nutritional losses. However, several studies have been reported that conventional antioxidant assays, e.g., TPC, ABTS, FRAP, and ORAC could not predict antioxidant performance in several foods. This study aimed to investigate the performance of two recently developed assays, e.g., the conjugated autoxidizable triene (CAT) and the apolar radical-initiated conjugated autoxidizable triene (ApoCAT) assays to predict the antioxidant effectiveness of gallic acid and its esters in selected food models in comparison with the conventional antioxidant assays. The results indicated that the polarities of the antioxidants have a strong impact on antioxidant activities. In addition, different oxidant locations demonstrated by the CAT and ApoCAT assays influenced the overall antioxidant performances of the antioxidants with different polarities. To validate the predictability of the assays, the antioxidative performance of gallic acid and its alkyl esters was investigated in oil-in-water (O/W) emulsions, bulk soybean oils, and roasted peanuts as the lipid food models. The results showed that only the ApoCAT assay could be able to predict the antioxidative performances in O/W emulsions regardless of the antioxidant polarities. This study demonstrated that the relevance of antioxidant assays to food models was strongly dependent on physical similarities between the tested assays and the food structure matrices.

Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

PubMed

Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

2015-01-01

A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Grafting C8-C16 alkyl groups altered the self-assembly and curcumin -loading properties of sodium caseinate in water.

PubMed

Zhang, Yaqiong; Yang, Puyu; Yao, Fangyi; Liu, Jie; Yu, Liangli Lucy

2018-02-01

The data presented here are related to the research article entitled "Synthesis and characterization of alkylated caseinate, and its structure-curcumin loading property relationship in water" (Zhang et al., 2018) [1]. This data article reports the detailed spectra information for 1 H NMR, 13 C NMR and UPLC-Q-TOF MS of the N-succinimidyl fatty acid esters with various alkyl chain lengths (Cn-NHSs, n = 8, 12, 14 and 16). 1 H NMR, 13 C NMR and UPLC-Q-TOF MS spectra for C16-NHS are shown as an example. Then the stacked 1 H NMR spectra of the obtained alkylated caseinates (Cn-caseinates, n = 8, 12, 14 and 16) are provided. The surface hydrophobicity index (S 0 ) of Cn-caseinates with different substitution degrees (SD) of alkyl groups is shown. Additionally, Visual appearances for the formed aqueous dispersions of curcumin-loaded native caseinate (NaCas) and Cn-caseinates self-assemblies are shown. X-ray diffraction patterns of curcumin, C16-caseinate, its physical mixture and curcumin-loaded C16-caseinate self-assemblies are examined. The re-dispersibility and short-term storage stability of the curcumin-loaded NaCas and C16-caseinate self-assemblies are also studied.

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

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-18

... result of pesticide use in residential settings. If EPA is able to determine that a finite tolerance is... of its composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed in...

40 CFR 721.9530 - Bis(2,2,6,6-tetra-methyl-piper-idinyl) ester of cycloalkyl spir-o-ke-tal.

Code of Federal Regulations, 2011 CFR

2011-07-01

...-clo-alkyl spir-o-ke-tal (PMN P-88-0083) is subject to reporting under this section for the significant... may cause: systemic effects, eye irritation. (iii) Industrial, commercial, and consumer activities....125 (a), (b), (c), (d), (f), (g), (h), (i), and (k). (2) Limitations or revocation of certain...

40 CFR 721.9530 - Bis(2,2,6,6-tetra-methyl-piper-idinyl) ester of cycloalkyl spir-o-ke-tal.

Code of Federal Regulations, 2012 CFR

2012-07-01

...-clo-alkyl spir-o-ke-tal (PMN P-88-0083) is subject to reporting under this section for the significant... may cause: systemic effects, eye irritation. (iii) Industrial, commercial, and consumer activities....125 (a), (b), (c), (d), (f), (g), (h), (i), and (k). (2) Limitations or revocation of certain...

Optimized Diazo Scaffold for Protein Esterification

PubMed Central

Mix, Kalie A.

2015-01-01

The O-alkylation of carboxylic acids with diazo compounds provides a means to esterify carboxylic acids in aqueous solution. A Hammett analysis of the reactivity of diazo compounds derived from phenylglycinamide revealed that the p-methylphenylglycinamide scaffold has an especially high reaction rate and ester:alcohol product ratio, and esterifies protein carboxyl groups more efficiently than does any known reagent. PMID:25938936

A highly selective and sensitive "turn-on" fluorescence chemodosimeter for the detection of mustard gas.

PubMed

Raghavender Goud, D; Purohit, Ajay Kumar; Tak, Vijay; Dubey, Devendra Kumar; Kumar, Pravin; Pardasani, Deepak

2014-10-21

A new chemodosimetric protocol based on a tandem S-alkylation followed by desulfurisation reaction of rhodamine-thioamide with mustard gas is reported. The chemodosimeter is highly selective for potential DNA alkylating agents like sulfur mustard, over other simple alkyl halides with the limit of detection of 4.75 μM.

In vitro analysis of the effect of alkyl-chain length of anionic surfactants on the skin by using a reconstructed human epidermal model.

PubMed

Yamaguchi, Fumiko; Watanabe, Shin-Ichi; Harada, Fusae; Miyake, Miyuki; Yoshida, Masaki; Okano, Tomomichi

2014-01-01

We investigated the effect of the alkyl-chain length of anionic surfactants on the skin using an in vitro model. The evaluated anionic surfactants were sodium alkyl sulfate (AS) and sodium fatty acid methyl ester sulfonate (MES), which had different alkyl-chain lengths (C8-C14). Skin tissue damage and permeability were examined using a reconstructed human epidermal model, LabCyte EPI-MODEL24. Skin tissue damage was examined by measuring cytotoxicity with an MTT assay. Liquid chromatography/tandem mass spectrometry (LC/MS-MS) and liquid chromatography/mass spectrometry (LC/MS) were used to detect surfactants that permeated into the assay medium through an epidermal model. To assess the permeation mechanism and cell damage caused by the surfactants through the epidermis, we evaluated the structural changes of Bovine Serum Albumin (BSA), used as a simple model protein, and the fluidity of 1,2-dipalmitoyl-sn-glycero-3-phosphpcholine (DPPC) liposome, which serves as one of the most abundant phospholipid models of living cell membranes in the epidermis. The effects of the surfactants on the proteins were measured using Circular Dichroism (CD) spectroscopy, while the effects on membrane fluidity were investigated by electron spin resonance (ESR) spectroscopy. ET50 (the 50% median effective time) increased as follows: C10 < C12 < C8 < C14 in AS and C8, C10 < C12 < C14 in MES. The order of permeation through the LabCyte EPI-MODEL24 was C10 > C12 > C14, for both AS and MES. For both AS and MES, the order parameter, which is the criteria for the microscopic viscosity of lipid bilayers, increased as follows: C10 < C12 < C14, which means the membrane fluidity is C10 > C12 > C14. It was determined that the difference in skin tissue damage in the LabCyte EPI-MODEL24 with C10 to C14 AS and MES was caused by the difference in permeation and cell membrane fluidity through the lipid bilayer path in the epidermis.

Main-group compounds selectively oxidize mixtures of methane, ethane, and propane to alcohol esters.

PubMed

Hashiguchi, Brian G; Konnick, Michael M; Bischof, Steven M; Gustafson, Samantha J; Devarajan, Deepa; Gunsalus, Niles; Ess, Daniel H; Periana, Roy A

2014-03-14

Much of the recent research on homogeneous alkane oxidation has focused on the use of transition metal catalysts. Here, we report that the electrophilic main-group cations thallium(III) and lead(IV) stoichiometrically oxidize methane, ethane, and propane, separately or as a one-pot mixture, to corresponding alcohol esters in trifluoroacetic acid solvent. Esters of methanol, ethanol, ethylene glycol, isopropanol, and propylene glycol are obtained with greater than 95% selectivity in concentrations up to 1.48 molar within 3 hours at 180°C. Experiment and theory support a mechanism involving electrophilic carbon-hydrogen bond activation to generate metal alkyl intermediates. We posit that the comparatively high reactivity of these d(10) main-group cations relative to transition metals stems from facile alkane coordination at vacant sites, enabled by the overall lability of the ligand sphere and the absence of ligand field stabilization energies in systems with filled d-orbitals.

Enhanced cytogenetic and antineoplastic effects by the combined action of two esteric steroidal derivatives of nitrogen mustards.

PubMed

Papageorgiou, A; Nikolaropoulos, S S; Arsenou, E S; Karaberis, E; Mourelatos, D; Kotsis, A; Chryssogelou, E

1999-01-01

The authors studied the effect of two modified steroids containing different proportions (%) of alkylating agents alone or in combination on sister chromatid exchange (SCE) rates and on human lymphocyte proliferation kinetics. The antitumor activity of these compounds was tested on leukemia P388- and leukemia L1210-bearing mice. The two chemicals in mixtures enhance SCE induction and antitumor activity in a synergistic manner. The homo-aza-steroidal ester of p-bis(2-chloroethyl)aminophenyl acetic acid was found to be more effective than the homo-aza-steroidal ester of o-bis(2-chloroethyl)aminobenzoic acid in causing cytogenetic damage and antineoplastic activity. A correlation was observed between the magnitude of the SCE response and the depression of the cell proliferation index. The order of the antitumor effectiveness of the five different treatments tested coincided with the order of the cytogenetic effects they induced.

Asymmetric Catalysis with Organic Azides and Diazo Compounds Initiated by Photoinduced Electron Transfer.

PubMed

Huang, Xiaoqiang; Webster, Richard D; Harms, Klaus; Meggers, Eric

2016-09-28

Electron-acceptor-substituted aryl azides and α-diazo carboxylic esters are used as substrates for visible-light-activated asymmetric α-amination and α-alkylation, respectively, of 2-acyl imidazoles catalyzed by a chiral-at-metal rhodium-based Lewis acid in combination with a photoredox sensitizer. This novel proton- and redox-neutral method provides yields of up to 99% and excellent enantioselectivities of up to >99% ee with broad functional group compatibility. Mechanistic investigations suggest that an intermediate rhodium enolate complex acts as a reductive quencher to initiate a radical process with the aryl azides and α-diazo carboxylic esters serving as precursors for nitrogen and carbon-centered radicals, respectively. This is the first report on using aryl azides and α-diazo carboxylic esters as substrates for asymmetric catalysis under photoredox conditions. These reagents have the advantage that molecular nitrogen is the leaving group and sole byproduct in this reaction.

Advanced oxidation kinetics of aqueous tri alkyl phosphate flame retardants and plasticizers

PubMed Central

Watts, Michael J.; Linden, Karl G.

2009-01-01

Tri alkyl phosphate esters are a class of anthropogenic organics commonly found in surface waters of Europe and North America, due to their frequent application as flame retardants, plasticizers, and solvents. Four tri alkyl phosphate esters were evaluated to determine second-order rates of reaction with ultraviolet- and ozone-generated •OH in water. In competition with nitrobenzene in UV irradiated hydrogen peroxide solutions tris(2-butoxyethyl) phosphate (TBEP) was fastest to react with •OH (kOH,TBEP=1.03×1010 M-1s-1), followed sequentially by tributyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), and tris(2-chloroisopropyl) phosphate (TCPP) (kOH,TBEP=6.40×109, kOH,TBEP=5.60×108, & kOH,TBEP=1.98×10 M-1s-1). A two-stage process was used to test the validity of the determined kOH for TBEP and the fastest reacting halogenated alkyl phosphate, TCEP. First, •OH oxidation of TCEP and TBEP, in competition with nitrobenzene, was measured in ozonated hydrogen peroxide solutions. Applying multiple regression analysis, it was determined that the UV-H2O2 and O3-H2O2 data sets were statistically identical for each compound. The subsequent validated kOH were used to predict TCEP and TBEP photodegradation in neutral pH, model surface water after chemical oxidant addition and UV irradiation (up to 1000 mJ/cm2). The insignificant difference, between the predicted TBEP and TCEP photodegradation and a best-fit of the first-order exponential decay function to the observed TBEP and TCEP concentrations with increasing UV fluence, was further evidence of the validity of the determined kOH. TBEP oxidation rates were similar in the surface waters tested. Substantial TCEP oxidation in the model surface water required a significant increase in H2O2. PMID:19475974

Simple introduction of carboxyl head group with alkyl spacer onto multiwalled carbon nanotubes by solution plasma process

NASA Astrophysics Data System (ADS)

Nemoto, Shimpei; Ueno, Tomonaga; Watthanaphanit, Anyarat; Hieda, Junko; Bratescu, Maria Antoaneta; Saito, Nagahiro

2017-09-01

A simple method of fabricating carboxyl-terminated multiwalled carbon nanotubes (MWCNTs) with alkyl spacers was developed to improve the dispersion quality of MWCNTs in aqueous solutions using solution plasma (SP) in a 6-aminocaproic acid solution. The formation of SP in the solution led to better dispersion of MWCNTs in aqueous solutions. Fourier transform infrared spectroscopy (FT-IR) results indicate that a carboxyl group with an alkyl spacer can be introduced by SP treatment in the 6-aminocaproic acid solution. Sedimentation tests show that the SP-treated MWCNTs in the 6-aminocaproic acid solution retained their good dispersion quality in aqueous solutions of pHs 5, 6, and 9. The alkyl spacer plays an important role in the preservation of dispersion states particularly at pH 6.

Effects of parabens on adipocyte differentiation.

PubMed

Hu, Pan; Chen, Xin; Whitener, Rick J; Boder, Eric T; Jones, Jeremy O; Porollo, Aleksey; Chen, Jiangang; Zhao, Ling

2013-01-01

Parabens are a group of alkyl esters of p-hydroxybenzoic acid that include methylparaben, ethylparaben, propylparaben, butylparaben, and benzylparaben. Paraben esters and their salts are widely used as preservatives in cosmetics, toiletries, food, and pharmaceuticals. Humans are exposed to parabens through the use of such products from dermal contact, ingestion, and inhalation. However, research on the effects of parabens on health is limited, and the effects of parabens on adipogenesis have not been systematically studied. Here, we report that (1) parabens promote adipogenesis (or adipocyte differentiation) in murine 3T3-L1 cells, as revealed by adipocyte morphology, lipid accumulation, and mRNA expression of adipocyte-specific markers; (2) the adipogenic potency of parabens is increased with increasing length of the linear alkyl chain in the following potency ranking order: methyl- < ethyl- < propyl- < butylparaben. The extension of the linear alkyl chain with an aromatic ring in benzylparaben further augments the adipogenic ability, whereas 4-hydroxybenzoic acid, the common metabolite of all parabens, and the structurally related benzoic acid (without the OH group) are inactive in promoting 3T3-L1 adipocyte differentiation; (3) parabens activate glucocorticoid receptor and/or peroxisome proliferator-activated receptor γ in 3T3-L1 preadipocytes; however, no direct binding to, or modulation of, the ligand binding domain of the glucocorticoid receptor by parabens was detected by glucocorticoid receptor competitor assays; and lastly, (4) parabens, butyl- and benzylparaben in particular, also promote adipose conversion of human adipose-derived multipotent stromal cells. Our results suggest that parabens may contribute to obesity epidemic, and the role of parabens in adipogenesis in vivo needs to be examined further.

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

PubMed

Ottenhaus, Vanessa; Rosemeyer, Helmut

2015-09-01

5-Fluorouridine (1) - a nucleoside antimetabolite with strong cancerostatic properties - was protected i) at the 2'- and 3'-OH groups with a heptan-4-ylidene residue and ii) at the 5'-OH group with a (4-methoxyphenyl)(diphenyl)methyl residue. This fully protected compound, 3, was submitted to a Mitsunobu reaction with the N-hydroxysuccinimide (NHS) ester, 5, of (2E)-10-hydroxydec-2-enoic acid (4) which gave nucleolipid 6. The latter was detritylated with Cl2 CHCOOH to yield the co-drug 7 as NHS ester. Copyright © 2015 Verlag Helvetica Chimica Acta AG, Zürich.

Alkyl Caffeates Improve the Antioxidant Activity, Antitumor Property and Oxidation Stability of Edible Oil

PubMed Central

Wang, Jun; Gu, Shuang-Shuang; Pang, Na; Wang, Fang-Qin; Pang, Fei; Cui, Hong-Sheng; Wu, Xiang-Yang; Wu, Fu-An

2014-01-01

Caffeic acid (CA) is distributed widely in nature and possesses strong antioxidant activity. However, CA has lower solubility in non-polar media, which limits its application in fat-soluble food. To increase the lipophilicity of natural antioxidant CA, a series of alkyl caffeates were synthesized and their antioxidant and antitumor activities were investigated. The antioxidant parameters, including the induction period, acid value and unsaturated fatty acid content, of the alkyl caffeates in edible oil were firstly investigated. The results indicated that alkyl caffeates had a lower DPPH IC50 (14–23 µM) compared to CA, dibutyl hydroxy toluene (BHT) and Vitamin C (24–51 µM), and significantly inhibited four human cancer cells (SW620, SW480, SGC7901 and HepG2) with inhibition ratio of 71.4–78.0% by a MTT assay. With regard to the induction period and acid value assays, methyl and butyl caffeates had higher abilities than BHT to restrain the oxidation process and improve the stability of edible oil. The addition of ethyl caffeate to oil allowed maintenance of a higher unsaturated fatty acid methyl ester content (68.53%) at high temperatures. Overall, the alkyl caffeats with short chain length (n<5) assessed better oxidative stability than those with long chain length. To date, this is the first report to the correlations among the antioxidant activity, anticancer activity and oxidative stability of alkyl caffeates. PMID:24760050

Decarbonylative Cross-Couplings: Nickel Catalyzed Functional Group Interconversion Strategies for the Construction of Complex Organic Molecules.

PubMed

Guo, Lin; Rueping, Magnus

2018-05-15

The utilization of carboxylic acid esters as electrophiles in metal-catalyzed cross-coupling reactions is increasingly popular, as environmentally friendly and readily available ester derivatives can be powerful alternatives to the commonly used organohalides. However, key challenges associated with the use of these chemicals remain to be addressed, including the stability of ester substrates and the high energy barrier associated with their oxidative addition to low-valent metal species. Due to recent developments in nickel catalysis that make it easier to perform oxidative additions, chemists have become interested in applying less reactive electrophiles as coupling counterparts in nickel-catalyzed transformations. Hence, our group and others have independently investigated various ester group substitutions and functionalizations enabled by nickel catalysis. Such methods are of great interest as they enable the exchange of ester groups, which can be used as directing groups in metal-catalyzed C-H functionalizations prior to their replacement. Here, we summarize our recent efforts toward the development of nickel-catalyzed decarbonylative cross-coupling reactions of carboxylic esters. Achievements accomplished by other groups in this area are also included. To this day, a number of new transformations have been successfully developed, including decarbonylative arylations, alkylations, cyanations, silylations, borylations, aminations, thioetherifications, stannylations, and hydrogenolysis reactions. These transformations proceed via a nickel-catalyzed decarbonylative pathway and have shown a high degree of reactivity and chemoselectivity, as well as several other unique advantages in terms of substrate availability, due to the use of esters as coupling partners. Although the mechanisms of these reactions have not yet been fully understood, chemists have already provided some important insights. For example, Yamamoto explored the stoichiometric nickel-mediated decarbonylation process of esters and proposed a reaction mechanism involving a C(acyl)-O bond cleavage and a CO extrusion. Key nickel intermediates were isolated and characterized by Shi and co-workers, supporting the assumption of a nickel/ N-heterocyclic carbene-promoted C(acyl)-O bond activation and functionalization. Our combined experimental and computational study of a ligand-controlled chemoselective nickel-catalyzed cross-coupling of aromatic esters with alkylboron reagents provided further insight into the reaction mechanism. We demonstrated that nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step, resulting in decarbonylative alkylations, while nickel complexes with monodentate phosphorus ligands promote the activation of the C(acyl)-O bond, leading to the production of ketone products. Although more detailed mechanistic investigations need to be undertaken, the successful development of decarbonylative cross-coupling reactions can serve as a solid foundation for future studies. We believe that this type of decarbonylative cross-coupling reactions will be of significant value, in particularly in combination with the retrosynthetic analysis and synthesis of natural products and biologically active molecules. Thus, the presented ester substitution methods will pave the way for successful applications in the construction of complex frameworks by late-stage modification and functionalization of carboxylic acid derivatives.

Anti-Aspergillus activity of green coffee 5-O-caffeoyl quinic acid and its alkyl esters.

PubMed

Suárez-Quiroz, M L; Alonso Campos, A; Valerio Alfaro, G; González-Ríos, O; Villeneuve, P; Figueroa-Espinoza, M C

2013-01-01

The antifungal activities of 5-O-caffeoyl quinic acid (5-CQA) and of methyl, butyl, octyl, and dodecyl esters or 5-CQA, were tested on five toxigenic moulds from the Aspergillus genus (Aspergillus flavus, Aspergillus nomius, Aspergillus ochraceus, Aspergillus parasiticus, Aspergillus westerdijkiae). These mycotoxin producers' moulds may contaminate many types of food crops throughout the food chain posing serious health hazard to animals and humans. The use of chemical methods to decrease mycotoxin producer moulds contamination on food crops in the field, during storage, and/or during processing, has been proved to be efficient. In this work, the antifungal effect of 5-CQA and a homologous series of 5-CQA esters (methyl, butyl, octyl, dodecyl), was investigated using the microdilution method and the minimum inhibitory concentrations (MIC50 and MIC80). All molecules presented antifungal activity, and two esters showed a MIC for all fungi: octyl (MIC50 ≤ 0.5-0.75 mg/mL, MIC80 = 1.0-1.5 mg/mL) and dodecyl (MIC50 = 0.75-1.25 mg/mL) chlorogenates. Dodecyl chlorogenate showed a MIC80 (1.5 mg/mL) only for A. parasiticus. The maximum percent of growth inhibition on aspergillii was observed with octyl (78.4-92.7%) and dodecyl (54.5-83.7%) chlorogenates, being octyl chlorogenate the most potent antifungal agent. It was thus concluded that lipophilization improved the antifungal properties of 5-CQA, which increased with the ester alkyl chain length, exhibiting a cut-off effect at 8 carbons. As far as we know, it is the first report demonstrating that lipophilization may improve the antifungal activity of 5-CQA on five toxigenic moulds from the Aspergillus genus. Lipophilization would be a novel way to synthesize a new kind of antifungal agents with a good therapeutic value or a potential use as preservative in food or cosmetics. Copyright © 2013 Elsevier Ltd. All rights reserved.

Structural effect of quaternary ammonium chitin derivatives on their bactericidal activity and specificity.

PubMed

Morkaew, Tirut; Pinyakong, Onruthai; Tachaboonyakiat, Wanpen

2017-08-01

The effect of the quaternary ammonium chitin structure on the bactericidal activity and specificity against Escherichia coli and Staphylococcus aureus was investigated. Quaternary ammonium chitins were synthesized by the separate acylation of chitin (CT) with carboxymethyl trimethylammonium chloride (CMA), 3-carboxypropyl trimethylammonium chloride (CPA) and N-dodecyl-N,N-(dimethylammonio)butyrate (DDMAB). The successful acylation was confirmed by newly formed ester linkage. All three derivatives had a higher surface charge than chitin due to the additional positively charged quaternary ammonium groups. The N-short alkyl substituent (methyl) of CTCMA and CTCPA increased the hydrophilicity whilst the N-long alkyl substituent (dodecyl) of CTDDMAB increased the hydrophobicity compared to chitin. Chitin did not exhibit any bactericidal activity, while CTCMA and CTCPA completely killed E. coli and S. aureus in 30 and 60min, respectively, and CTDDMAB completely killed S. aureus in 10min but did not kill E. coli after a 2-h exposure. Therefore, the N-short alkyl substituent was more effective for killing E. coli and the N-long alkyl substituent conferred specific bactericidal activity against S. aureus. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis of methyl (13(2)R/S)-alkyl-pyropheophorbide a and a non-epimerized chlorophyll a mimic.

PubMed

Ogasawara, Shin; Tamiaki, Hitoshi

2015-10-15

The (13(2)R/S)-methoxycarbonyl group of methyl pheophorbides a/a' (chlorophyll a/a' derivatives) was converted to methyl, ethyl, propyl, and isopropyl groups through the C13(2)-alkylation under basic conditions followed by pyrolysis in 2,4,6-collidine with lithium iodide. All the resulting products, methyl 13(2)-alkyl-pyropheophorbides a, predominantly gave the (13(2)R)-stereoisomers with about one tenth of the (13(2)S)-epimers. Their stereochemistry was determined by 1D/2D NMR and their optical properties were characterized by visible absorption and circular dichroism spectroscopy. Methyl (13(2)R)-propyl-pyropheophorbide a was converted to (13(2)R)-propyl-pyrochlorophyll a by ester exchanging and magnesium chelating reactions. The synthetic chlorophyll a analogue showed non-epimerization at the 13(2)-position in pyridine-d5 at 40°C, while naturally occurring chlorophyll a was easily epimerized under the same conditions to give its epimeric mixture. Copyright © 2015 Elsevier Ltd. All rights reserved.

JPRS Report Science & Technology USSR: Life Sciences.

DTIC Science & Technology

1988-07-18

SOTSIALISTICHESKAYA INDUSTRIYA, 31 Jan 87, 1 Feb 87) 79 PSYCHOLOGY Psychoprevention and Psychotherapy of Alcoholism (V.Ye. Rozhnov, M.Ye. Burno...IMMOBILIZOVANNYYE FERMENTY V MEDITSINE INOVOYE V ZHIZNI, NAUKE, TEKHNIKE: SERIYA "KRTMIYA"] , No 9, Sep 86) 3 Isolation of Cholesterol Oxidase ...No 5, Sep-Oct 86) 17 Alkylation of Benzo- and Dibenzocrown Esters With Various Alcohols (A. K. Tashmukhamedova, I. A. Stempnevskaya, et al

Order of functionality loss during photodegradation of aquatic humic substances

USGS Publications Warehouse

Thorn, Kevin A.; Younger, Steven J.; Cox, Larry G.

2009-01-01

The time course photodegradation of the Nordic aquatic fulvic and humic acids and Suwannee River XAD-4 acids subjected to UV irradiation with an unfiltered medium pressure mercury lamp was studied by liquid-state 13C nuclear magnetic resonance. Photodecarboxylation was a significant pathway in all cases. Decreases in ketone, aromatic, and O-alkyl carbons were observed throughout the course of the irradiations, whereas C-alkyl carbons resisted photodegradation. Peaks attributable to the low-molecular-weight photodegradation products bicarbonate, formate, acetate, and succinate grew in intensity with irradiation time. The final products of the irradiations were decarboxylated, hydrophobic, predominantly C-alkyl and O-alkyl materials that were resistant to further photodegradation. The total amount of carbon susceptible to loss appeared to be related mainly to the total concentration of carbonyl and aromatic carbons and partly to the concentration of O-alkyl carbons in the fulvic, humic, and XAD-4 acids. The carbon losses for Nordic fulvic, Nordic Humic, Suwannee fulvic, and Suwannee XAD-4 acids were estimated to be 75, 63, 56, and 17%, respectively. More detailed analyses of the effects of irradiation on the carbonyl functionality in Nordic humic acid and Laurentian soil fulvic acid through reaction with hydroxylamine in conjunction with 15N nuclear magnetic resonance analysis confirmed preferential photodegradation of the quinone/hydroquinone functionality over ketone groups and the loss of ester groups in Laurentian fulvic acid.

Amide and Ester-Functionalized Humic Acid for Fuel Combustion Enhancement

NASA Astrophysics Data System (ADS)

Riggs, Mark

Humic acid is a class of naturally occurring molecules composed of large sheet-like regions of cyclic aromatic hydrocarbon networks with surface and edge functional groups including phenols, carboxylic acids, and epoxides. These naturally occurring molecules are found in brown coal deposits near lignite formations. Humic acid has gained attention from the scientific community as a precursor for graphene. Graphene is a 2-dimensional honeycomb structure of fully unsaturated carbon atoms that has exceptional material properties and inherent aromaticity. Graphene's incredible properties are matched by the difficulty associated with reproducibly manufacturing it on a large scale. This issue has limited the use of graphene for commercial applications. The polar functional groups of humic acid contribute to the hydrophilic nature of the molecule, limiting its miscibility in any alkyl-based solvent. Surfactants containing long alkyl chains can affect the miscibility of the molecule in an organic solvent. Surfactants are often difficult to remove from the system. It is theorized that alkylation of the functional sites of humic acid can affect the hydrophilic nature of the molecule, and effectively enable its dispersion into organic solvents without simultaneous incorporation of surfactants. This dissertation investigated the amidation and esterification of humic acid molecules extracted from leonardite. The resulting change in the modified humic acid dispersibility in organic solvents and its potential usage as a fuel additive were evaluated. Butyl, hexyl, octyl, and decyl amide-modified and ester-modified humic acids were synthesized. These products were characterized to confirm successful chemical reaction through thermogravimetric analysis, Fourier-transform infrared spectroscopy, and scanning electron microscopy. The decyl-modified humic acids remained suspended in kerosene mixtures for longer than 1 week. Other organo-humic acids showed varying degrees of flocculation. The modified humic acid samples were diluted with kerosene to identify the influence on combustion properties. Butyl-modified humic acid samples decreased the molar enthalpy of combustion. Hexyl, octyl, and decyl-modified humic acids improved the combustion values. Decyl amide-modified humic acid showed the largest improvement of these mixtures with a 0.9% increase from the expected molar enthalpy of combustion with a loading percentage of 0.36% in kerosene. Octyl amide-modified and octyl ester-modified humic acid mixtures were prepared in 0.05, 0.1, and 1% loading percentage dilutions to study the effect of modified humic acid loading percent on combustion properties. The 0.1% dilution showed the largest increase of the expected molar enthalpy of combustion by 1.14% and 0.4% for amide-modified HA and ester-modified HA, respectively.

A novel type of highly effective nonionic gemini alkyl O-glucoside surfactants: a versatile strategy of design.

PubMed

Liu, Songbai; Sang, Ruocheng; Hong, Shan; Cai, Yujing; Wang, Hua

2013-07-09

A novel type of highly effective gemini alkyl glucosides has been rationally designed and synthesized. The gemini surfactants have been readily prepared by glycosylation of the gemini alkyl chains that are synthesized with regioselective ring-opening of ethylene glycol epoxides by the alkyl alcohols. The new gemini alkyl glucosides exhibit significantly better surface activity than the known results. Then rheological, DLS, and TEM studies have revealed the intriguing self-assembly behavior of the novel gemini surfactants. This study has proved the effectiveness of the design of gemini alkyl glucosides which is modular, extendable, and synthetically simple. The new gemini surfactants have great potential as nano carriers in drug and gene delivery.

Alkylating agent induced NRF2 blocks endoplasmic reticulum stress-mediated apoptosis via control of glutathione pools and protein thiol homeostasis

PubMed Central

Zanotto-Filho, Alfeu; Masamsetti, V. Pragathi; Loranc, Eva; Tonapi, Sonal S.; Gorthi, Aparna; Bernard, Xavier; Gonçalves, Rosângela Mayer; Moreira, José C. F.; Chen, Yidong; Bishop, Alexander J. R.

2016-01-01

Alkylating agents are a commonly used cytotoxic class of anticancer drugs. Understanding the mechanisms whereby cells respond to these drugs is key to identify means to improve therapy while reducing toxicity. By integrating genome-wide gene expression profiling, protein analysis and functional cell validation, we herein demonstrated a direct relationship between NRF2 and Endoplasmic Reticulum (ER) stress pathways in response to alkylating agents, which is coordinated by the availability of glutathione (GSH) pools. GSH is essential for both drug detoxification and protein thiol homeostasis within the ER, thus inhibiting ER stress induction and promoting survival; an effect independent of its antioxidant role. NRF2 accumulation induced by alkylating agents resulted in increased GSH synthesis via GCLC/GCLM enzyme, and interfering with this NRF2 response by either NRF2 knockdown or GCLC/GCLM inhibition with buthionine sulfoximine (BSO) caused accumulation of damaged proteins within the ER, leading to PERK-dependent apoptosis. Conversely, upregulation of NRF2, through KEAP1 depletion or NRF2-myc overexpression, or increasing GSH levels with N-acetylcysteine (NAC) or glutathione-ethyl-ester (GSH-E), decreased ER stress and abrogated alkylating agents-induced cell death. Based on these results, we identified a subset of lung and head-and-neck carcinomas with mutations in either KEAP1 or NRF2/NFE2L2 genes that correlate with NRF2 targets overexpression and poor survival. In KEAP1 mutant cancer cells, NRF2 knockdown and GSH depletion increased cell sensitivity via ER stress induction in a mechanism specific to alkylating drugs. Overall, we show that the NRF2-GSH influence on ER homeostasis implicates defects in NRF2-GSH or ER stress machineries as affecting alkylating therapy toxicity. PMID:27638861

Catalyst-free dehydrative α-alkylation of ketones with alcohols: green and selective autocatalyzed synthesis of alcohols and ketones.

PubMed

Xu, Qing; Chen, Jianhui; Tian, Haiwen; Yuan, Xueqin; Li, Shuangyan; Zhou, Chongkuan; Liu, Jianping

2014-01-03

Direct dehydrative α-alkylation reactions of ketones with alcohols are now realized under simple, practical, and green conditions without using external catalysts. These catalyst-free autocatalyzed alkylation methods can efficiently afford useful alkylated ketone or alcohol products in a one-pot manner and on a large scale by CC bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid-phase characterization of molecular interactions in polyunsaturated and n-fatty acid methyl esters by (1)H low-field nuclear magnetic resonance.

PubMed

Meiri, Nitzan; Berman, Paula; Colnago, Luiz Alberto; Moraes, Tiago Bueno; Linder, Charles; Wiesman, Zeev

2015-01-01

To identify and develop the best renewable and low carbon footprint biodiesel substitutes for petroleum diesel, the properties of different biodiesel candidates should be studied and characterized with respect to molecular structures versus biodiesel liquid property relationships. In our previous paper, (1)H low-field nuclear magnetic resonance (LF-NMR) relaxometry was investigated as a tool for studying the liquid-phase molecular packing interactions and morphology of fatty acid methyl esters (FAMEs). The technological potential was demonstrated with oleic acid and methyl oleate standards having similar alkyl chains but different head groups. In the present work, molecular organization versus segmental and translational movements of FAMEs in their pure liquid phase, with different alkyl chain lengths (10-20 carbons) and degrees of unsaturation (0-3 double bonds), were studied with (1)H LF-NMR relaxometry and X-ray, (1)H LF-NMR diffusiometry, and (13)C high-field NMR. Based on density values and X-ray measurements, it was proposed that FAMEs possess a liquid crystal-like order above their melting point, consisting of random liquid crystal aggregates with void spaces between them, whose morphological properties depend on chain length and degree of unsaturation. FAMEs were also found to exhibit different degrees of rotational and translational motions, which were rationalized by chain organization within the clusters, and the degree and type of molecular interactions and temperature effects. At equivalent fixed temperature differences from melting point, saturated FAME molecules were found to have similar translational motion regardless of chain length, expressed by viscosity, self-diffusion coefficients, and spin-spin (T 2) (1)H LF-NMR. T 2 distributions suggest increased alkyl chain rigidity, and reduced temperature response of the peaks' relative contribution with increasing unsaturation is a direct result of the alkyl chain's morphological packing and molecular interactions. Both the peaks' assignments for T 2 distributions of FAMEs and the model for their liquid crystal-like morphology in the liquid phase were confirmed. The study of morphological structures within liquids and their response to temperature changes by (1)H LF-NMR has a high value in the field of biodiesel and other research and applied disciplines in numerous physicochemical- and organizational-based properties, processes, and mechanisms of alkyl chains, molecular interactions, and morphologies.

LFER and CoMFA studies on optical resolution of alpha-alkyl alpha-aryloxy acetic acid methyl esters on DACH-DNB chiral stationary phase.

PubMed

Carotti, A; Altomare, C; Cellamare, S; Monforte, A; Bettoni, G; Loiodice, F; Tangari, N; Tortorella, V

1995-04-01

The HPLC resolution of a series of racemic alpha-substituted alpha-aryloxy acetic acid methyl esters I on a pi-acid N,N'-(3,5-dinitrobenzoyl)-trans-1,2-diaminocyclohexane as chiral selector was modelled by linear free energy-related (LFER) equations and comparative molecular field analysis (CoMFA). Our results indicate that the retention process mainly depends on solute lipophilicity and steric properties, whereas enantioselectivity is primarily influenced by electrostatic and steric interactions. CoMFA provided additional information with respect to the LFER study, allowed the mixing of different subsets of I and led to a quantitative 3D model of steric and electrostatic factors responsible for chiral recognition.

Combining regio- and enantioselectivity of lipases for the preparation of (R)-4-chloro-2-butanol.

PubMed

Méndez, Jonh J; Oromi, Mireia; Cervero, Maria; Balcells, Mercè; Torres, Mercè; Canela, Ramon

2007-01-01

Preparation of 98% ee (R)-4-chloro-2-butanol was carried out by the enzymatic hydrolysis of chlorohydrin esters, using fungal resting cells and commercial enzymes. Hydrolyzes were carried out using lipases from Candida antarctica (Novozym 435), C. rugosa, Rhizomucor miehei (Lipozyme IM), Burkolia cepacia, and resting cells of Rhizopus oryzae and Aspergillus flavus. The influence of the enzyme, the solvent, the temperature, and the alkyl chain length on the selectivity of hydrolyzes of isomeric mixtures of chlorohydrin esters is described. Regioselectivity was higher than 95% for some of the tested lipases. Novozym 435 allowed preparation of the (R)-4-chloro-2-butanol after 15 min of reaction at 30-40 degrees C. (c) 2006 Wiley-Liss, Inc.

Silicate Esters of Paclitaxel and Docetaxel: Synthesis, Hydrophobicity, Hydrolytic Stability, Cytotoxicity, and Prodrug Potential

PubMed Central

2015-01-01

We report here the synthesis and selected properties of various silicate ester derivatives (tetraalkoxysilanes) of the taxanes paclitaxel (PTX) and docetaxel (DTX) [i.e., PTX-OSi(OR)3 and DTX-OSi(OR)3]. Both the hydrophobicity and hydrolytic lability of these silicates can be (independently) controlled by choice of the alkyl group (R). The synthesis, structural characterization, hydrolytic reactivity, and in vitro cytotoxicity against the MDA-MB-231 breast cancer cell line of most of these derivatives are described. We envision that the greater hydrophobicity of these silicates (vis-à-vis PTX or DTX itself) should be advantageous from the perspective of preparation of stable aqueous dispersions of amphiphilic block-copolymer-based nanoparticle formulations. PMID:24564494

A poly(alkyl methacrylate-divinylbenzene-vinylbenzyl trimethylammonium chloride) monolithic column for solid-phase microextraction.

PubMed

Liu, Wan-Ling; Lirio, Stephen; Yang, Yicong; Wu, Lin-Tai; Hsiao, Shu-Ying; Huang, Hsi-Ya

2015-05-22

In this study, an organic polymer monolithic columns, which were prepared via in situ polymerization of alkyl methacrylate-ester (AMA), divinylbenzene (DVB) and vinylbenzyl trimethylammonium chloride (VBTA, charged monomer), were developed as adsorbent for solid-phase microextraction (SPME). Different parameters affecting the extraction efficiency for nine (9) non-steroidal anti-inflammatory drugs (NSAIDs) such as the ratio of the stearyl methacrylate (SMA) to DVB monomer, column length, sample pH, extraction flow rate and desorption solvent were investigated to obtain the optimal SPME condition. Also, the permeability for each poly(AMA-DVB-VBTA) monolithic column was investigated by adding porogenic solvent (poly(ethylene glycol), PEG). Using the optimized condition, a series of AMA-based poly(AMA-DVB-VBTA) monolith columns were developed to determine the effect the extraction efficiency of NSAIDs by varying the alkyl chain length of the methacrylate ester (methyl-, butyl-, octyl-, or lauryl-methacrylate; (MMA, BMA, OMA, LMA)). Results showed that decreasing the AMA chain length increases the extraction efficiency of some NSAIDs (i.e. sulindac (sul), naproxen (nap), ketoprofen (ket) and indomethacin (idm)). Among the poly(AMA-DVB-VBTA) monolithic columns, poly(BMA-DVB-VBTA) showed a highly repeatable extraction efficiency for NSAIDs with recoveries ranging from 85.0 to 100.2% with relative standard deviation (RSD) less than 6.8% (n=3). The poly(BMA-DVB-VBTA) can also be reused for at least 50 times without any significant effect in extraction efficiency for NSAIDs. Finally, using the established conditions, the poly(BMA-DVB-VBTA) was used to extract trace-level NSAIDs (100μgL(-1)) in river water with good recoveries ranging from 75.8 to 90.8% (RSD<14.9%). Copyright © 2015 Elsevier B.V. All rights reserved.

Poor recognition of O6-isopropyl dG by MGMT triggers double strand break-mediated cell death and micronucleus induction in FANC-deficient cells

PubMed Central

Hashimoto, Kiyohiro; Sharma, Vyom; Sasanuma, Hiroyuki; Tian, Xu; Takata, Minoru; Takeda, Shunichi; Swenberg, James A.; Nakamura, Jun

2016-01-01

Isopropyl methanesulfonate (IPMS) is the most potent genotoxic compound among methanesulfonic acid esters. The genotoxic potential of alkyl sulfonate esters is believed to be due to their alkylating ability of the O6 position of guanine. Understanding the primary repair pathway activated in response to IPMS-induced DNA damage is important to profile the genotoxic potential of IPMS. In the present study, both chicken DT40 and human TK6 cell-based DNA damage response (DDR) assays revealed that dysfunction of the FANC pathway resulted in higher sensitivity to IPMS compared to EMS or MMS. O6-alkyl dG is primarily repaired by methyl guanine methyltransferase (MGMT), while isopropyl dG is less likely to be a substrate for MGMT. Comparison of the cytotoxic potential of IPMS and its isomer n-propyl methanesulfonate (nPMS) revealed that the isopropyl moiety avoids recognition by MGMT and leads to higher cytotoxicity. Next, the micronucleus (MN) assay showed that FANC deficiency increases the sensitivity of DT40 cells to MN induction by IPMS. Pretreatment with O6-benzyl guanine (OBG), an inhibitor of MGMT, increased the MN frequency in DT40 cells treated with nPMS, but not IPMS. Lastly, IPMS induced more double strand breaks in FANC-deficient cells compared to wild-type cells in a time-dependent manner. All together, these results suggest that IPMS-derived O6-isopropyl dG escapes recognition by MGMT, and the unrepaired DNA damage leads to double strand breaks, resulting in MN induction. FANC, therefore, plays a pivotal role in preventing MN induction and cell death caused by IPMS. PMID:27486975

Enantioselective synthesis of α-phenyl- and α-(dimethylphenylsilyl)alkylboronic esters by ligand mediated stereoinductive reagent-controlled homologation using configurationally labile carbenoids.

PubMed

Barsamian, Adam L; Wu, Zhenhua; Blakemore, Paul R

2015-03-28

Chain extension of boronic esters by the action of configurationally labile racemic lithium carbenoids in the presence of scalemic bisoxazoline ligands was explored for the enantioselective synthesis of the two title product classes. Enantioenriched 2° carbinols generated by oxidative work-up (NaOOH) of initial α-phenylalkylboronate products were obtained in 35-83% yield and 70-96% ee by reaction of B-alkyl and B-aryl neopentyl glycol boronates with a combination of O-(α-lithiobenzyl)-N,N-diisopropylcarbamate and ligand 3,3-bis[(4S)-4,5-dihydro-4-isopropyloxazol-2-yl] pentane in toluene solvent (-78 °C to rt) with MgBr2·OEt2 additive. Enantioenriched α-(dimethylsilylphenylsilyl)alkylboronates were obtained in 35-69% yield and 9-57% ee by reaction of B-alkyl pinacol boronates with a combination of lithio(dimethylphenylsilyl)methyl 2,4,6-triisopropylbenzoate and ligand 2,2-bis[(4S)-4,5-dihydro-4-isopropyloxazol-2-yl]propane in cumene solvent (-45 °C to -95 °C to rt). The stereochemical outcome of the second type of reaction depended on the temperature history of the organolithium·ligand complex indicating that the stereoinduction mechanism in this case involves some aspect of dynamic thermodynamic resolution.

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

NASA Technical Reports Server (NTRS)

Huang, Chen-Kuo (Inventor); Smart, Marshall C. (Inventor); Surampudi, Subbarao (Inventor); Bugga, Ratnakumar V. (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

Palladium-Catalyzed Asymmetric Alkylation in the Synthesis of Cyclopentanoid and Cycloheptanoid Core Structures Bearing All-Carbon Quaternary Stereocenters

PubMed Central

Hong, Allen Y.; Bennett, Nathan B.; Krout, Michael R.; Jensen, Thomas; Harned, Andrew. M.

2011-01-01

General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems. PMID:22347731

De novo Biosynthesis of Biodiesel by Escherichia coli in Optimized Fed-Batch Cultivation

PubMed Central

Cai, Ke; Tan, Xiaoming; Lu, Xuefeng

2011-01-01

Biodiesel is a renewable alternative to petroleum diesel fuel that can contribute to carbon dioxide emission reduction and energy supply. Biodiesel is composed of fatty acid alkyl esters, including fatty acid methyl esters (FAMEs) and fatty acid ethyl esters (FAEEs), and is currently produced through the transesterification reaction of methanol (or ethanol) and triacylglycerols (TAGs). TAGs are mainly obtained from oilseed plants and microalgae. A sustainable supply of TAGs is a major bottleneck for current biodiesel production. Here we report the de novo biosynthesis of FAEEs from glucose, which can be derived from lignocellulosic biomass, in genetically engineered Escherichia coli by introduction of the ethanol-producing pathway from Zymomonas mobilis, genetic manipulation to increase the pool of fatty acyl-CoA, and heterologous expression of acyl-coenzyme A: diacylglycerol acyltransferase from Acinetobacter baylyi. An optimized fed-batch microbial fermentation of the modified E. coli strain yielded a titer of 922 mg L−1 FAEEs that consisted primarily of ethyl palmitate, -oleate, -myristate and -palmitoleate. PMID:21629774

Methodology for in situ protection of aldehydes and ketones using trimethylsilyl trifluoromethanesulfonate and phosphines: selective alkylation and reduction of ketones, esters, amides, and nitriles.

PubMed

Yahata, Kenzo; Minami, Masaki; Yoshikawa, Yuki; Watanabe, Kei; Fujioka, Hiromichi

2013-01-01

A methodology for selective transformations of ketones, esters, Weinreb amides, and nitriles in the presence of aldehydes has been developed. The use of a combination of PPh(3)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) promotes selective transformation of aldehydes to their corresponding, temporarily protected, O,P-acetal type phosphonium salts. Because, hydrolytic work-up following ensuing reactions of other carbonyl moieties in the substrates liberates the aldehyde moiety, a sequence involving aldehyde protection, transformation of other carbonyl groups, and deprotection can be accomplished in a one-pot manner. Furthermore, the use of PEt(3) instead of PPh(3) enables ketones to be converted in situ to their corresponding O,P-ketal type phosphonium salts and, consequently, selective transformations of esters, Weinreb amides, and nitriles in the presence of ketones can be performed. This methodology is applicable to various dicarbonyl compounds, including substrates that possess heteroaromatic skeletons and hydroxyl protecting groups.

Protection Against the Acute and Delayed Toxicity of Mustards and Mustard-Like Compounds

DTIC Science & Technology

1987-02-01

environ- mental agents can be more important than modification at the major alkylation sites, an important inicial objective of this work was to identify...position of guanine in DNA. A mechanism has been discovered for certain antitumor agents which leads to DNA cross-linking following alkylation of the O...been discovered. Simple monofunctional alkylating agents , including methylating agents , appear to cause cross-link- ing through the reactions of the

Tailored dendritic core-multishell nanocarriers for efficient dermal drug delivery: A systematic top-down approach from synthesis to preclinical testing.

PubMed

Hönzke, Stefan; Gerecke, Christian; Elpelt, Anja; Zhang, Nan; Unbehauen, Michael; Kral, Vivian; Fleige, Emanuel; Paulus, Florian; Haag, Rainer; Schäfer-Korting, Monika; Kleuser, Burkhard; Hedtrich, Sarah

2016-11-28

Drug loaded dendritic core-multishell (CMS) nanocarriers are of especial interest for the treatment of skin diseases, owing to their striking dermal delivery efficiencies following topical applications. CMS nanocarriers are composed of a polyglycerol core, connected by amide-bonds to an inner alkyl shell and an outer methoxy poly(ethylene glycol) shell. Since topically applied nanocarriers are subjected to biodegradation, the application of conventional amide-based CMS nanocarriers (10-A-18-350) has been limited by the potential production of toxic polyglycerol amines. To circumvent this issue, three tailored ester-based CMS nanocarriers (10-E-12-350, 10-E-15-350, 10-E-18-350) of varying inner alkyl chain length were synthesized and comprehensively characterized in terms of particle size, drug loading, biodegradation and dermal drug delivery efficiency. Dexamethasone (DXM), a potent drug widely used for the treatment of inflammatory skin diseases, was chosen as a therapeutically relevant test compound for the present study. Ester- and amide-based CMS nanocarriers delivered DXM more efficiently into human skin than a commercially available DXM cream. Subsequent in vitro and in vivo toxicity studies identified CMS (10-E-15-350) as the most biocompatible carrier system. The anti-inflammatory potency of DXM-loaded CMS (10-E-15-350) nanocarriers was assessed in TNFα supplemented skin models, where a significant reduction of the pro-inflammatory cytokine IL-8 was seen, with markedly greater efficacy than commercial DXM cream. In summary, we report the rational design and characterization of tailored, biodegradable, ester-based CMS nanocarriers, and their subsequent stepwise screening for biocompatibility, dermal delivery efficiency and therapeutic efficacy in a top-down approach yielding the best carrier system for topical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Intramolecular cyclization of N-phenyl N'(2-chloroethyl)ureas leads to active N-phenyl-4,5-dihydrooxazol-2-amines alkylating β-tubulin Glu198 and prohibitin Asp40.

PubMed

Trzeciakiewicz, Anna; Fortin, Sébastien; Moreau, Emmanuel; C-Gaudreault, René; Lacroix, Jacques; Chambon, Christophe; Communal, Yves; Chezal, Jean-Michel; Miot-Noirault, Elisabeth; Bouchon, Bernadette; Degoul, Françoise

2011-05-01

The cyclization of anticancer drugs into active intermediates has been reported mainly for DNA alkylating molecules including nitrosoureas. We previously defined the original cytotoxic mechanism of anticancerous N-phenyl-N'-(2-chloroethyl)ureas (CEUs) that involves their reactivity towards cellular proteins and not against DNA; two CEU subsets have been shown to alkylate β-tubulin and prohibitin leading to inhibition of cell proliferation by G₂/M or G₁/S cell cycle arrest. In this study, we demonstrated that cyclic derivatives of CEUs, N-phenyl-4,5-dihydrooxazol-2-amines (Oxas) are two- to threefold more active than CEUs and share the same cytotoxic properties in B16F0 melanoma cells. Moreover, the CEU original covalent binding by an ester linkage on β-tubulin Glu198 and prohibitin Asp40 was maintained with Oxas. Surprisingly, we observed that Oxas were spontaneously formed from CEUs in the cell culture medium and were also detected within the cells. Our results suggest that the intramolecular cyclization of CEUs leads to active Oxas that should then be considered as the key intermediates for protein alkylation. These results will be useful for the design of new prodrugs for cancer chemotherapy. Copyright © 2011 Elsevier Inc. All rights reserved.

Study of magnetization switching for MRAM based memory technologies

NASA Astrophysics Data System (ADS)

Pham, Huy

Amphibian alkaloids are attractive targets for synthesis due to their biological activity. An important class of amphibian alkaloids is the 2,5-disubstituted pyrrolidine-based family of compounds. There are many synthetic approaches for the preparation of the trans-2,5-disubstituted pyrrolidines, but methods for the construction of the cis-2,5-pyrrolidines are limited. Therefore, it was desired to develop an enantioselective approach for the preparation of cis-2,5-disubsituted pyrrolidines. (+)-Tropin-2-one derived from cocaine was used as starting material to exploit the inherent stereochemistry for construction of the cis-pyrrolidine ring. This permitted the unequivocal assignment of the absolute configuration of the target pyrrolidine. The structurally simple pyrrolidine alkaloid, 225H, was selected as a target to develop a general synthetic approach. The enantioselective synthesis of 225H was achieved in nine steps and good overall yield. The search for potent cannabinoid receptor partial agonist ligands as potential marijuana addiction therapeutic agents has led to an investigation of the synthesis of diaryl ether hybrid analogues of BAY 59-3074. A series of 2-(3-alkyl-5-hydroxyphenoxy)-6-(trifluoromethyl)benzonitriles, 3-(2-cyano-3-(trifluoromethyl)phenoxy)phenylalkanoates, and (3-(benzyloxy)phenoxy)-6-(trifluoromethyl)benzonitriles were synthesized and evaluated in vitro for CB1 affinity. The olivetol diaryl ether analogue was the most potent ligand of the alkyl series, but the diaryl ester analogues exhibited modest affinity for CB1 receptors. The most potent compound of the series was the 2-(3-(benzyloxy)phenoxy)-6-(trifluoromethyl)benzonitrile. Keywords. amphibian alkaloids, enantioselective synthesis, pyrrolidine, cannabinoid receptor, marijuana.

A simple synthesis of 2-keto-3-deoxy-D-erythro-hexonic acid isopropyl ester, a key sugar for the bacterial population living under metallic stress.

PubMed

Grison, Claire M; Renard, Brice-Loïc; Grison, Claude

2014-02-01

2-Keto-3-deoxy-D-erythro-hexonic acid (KDG) is the key intermediate metabolite of the Entner Doudoroff (ED) pathway. A simple, efficient and stereoselective synthesis of KDG isopropyl ester is described in five steps from 2,3-O-isopropylidene-D-threitol with an overall yield of 47%. KDG isopropyl ester is studied as an attractive marker of a functional Entner Doudoroff pathway. KDG isopropyl ester is used to promote growth of ammonium producing bacterial strains, showing interesting features in the remediation of heavy-metal polluted soils. Copyright © 2013 Elsevier Inc. All rights reserved.

Novel agrochemical conjugates with self-assembling behaviour.

PubMed

Liu, Qingtao; Graham, Bim; Hawley, Adrian; Dong, Yao-Da; Boyd, Ben J

2018-02-15

That conjugation of agrichemicals to pro-assembly hydrophobic moieties will enable enhanced compatibility and loading with host lyotropic liquid crystalline carrier matrix, and potentially self-assemble in their own right in aqueous environments. A series of lipid-like agrochemical-conjugates were synthesized using specific amphiphilic entities conjugated onto the agrochemicals, picloram and 2,4-dichlorophenoxyacetic acid (2,4-D). The self-assembly behaviour and compatibility of the novel entities when incorporated into phytantriol and monoolein-based liquid crystalline systems were examined using small angle X-ray scattering, cryo-TEM and polarized optical microscopy. Compared to agrochemical-conjugates with simple alkyl ester groups, the esterification of the agrochemicals with amphiphilic groups such as phytantriol and monoolein led to greater structural compatibility and consequently a greater loading of the agrochemicals in the liquid crystalline systems without destabilizing phase structure. Picloram-monoolein and picloram-monoelaidin can self-assemble to form lamellar structures in water. However, certain agrochemical-conjugates such as picloram-monoelaidin and picloram-PEGn-oleate showed poor compatibility with liquid crystalline systems, resulting in phase separation. Copyright © 2017 Elsevier Inc. All rights reserved.

Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides.

PubMed

Hoang, G L; Zhang, S; Takacs, J M

2018-05-08

γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.

A study of the natural bitumen of the Mariel deposit (Republic of Cuba)

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

Platanov, V.V.; Ivleva, L.N.; Kalyavina, O.A.

The bitumen of the Mariel deposit, province of Havana, Republic of Cuba, and the products of its ozonolysis and thermal degradation have been studied by a group of physicochemical and chemical methods. It has been shown that the organic part of the bitumen has an aromatic polycondensed structure with mainly short alkyl substituents and ketone, ester, phenol, and quinoid functional groups together with organic sulfur and nitrogen.

Friedel-Crafts Alkylation Using Elemental Aluminum Catalyst: An Undergraduate Laboratory Experiment.

ERIC Educational Resources Information Center

Meeks, B. Spencer; Lucas, Anita R.

1989-01-01

Provides methodology for carrying out the synthesis of sec-butyltoluene by the Friedel-Crafts alkylation of toluene. Suggests using simple elemental aluminum as the catalyst in place of AlCl3 or amalgamated aluminum. Notes satisfactory results for both macro- and microscale operations. (MVL)

Characteristics of oxidative homolytic alkylation of imidazoles and organic-inorganic hybrid extended networks from large aromatic building blocks

NASA Astrophysics Data System (ADS)

Li, Kunhao

The discovery of the dramatic in vitro antimalarial activity of 2-iodo-L-histidine and 2-fluoro-L-histidine, as well as their in vivo limitations, has prompted a systematic search for novel 2-substituted imidazoles and bioimidazoles as agents against human malaria. Previous research has shown that the regioselective alkyl free radical substitution on imidazoles and bioimidazoles could serve as a simple and efficient route to a wide variety of 2-alkylimidazoles. In this research, this methodology was successfully extended to include alkyl radicals substituted with various functional groups such as amide or ester. While this novel methodology should be of some synthetic utility when tertiary radicals are used, poorer yields are usually encountered in the cases of primary radicals. In the second part of this dissertation, a series of novel ligands containing multiple ortho-bis(organothio) groups were synthesized and their coordination and network forming properties were studied in the context of crystalline organic-inorganic hybrid extended networks. For the syntheses of HRTTs [2,3,6,7,10,11-hexakis(alkylthio)triphenylenes], a simpler, safer and higher yielding one-pot process was developed. Quenching the hexa-anions (formed when sodium methylthiolate was refluxed with hexabromotriphenylene) with alkyl halides or acid chlorides afforded HRTTs. This newly developed process was also successfully expanded to the pyrene system. In the syntheses of unsymmetrically substituted triphenlyenes, it was shown for the first time that the oxidative cyclization process is applicable to thioether containing systems, pointing to a novel strategy for the preparation of this type of unsymmetrically substituted triphenlyenes. Treating these novel ligands with various metal salts [i.e. bismuth(III) chloride and bismuth(III) bromide] under carefully controlled conditions resulted in a series of air-stable semiconductive coordination networks. Their single crystal structures were determined by X-ray diffraction and properties such as semiconductivity and solution processability, as well as the structure-property relationship, were also studied. As a reasonable extension of this research, two phenylacetylene-based thioether containing ligands L1 and L2, were prepared. Similar to the triphenylene-based ligands, they also formed semiconductive extended networks with bismuth(III) bromide. The preparation of HArTTs [2,3,6,7,10,11-hexakis-(arylthio)triphenlyenes] and a series of crystalline extended networks based on the coordination of these ligands and various silver salts are reported in Chapter 5.

A palladium iodide-catalyzed carbonylative approach to functionalized pyrrole derivatives.

PubMed

Gabriele, Bartolo; Veltri, Lucia; Mancuso, Raffaella; Salerno, Giuseppe; Maggi, Sabino; Aresta, Brunella Maria

2012-04-20

A novel and convenient approach to functionalized pyrroles is presented, based on Pd-catalyzed oxidative heterocyclization-alkoxycarbonylation of readily available N-Boc-1-amino-3-yn-2-ols. Reactions were carried out in alcoholic solvents at 80-100 °C and under 20 atm (at 25 °C) of a 4:1 mixture of CO-air, in the presence of the PdI(2)-KI catalytic system (2-5 mol % of PdI(2), KI/PdI(2) molar ratio = 10). In the case of N-Boc-1-amino-3-yn-2-ols 3, bearing alkyl or aryl substituents, the carbonylation reaction led to a mixture of Boc-protected and N-unsubstituted pyrrole-3-carboxylic esters 4 and 5, respectively. This mixture could be conveniently and quantitatively converted into deprotected pyrrole-3-carboxylic esters 5 by a simple basic treatment. In the case of diastereomeric (3RS,4RS)- and (3RS,4SR)-N-Boc-3-amino-2-methyldec-5-yn-4-ol (syn-3f and anti-3f, respectively, whose relative configuration was determined by X-ray crystallographic analysis), no particular difference was observed in the reactivity of the two diastereomers between them and with respect to the diastereomeric mixture (3S,4S) + (3S,4R). Interestingly, N-Boc-2-alkynyl-1-amino-3-yn-2-ols 6, bearing an additional alkynyl substituent α to the hydroxyl group, spontaneously underwent N-deprotection under the reaction conditions and regioselective water addition to the alkynyl group at C-3 of the corresponding pyrrole-3-carboxylic ester derivative, thus directly affording highly functionalized pyrrole derivatives 7 in one step. In a similar manner, a novel functionalized dihydropyrrolizine derivative 9 was directly synthesized starting from (S)-7-(pyrrolidin-2-yl)trideca-5,8-diyn-7-ol 8. © 2012 American Chemical Society

Preparation and characterization of bio-diesels from various bio-oils.

PubMed

Lang, X; Dalai, A K; Bakhshi, N N; Reaney, M J; Hertz, P B

2001-10-01

Methyl, ethyl, 2-propyl and butyl esters were prepared from canola and linseed oils through transesterification using KOH and/ or sodium alkoxides as catalysts. In addition, methyl and ethyl esters were prepared from rapeseed and sunflower oils using the same catalysts. Chemical composition of the esters was determined by HPLC for the class of lipids and by GC for fatty acid compositions. The bio-diesel esters were characterized for their physical and fuel properties including density, viscosity, iodine value, acid value, cloud point, pure point, gross heat of combustion and volatility. Methyl and ethyl esters prepared from a particular vegetable oil had similar viscosities, cloud points and pour points, whereas methyl, ethyl, 2-propyl and butyl esters derived from a particular vegetable oil had similar gross heating values. However, their densities, which were 2 7% higher than those of diesel fuels, statistically decreased in the order of methyl approximately 2-propyl > ethyl > butyl esters. Butyl esters showed reduced cloud points (-6 degrees C to -10 degrees C) and pour points (-13 degrees C to -16 degrees C) similar to those of summer diesel fuel having cloud and pour points of -8 degrees C and -15 degrees C, respectively. The viscosities of bio-diesels (3.3-7.6 x 10(-4) Pa s at 40 degrees C) were much less than those of pure oils (22.4-45.1 x 10(-4) Pa s at 40 degrees C) and were twice those of summer and winter diesel fuels (3.50 and 1.72 x 10(-4) Pa s at 40 degrees C), and their gross heat contents of approximately 40 MJ/kg were 11% less than those of diesel fuels (approximately 45 MJ/kg). For different esters from the same vegetable oil, methyl esters were the most volatile, and the volatility decreased as the alkyl group grew bulkier. However, the bio-diesels were considerably less volatile than the conventional diesel fuels.

Practical Alkoxythiocarbonyl Auxiliaries for Iridium(I)-Catalyzed C-H Alkylation of Azacycles.

PubMed

Tran, Anh T; Yu, Jin-Quan

2017-08-21

The development of new and practical 3-pentoxythiocarbonyl auxiliaries for Ir I -catalyzed C-H alkylation of azacycles is described. This method allows for the α-C-H alkylation of a variety of substituted pyrrolidines, piperidines, and tetrahydroisoquinolines through alkylation with alkenes. While the practicality of these simple carbamate-type auxiliaries is underscored by the ease of installation and removal, the method's utility is demonstrated in its ability to functionalize biologically relevant l-proline and l-trans-hydroxyproline, delivering unique 2,5-dialkylated amino acid analogues that are not accessible by other C-H functionalization methods. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alkyl halide-free heteroatom alkylation and epoxidation facilitated by a recyclable polymer-supported oxidant for the in-flow preparation of diazo compounds.

PubMed

Nicolle, Simon M; Hayes, Christopher J; Moody, Christopher J

2015-03-16

Highly reactive metal carbenes, generated from simple ketones via diazo compounds, including diazo-amides and -phosphonates, using a recyclable reagent in-flow, are transient but versatile electrophiles for heteroatom alkylation reactions and for epoxide formation. The method produces no organic waste, with the only by-products being water, KI and nitrogen, without the attendant hazards of isolation of intermediate diazo compounds. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Synthesis of Phenyl Acetylene Phenols for Development of New Explosives

NASA Astrophysics Data System (ADS)

Chikhradze, Nikoloz; Nadirashvili, Merab; Khomeriki, Sergo; Varshanidze, Iasha

2017-12-01

The purpose of this research is to produce derivatives of simple phenols as “raw material” for the synthesis of new phenolic explosives. A big number of valuable products is synthesized from phenol and its homologues including well-known explosives - picric acid, methyl picrate, cresolite, etc. In general, a structural modification of well-known explosives’ molecules is the most important among the methods for the synthesis of new explosives. This method can be used in certain modifications. For example, the synthesis of methyl picrate is possible not only to replace picric acid’s hydroxyl with metoxyl, but with nitration of anisole as well, i. e, by the reciprocating synthesis. Thus, to produce the new analogues of well-known phenolic explosives, the preliminary modification of simple phenols’ molecules and further nitration, presumably by a formation of dinitro derivatives may be performed. The alkylation of phenol, anisole and m - cresol by the secondary phenyl acetylene alcohols in the presence of concentrated phosphoric acid was carried out. Para-substituted alkynyl phenols with high yields were developed. The chemical transformations were carried out by a participation of their molecules’ active centres. The corresponding ethers, esters and saturated isologues have been synthesized. The article describes the conditions of a synthesis of 14 new phenyl acetylenes’ substances that may be used as substrates in a nitration reaction.

Method for the determination of natural ester-type gum bases used as food additives via direct analysis of their constituent wax esters using high-temperature GC/MS.

PubMed

Tada, Atsuko; Ishizuki, Kyoko; Yamazaki, Takeshi; Sugimoto, Naoki; Akiyama, Hiroshi

2014-07-01

Natural ester-type gum bases, which are used worldwide as food additives, mainly consist of wax esters composed of long-chain fatty acids and long-chain fatty alcohols. There are many varieties of ester-type gum bases, and thus a useful method for their discrimination is needed in order to establish official specifications and manage their quality control. Herein is reported a rapid and simple method for the analysis of different ester-type gum bases used as food additives by high-temperature gas chromatography/mass spectrometry (GC/MS). With this method, the constituent wax esters in ester-type gum bases can be detected without hydrolysis and derivatization. The method was applied to the determination of 10 types of gum bases, including beeswax, carnauba wax, lanolin, and jojoba wax, and it was demonstrated that the gum bases derived from identical origins have specific and characteristic total ion chromatogram (TIC) patterns and ester compositions. Food additive gum bases were thus distinguished from one another based on their TIC patterns and then more clearly discriminated using simultaneous monitoring of the fragment ions corresponding to the fatty acid moieties of the individual molecular species of the wax esters. This direct high-temperature GC/MS method was shown to be very useful for the rapid and simple discrimination of varieties of ester-type gum bases used as food additives.

Method for the determination of natural ester-type gum bases used as food additives via direct analysis of their constituent wax esters using high-temperature GC/MS

PubMed Central

Tada, Atsuko; Ishizuki, Kyoko; Yamazaki, Takeshi; Sugimoto, Naoki; Akiyama, Hiroshi

2014-01-01

Natural ester-type gum bases, which are used worldwide as food additives, mainly consist of wax esters composed of long-chain fatty acids and long-chain fatty alcohols. There are many varieties of ester-type gum bases, and thus a useful method for their discrimination is needed in order to establish official specifications and manage their quality control. Herein is reported a rapid and simple method for the analysis of different ester-type gum bases used as food additives by high-temperature gas chromatography/mass spectrometry (GC/MS). With this method, the constituent wax esters in ester-type gum bases can be detected without hydrolysis and derivatization. The method was applied to the determination of 10 types of gum bases, including beeswax, carnauba wax, lanolin, and jojoba wax, and it was demonstrated that the gum bases derived from identical origins have specific and characteristic total ion chromatogram (TIC) patterns and ester compositions. Food additive gum bases were thus distinguished from one another based on their TIC patterns and then more clearly discriminated using simultaneous monitoring of the fragment ions corresponding to the fatty acid moieties of the individual molecular species of the wax esters. This direct high-temperature GC/MS method was shown to be very useful for the rapid and simple discrimination of varieties of ester-type gum bases used as food additives. PMID:25473499

Flavonoids and terpenoids from Luma gayana (Barn.) Burret.

PubMed

Wächter, G A; Wangmaneerat, A; Caple, K M; Montenegro, G; Timmermann, B N

1999-12-01

The flavonoids 5-hydroxy-7-methoxyflavanone, 6,8-dimethyl-5,7-dihydroxyflavanone and 2',4'-dihydroxy-6'-methoxy-3',5'-dimethylchalcone, a mixture of alkyl esters of p-coumaric acid, the triterpenoids oleanolic acid and maslinic acid, the monoterpenoid 1 alpha,2 beta,4 beta-trihydroxy-p-menthane, the sesquiterpenoid clovandiol and beta-sitosterol were isolated from the aerial parts of Luma gayana (Barn.) Burret. This is the first report on the chemistry of this species.

[Synthesis of 1-substituted nitroimidazoles and its evaluation as radiosensitizing agents].

PubMed

Adams, D R; Martul, R; Alvarez, M V; López Zumel, M C; Espada, M

1991-01-01

The synthesis of various substituted nitroimidazoles with lipophilic and hydrophilic side chains as potential radiosensitizing agents is described. The starting material employed was 4(5)-nitroimidazole, which was alkylated via the sodium salt with various chloro-methylated, substituted alcohols and esters, in order to obtain analogues of misonidazole, metronidazole and desmethylmisonidazole of known radiosensitizing and bactericidal activity. Some final products were assayed for their radiosensitizing properties giving negative results under the testing conditions used.

Alkylating Agent-Induced NRF2 Blocks Endoplasmic Reticulum Stress-Mediated Apoptosis via Control of Glutathione Pools and Protein Thiol Homeostasis.

PubMed

Zanotto-Filho, Alfeu; Masamsetti, V Pragathi; Loranc, Eva; Tonapi, Sonal S; Gorthi, Aparna; Bernard, Xavier; Gonçalves, Rosângela Mayer; Moreira, José C F; Chen, Yidong; Bishop, Alexander J R

2016-12-01

Alkylating agents are a commonly used cytotoxic class of anticancer drugs. Understanding the mechanisms whereby cells respond to these drugs is key to identify means to improve therapy while reducing toxicity. By integrating genome-wide gene expression profiling, protein analysis, and functional cell validation, we herein demonstrated a direct relationship between NRF2 and Endoplasmic Reticulum (ER) stress pathways in response to alkylating agents, which is coordinated by the availability of glutathione (GSH) pools. GSH is essential for both drug detoxification and protein thiol homeostasis within the ER, thus inhibiting ER stress induction and promoting survival, an effect independent of its antioxidant role. NRF2 accumulation induced by alkylating agents resulted in increased GSH synthesis via GCLC/GCLM enzyme, and interfering with this NRF2 response by either NRF2 knockdown or GCLC/GCLM inhibition with buthionine sulfoximine caused accumulation of damaged proteins within the ER, leading to PERK-dependent apoptosis. Conversely, upregulation of NRF2, through KEAP1 depletion or NRF2-myc overexpression, or increasing GSH levels with N-acetylcysteine or glutathione-ethyl-ester, decreased ER stress and abrogated alkylating agents-induced cell death. Based on these results, we identified a subset of lung and head-and-neck carcinomas with mutations in either KEAP1 or NRF2/NFE2L2 genes that correlate with NRF2 target overexpression and poor survival. In KEAP1-mutant cancer cells, NRF2 knockdown and GSH depletion increased cell sensitivity via ER stress induction in a mechanism specific to alkylating drugs. Overall, we show that the NRF2-GSH influence on ER homeostasis implicates defects in NRF2-GSH or ER stress machineries as affecting alkylating therapy toxicity. Mol Cancer Ther; 15(12); 3000-14. ©2016 AACR. ©2016 American Association for Cancer Research.

Enantioselective synthesis of anti-β-hydroxy-α-amido esters via transfer hydrogenation.

PubMed

Seashore-Ludlow, Brinton; Villo, Piret; Häcker, Christine; Somfai, Peter

2010-11-19

The asymmetric transfer hydrogenation of α-amido-β-keto esters to provide the corresponding anti-β-hydroxy-α-amido esters in good to excellent yields, diastereoselectivity, and enantioselectivity is reported. The procedure is operationally simple, and delicate handling of the catalyst is not necessary.

A Green Alternative to Aluminum Chloride Alkylation of Xylene

ERIC Educational Resources Information Center

Sereda, Grigoriy A.; Rajpara, Vikul B.

2007-01-01

An acutely less toxic 2-bromobutane is used to develop a simple graphite-promoted procedure of alkylation of p-xylene. It is further demonstrated that aluminum chloride is not required, the need for aqueous workup is eliminated, waste solutions are not produced and the multiple use of the catalyst is allowed.

Cytotoxicity of alkylphenols and alkylated non-phenolics in a primary culture of rainbow trout (Onchorhynchus mykiss) hepatocytes.

PubMed

Tollefsen, K-E; Blikstad, Camilla; Eikvar, Sissel; Farmen Finne, Eivind; Katharina Gregersen, Inger

2008-01-01

Alkylphenols are common aquatic pollutants originating from industrial use of the compounds themselves or as biodegradation products of alkylphenol polyethoxylates. The cytotoxicity of a range of alkylphenols and alkylated non-phenolics were assessed in a primary culture of rainbow trout (Onchorhynchus mykiss) hepatocytes to construct a structure-toxicity relationship for this group of ubiquitous aquatic pollutants. Metabolic inhibition and loss of membrane integrity were used as cytotoxic endpoints through use of the cellular markers Alamar blue and 5-carboxyfluorescein diacetate acetoxymethyl ester, respectively. The results show that cytotoxicity increased with the hydrophobicity of the alkylphenols for compounds with logK(OW)<4.9. Normal chained alkylphenols, branched alkylphenols and multi-substituted alkylphenols with logK(OW)4.9 deviated clearly from this relationship. The alkylphenols displayed greater cytotoxicity than alkylated non-phenolics and it is proposed that most alkylated non-phenolic caused non-polar narcosis (baseline toxicity) whereas the alkylphenols caused polar narcosis. Observations that metabolic inhibition occurred at lower concentrations than loss of membrane integrity for most chemicals indicated that interference with cellular metabolic functions was the main cause of cytotoxicity. Metabolic inhibition corresponded better than loss of membrane integrity to reported acute toxicity to fish, although the in vivo acute toxicity of hydrophobic compounds (logK(OW)>2-3) was clearly underestimated by both endpoints.

Injectable hyperbranched poly(β-amino ester) hydrogels with on-demand degradation profiles to match wound healing processes.

PubMed

Xu, Qian; Guo, Linru; A, Sigen; Gao, Yongsheng; Zhou, Dezhong; Greiser, Udo; Creagh-Flynn, Jack; Zhang, Hong; Dong, Yixiao; Cutlar, Lara; Wang, Fagang; Liu, Wenguang; Wang, Wei; Wang, Wenxin

2018-02-28

Adjusting biomaterial degradation profiles to match tissue regeneration is a challenging issue. Herein, biodegradable hyperbranched poly(β-amino ester)s (HP-PBAEs) were designed and synthesized via "A2 + B4" Michael addition polymerization, and displayed fast gelation with thiolated hyaluronic acid (HA-SH) via a "click" thiol-ene reaction. HP-PBAE/HA-SH hydrogels showed tunable degradation profiles both in vitro and in vivo using diamines with different alkyl chain lengths and poly(ethylene glycol) diacrylates with varied PEG spacers. The hydrogels with optimized degradation profiles encapsulating ADSCs were used as injectable hydrogels to treat two different types of humanized excisional wounds - acute wounds with faster healing rates and diabetic wounds with slower healing and neo-tissue formation. The fast-degrading hydrogel showed accelerated wound closure in acute wounds, while the slow-degrading hydrogel showed better wound healing for diabetic wounds. The results demonstrate that the new HP-PBAE-based hydrogel in combination with ADSCs can be used as a well-controlled biodegradable skin substitute, which demonstrates a promising approach in the treatment of various types of skin wounds.

Mechanism of alkoxy groups substitution by Grignard reagents on aromatic rings and experimental verification of theoretical predictions of anomalous reactions.

PubMed

Jiménez-Osés, Gonzalo; Brockway, Anthony J; Shaw, Jared T; Houk, K N

2013-05-01

The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone, and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated.

Mechanism of Alkoxy Groups Substitution by Grignard Reagents on Aromatic Rings and Experimental Verification of Theoretical Predictions of Anomalous Reactions

PubMed Central

Jiménez-Osés, Gonzalo; Brockway, Anthony J.; Shaw, Jared T.; Houk, K. N.

2013-01-01

The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated. PMID:23601086

Spiroborate Ester-Mediated Asymmetric Synthesis of β-Hydroxy Ethers and its Conversion to Highly Enantiopure β-Amino Ethers

PubMed Central

Huang, Kun; Ortiz-Marciales, Margarita; Correa, Wildeliz; Pomales, Edgardo; López, Xaira Y.

2009-01-01

Borane-mediated reduction of aryl and alkyl ketones with α-aryl- and α-pyridyloxy groups affords β-hydroxy ethers in high enantiomeric purity (up to 99% ee) and in good yield, using as catalyst 10 mol % of spiroborate ester 1 derived from (S)-diphenylprolinol. Representative β-hydroxy ethers are successfully converted to β-amino ethers, with minor epimerization, by phthalimide substitution under Mitsunobu’s conditions followed by hydrazinolysis, to obtain primary amino ethers or by imide reduction with borane to afford β-2,3-dihydro-1H-isoindol ethers. Non-racemic Mexiletine and nAChR analogues with potential biological activity are also synthesized in excellent yield by mesylation of key β-hydroxy pyridylethers and substitution with 5, 6 and 7 member ring heterocyclic amines. PMID:19413288

Enzyme-synthesized Poly(amine-co-esters) as Non-viral Vectors for Gene Delivery

PubMed Central

Liu, Jie; Jiang, Zhaozhong; Zhou, Jiangbing; Zhang, Shengmin; Saltzman, W. Mark

2010-01-01

A family of biodegradable poly(amine-co-esters) was synthesized in one step via enzymatic copolymerization of diesters with amino-substituted diols. Diesters of length C4–C12 (i.e., from succinate to dodecanedioate) were successfully copolymerized with diethanolamines with either an alkyl (methyl, ethyl, n-butyl, t-butyl) or an aryl (phenyl) substituent on the nitrogen. Upon protonation at slightly acidic conditions, these poly(amine-co-esters) readily turned to cationic polyelectrolytes, which were capable of condensing with polyanionic DNA to form nanometer-sized polyplexes. In vitro screening with pLucDNA revealed that two of the copolymers, poly(N-methyldiethyleneamine sebacate) (PMSC) and poly(N-ethyldiethyleneamine sebacate) (PESC), possessed comparable or higher transfection efficiencies compared to Lipofectamine 2000. PMSC/pLucDNA and PESC/pLucDNA nanoparticles had desirable particle sizes (40–70 nm) for cellular uptake and were capable of functioning as proton sponges to facilitate endosomal escape after cellular uptake. These polyplex nanoparticles exhibited extremely low cytotoxicity. Furthermore, in vivo gene transfection experiments revealed that PMSC is a substantially more effective gene carrier than PEI in delivering pLucDNAto cells in tumors in mice. All these properties suggest that poly(amine-co-esters) are promising non-viral vectors for safe and efficient DNA delivery in gene therapy. PMID:21171165

Composition and Process for Retarding the Premature Aging of PMR Monomer Solutions and PMR Prepegs

NASA Technical Reports Server (NTRS)

Alston, William B. (Inventor); Gahn, Gloria S. (Inventor)

2000-01-01

Polyimides are derived from solutions of at least one low-boiling organic solvent, e.g. isopropanol containing a mixture of polyimide-forming monomers. The monomeric solutions have an extended shelf life at ambient (room) temperatures as high as 80 C, and consist essentially of a mixture of monoalkyl ester-acids, alkyl diester-diacids and aromatic polyamines wherein the alkyl radicals of the esteracids are derived from lower molecular weight aliphatic secondary alcohols having 3 to 5 carbon atoms per molecule such as isopropanol, secondary butanol, 2-methyl-3-butanol, 2 pentanol or 3-pentanol. The solutions of the polyimide-forming monomers have a substantially improved shelf-life and are particularly useful in the aerospace and aeronautical industry for the preparation of polyimide reinforced fiber composites such as the polyimide cured carbon composites used in jet engines, missiles, and for other high temperature applications.

Adsorption at air-water and oil-water interfaces and self-assembly in aqueous solution of ethoxylated polysorbate nonionic surfactants.

PubMed

Penfold, Jeffrey; Thomas, Robert K; Li, Peixun X; Petkov, Jordan T; Tucker, Ian; Webster, John R P; Terry, Ann E

2015-03-17

The Tween nonionic surfactants are ethoxylated sorbitan esters, which have 20 ethylene oxide groups attached to the sorbitan headgroup and a single alkyl chain, lauryl, palmityl, stearyl, or oleyl. They are an important class of surfactants that are extensively used in emulsion and foam stabilization and in applications associated with foods, cosmetics and pharmaceuticals. A range of ethoxylated polysorbate surfactants, with differing degrees of ethoxylation from 3 to 50 ethylene oxide groups, have been synthesized and characterized by neutron reflection, small-angle neutron scattering, and surface tension. In conjunction with different alkyl chain groups, this provides the opportunity to modify their surface properties, their self-assembly in solution, and their interaction with macromolecules, such as proteins. Adsorption at the air-water and oil-water interfaces and solution self-assembly of the range of ethoxylated polysorbate surfactants synthesized are presented and discussed.

Cobalt co-catalysis for cross-electrophile coupling: diarylmethanes from benzyl mesylates and aryl halides† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03106g Click here for additional data file.

PubMed Central

Ackerman, Laura K. G.; Anka-Lufford, Lukiana L.; Naodovic, Marina

2015-01-01

The nickel-catalyzed cross-coupling of aryl halides with alkyl radicals derived from alkyl halides has recently been extended to couplings with carbon radicals generated by a co-catalyst. In this study, a new co-catalyst, cobalt phthalocyanine (Co(Pc)), is introduced and demonstrated to be effective for coupling substrates not prone to homolysis. This is because Co(Pc) reacts with electrophiles by an SN2 mechanism instead of by the electron-transfer or halogen abstraction mechanisms previously explored. Studies demonstrating the orthogonal reactivity of (bpy)Ni and Co(Pc), applying this selectivity to the coupling of benzyl mesylates with aryl halides, and the adaptation of these conditions to the less reactive benzyl phosphate ester and an enantioconvergent reaction are presented. PMID:25685312

Molecular water oxidation catalyst

DOEpatents

Gratzel, Michael; Munavalli, Shekhar; Pern, Fu-Jann; Frank, Arthur J.

1993-01-01

A dimeric composition of the formula: ##STR1## wherein L', L", L'", and L"" are each a bidentate ligand having at least one functional substituent, the ligand selected from bipyridine, phenanthroline, 2-phenylpyridine, bipyrimidine, and bipyrazyl and the functional substituent selected from carboxylic acid, ester, amide, halogenide, anhydride, acyl ketone, alkyl ketone, acid chloride, sulfonic acid, phosphonic acid, and nitro and nitroso groups. An electrochemical oxidation process for the production of the above functionally substituted bidentate ligand diaqua oxo-bridged ruthenium dimers and their use as water oxidation catalysts is described.

Oxidation of Peptides by Methyl(trifluoromethyl)dioxirane: the Protecting Group Matters

PubMed Central

Rella, Maria Rosaria; Williard, Paul G.

2011-01-01

Representative Boc protected and acetyl protected peptide methyl esters bearing alkyl side chains undergo effective oxidation using methyl(trifluoromethyl)dioxirane (1b) under mild conditions. We observe a protecting group dependency in the chemoselectivity displayed by the dioxirane 1b. N-hydroxylation occurs in the case of the Boc protected peptides, side chain hydroxylation takes place in the case of acetyl protected peptides. Both are attractive transformations since they yield derivatized peptides that serve as valuable synthons. PMID:17221970

Development of polyimide foams with blowing agents

NASA Technical Reports Server (NTRS)

Gagliani, John (Inventor); Sorathia, Usman A. K. (Inventor); Lee, Raymond (Inventor)

1985-01-01

A method of preparing a polyimide foam which includes the steps of: preparing, foaming, and curing a precursor containing at least one alkyl ester of 3,3'4,4'-benzophenonetetracarboxylic acid; a meta- or para-substituted aromatic diamine; a heterocyclic diamine; an aliphatic diamine; and a solid blowing agent. The blowing agent is added to said precursor in a concentration which is sufficient to effect at least one of the following attributes of the foam: cell size, proportion of open cells, cell density, and indentation load deflection.

A new hypercrosslinked supermicroporous polymer, with scope for sulfonation, and its catalytic potential for the efficient synthesis of biodiesel at room temperature.

PubMed

Bhunia, Subhajit; Banerjee, Biplab; Bhaumik, Asim

2015-03-25

We have designed a new hypercrosslinked supermicroporous polymer (HMP-1) with a BET surface area of 913 m(2) g(-1) by FeCl3 via a catalyzed Friedel-Crafts alkylation reaction between carbazole and α,α'-dibromo-p-xylene. Upon sulfonation HMP-1 yielded a very efficient solid acid catalyst for the production of biodiesels via esterification/transesterification of free fatty acids (FFA)/esters at room temperature.

Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

PubMed

Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

2014-02-05

The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

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

PubMed

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

2013-10-01

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

A Simple, Safe Method for Preparation of Biodiesel

ERIC Educational Resources Information Center

Behnia, Mahin S.; Emerson, David W.; Steinberg, Spencer M.; Alwis, Rasika M.; Duenas, Josue A.; Serafino, Jessica O.

2011-01-01

An experiment suitable for organic chemistry students is described. Biodiesel, a "green" fuel, consists of methyl or ethyl esters of long-chain fatty acids called FAMES (fatty acid methyl esters) or FAEES (fatty acid ethyl esters). A quick way to make FAMES is a base-catalyzed transesterification of oils or fats derived from plants or from animal…

Enantioconvergent Cross-Couplings of Racemic Alkylmetal Reagents with Unactivated Secondary Alkyl Electrophiles: Catalytic Asymmetric Negishi α-Alkylations of N-Boc-pyrrolidine

PubMed Central

Cordier, Christopher J.; Lundgren, Rylan J.; Fu, Gregory C.

2013-01-01

Although enantioconvergent alkyl-alkyl couplings of racemic electrophiles have been developed, there have been no reports of the corresponding reactions of racemic nucleophiles. Herein, we describe Negishi cross-couplings of racemic α-zincated N-Boc-pyrrolidine with unactivated secondary halides, thus providing a one-pot, catalytic asymmetric method for the synthesis of a range of 2-alkylpyrrolidines (an important family of target molecules) from N-Boc-pyrrolidine, a commercially available precursor. Preliminary mechanistic studies indicate that two of the most straightforward mechanisms for enantioconvergence (a dynamic kinetic resolution of the organometallic coupling partner and a simple β-hydride elimination/β-migratory insertion pathway) are unlikely to be operative. PMID:23869442

Polyfluorinated surfactants (PFS) in paper and board coatings for food packaging.

PubMed

Trier, Xenia; Granby, Kit; Christensen, Jan H

2011-08-01

In this study, we explore the identity of a range of polyfluorinated surfactants (PFS) used for food contact materials, primarily to impart oil and water repellency on paper and board. PFS are of interest, as they can be precursors of poly- and perfluorinated alkyl substances (PFAS), of which several are persistent and are found worldwide in human blood and in the environment. To determine the elemental composition of PFS, we combined information from patents, chemical suppliers and analyses of industrial blends using ultra performance liquid chromatography-negative electrospray ionisation quadrupole time-of-flight mass spectrometry. At a high pH of 9.7, both non-ionic and anionic PFS were ionised and were recognised by negative mass defects of exact masses, and neutral fragment losses of n × 20 or n × 100 Da. More than 115 molecular structures were found in industrial blends from the EU, US and China, belonging to the groups of polyfluoroalkyl-mono- and di-ester phosphates (monoPAPS, diPAPS and S-diPAPS), -ethoxylates, -acrylates, -amino acids, -sulfonamide phosphates and -thio acids, together with residuals and synthesis byproducts. In addition, a number of starting materials such as perfluorooctane sulfonamide N-alkyl esters were analysed. Di- and trialkylated PAPS and S-diPAPS were found in migrates from European food contact materials. This study highlights the need to monitor for more types of PFS in order to map the sources of PFAS in humans and the environment.

Versatile Synthesis of Stable, Functional Polypeptides via Reaction with Epoxides.

PubMed

Gharakhanian, Eric G; Deming, Timothy J

2015-06-08

Methodology was developed for efficient alkylation of methionine residues using epoxides as a general strategy to introduce a wide range of functional groups onto polypeptides. Use of a spacer between epoxide and functional groups further allowed addition of sterically demanding functionalities. Contrary to other methods to alkylate methionine residues, epoxide alkylations allow the reactions to be conducted in wet protic media and give sulfonium products that are stable against dealkylation. These functionalizations are notable since they are chemoselective, utilize stable and readily available epoxides, and allow facile incorporation of an unprecedented range of functional groups onto simple polypeptides using stable linkages.

Benzylation of Nitroalkanes Using Copper-Catalyzed Thermal Redox Catalysis: Toward the Facile C-Alkylation of Nitroalkanes

PubMed Central

Gildner, Peter G.; Gietter, Amber A. S.; Cui, Di; Watson, Donald A.

2012-01-01

The C-alkylation of nitroalkanes under mild conditions has been a significant challenge in organic synthesis for more than a century. Herein, we report a simple Cu(I) catalyst, generated in situ, that is highly effective for C-benzylation of nitroalkanes using abundant benzyl bromides and related heteroaromatic compounds. This process, which we believe proceeds via a thermal redox mechanism, allows access to a variety of complex nitroalkanes under mild reaction conditions and represents the first step towards developing a general catalytic system for the alkylation of nitroalkanes. PMID:22691127

Structural analysis of pyridine-imino boronic esters involving secondary interactions on solid state

NASA Astrophysics Data System (ADS)

Sánchez-Portillo, Paola; Arenaza-Corona, Antonino; Hernández-Ahuactzi, Irán F.; Barba, Victor

2017-04-01

Twelve boronic esters (1a-1l) synthesized from 4-halo- substituted arylboronic acids (halo = F, Cl, Br, I and CF3) with 2-amino-2- alkyl (H, Me) -1,3-propanediol in presence of (3- or 4)-pyridine carboxaldehyde are described. A solvent mixture toluene/methanol 1:4 ratio was used. All compounds include both donor/acceptor functional groups, which are the necessary elements to self-assembly of the molecular species. Several secondary interactions as I⋯N, Br⋯Br, Br⋯B, F⋯B, Csbnd H⋯N, Csbnd H⋯O, Br⋯π and Csbnd H⋯π support the 1D and 2D polymeric frameworks in solid state. The coordination of the nitrogen atom from the pyridine moiety with the boron atom was not observed in either solution or solid state.

Rapid and simple micromethod for the simultaneous determination of 3-MCPD and 3-MCPD esters in different foodstuffs.

PubMed

Küsters, Markus; Bimber, Ute; Ossenbrüggen, Alexandra; Reeser, Sebastian; Gallitzendörfer, Rainer; Gerhartz, Michael

2010-06-09

This paper describes for the first time a micromethod for the simultaneous determination of 3-monochloropropane-1,2-diol (3-MCPD) and fatty acid esters of 3-MCPD (3-MCPD esters) in different foodstuffs. 3-MCPD and 3-MCPD esters were isolated from food products using a single extraction step separating hydrophilic and lipophilic compounds. An aliquot of the aqueous layer was analyzed for the content of 3-MCPD while a part of the organic layer was analyzed for 3-MCPD esters after cleavage with sodium methoxide. After a simple derivatization procedure with phenylboronic acid (PBA), the determination was achieved by isotope dilution GC-MS using isotope-labeled 3-MCPD and 3-MCPD ester as internal standards. The method was validated for various foodstuffs like bakery products, meat and fish products, and soups as well as seasonings with LOD of 1-2 microg/kg (3-MCPD) and 6 microg/kg (3-MCPD esters), respectively. Recoveries ranged within 95 +/- 9% and 96 +/- 10% at spiking levels of 15 and 25 microg/kg in all matrices for 3-MCPD and 84 +/- 9% and 85 +/- 7% at spiking levels of 0.05 mg/kg and 2 mg/kg for 3-MCPD esters. The method avoids tedious and laborious sample preparation and was successfully applied to the rapid screening of samples conforming to the EU performance criteria for methods of analysis for 3-MCPD.

Direct, enantioselective α-alkylation of aldehydes using simple olefins.

PubMed

Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Direct, enantioselective α-alkylation of aldehydes using simple olefins

PubMed Central

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-01-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons. PMID:29064486

Direct, enantioselective α-alkylation of aldehydes using simple olefins

NASA Astrophysics Data System (ADS)

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

A fluorescent radioiodinated oligonucleotidic photoaffinity probe for protein labeling: synthesis and photolabeling of thrombin.

PubMed

Berens, C; Courtoy, P J; Sonveaux, E

1999-01-01

To study the interactions between oligonucleotides and proteins, an original photoaffinity radiolabeling probe has been synthesized. Starting with a 5'-pyridyldithio-3'-amino-oligonucleotide, the photophore benzophenone was first coupled to the 3' end, through acylation by an activated ester of benzoylbenzoic acid. A fluorescein molecule was grafted by alkylation of the free 5'-SH. This compound was finally radiolabeled with 125I using IodoBeads. The selective photolabeling of thrombin in a complex protein mixture by the radioiodinated probe validates this strategy to identify oligonucleotide-binding proteins.

Dihydronaphthalenone Carboxylates - Spectral Characteristics and Structure

NASA Astrophysics Data System (ADS)

Bakalova, Sn.; Georgieva, A.; Nikolov, P.; Stanoeva, E.

1997-05-01

The absorption and luminescence characteristics of a group of newly synthesized methyl esters of 2-alkyl (p-substituted-aryl) -aminomethylene-3,4-dihydro-1(2 H)-naphthalenone-4-carboxylic acids have been investigated. The studied compounds may exist in three tautomeric forms. On the basis of comparison of their electronic spectra to those of similar substances, the observed substituent effect on the position of the UV-VIS absorption bands, the IR spectra and the results of PPP-SCF-CI quantum-chemical calculations it is concluded that the keto tautomer predominates in solution.

Pauson-Khand adducts of N-Boc-propargylamine: a new approach to 4,5-disubstituted cyclopentenones.

PubMed

Aiguabella, Nuria; Pesquer, Albert; Verdaguer, Xavier; Riera, Antoni

2013-06-07

A new approach to the synthesis of 4,5-disubstituted cyclopentenones is described. The strategy is based on the Pauson-Khand (PK) reaction of norbornadiene and N-Boc-propargylamine as an alkyne with a masked leaving group, which can be eliminated at will. This approach to the synthesis of 4,5-disubstituted cyclopentenones overcomes the problem of using the alkylation to introduce the α side chain. As an example, prostane 13-epi-12-oxo-phytodienoic acid (13-epi-12-oxo-PDA) methyl ester was synthesized.

High-Solids Polyimide Precursor Solutions

NASA Technical Reports Server (NTRS)

Chuang, Chun-Hua (Inventor)

2004-01-01

The invention is a highly concentrated stable solution of polymide precursors (monometers) having a solids content ranging from about 80 to 98 percent by weight in lower aliphatic alcohols i.e. methyl and/or ethylalcohol. the concentrated polyimide precursos solution comparisons effective amounts of at least one aromatic diamine, at least one aromatic dianhydride, and a monofunctional endcap including monoamines, monoanhydrides and lower alkyl esters of said monoanhydrides. These concentrated polyimide precursor solutions are particularly useful for the preparation of fibrous prepregs and composites for use in structural materials for military and civil applications.

Organic Nitrates: A Complex Family of Atmospheric Trace Constituents

NASA Astrophysics Data System (ADS)

Ballschmiter, K.; Fischer, R. G.; Grünert, A.; Kastler, J.; Schneider, M.; Woidich, S.

2003-04-01

Biogenic and geogenic hydrocarbons are the precursors of organic nitrates that are formed as tropospheric photo-oxidation products in the presence of NOx. Air chemistry leads to a very complex pattern of nitric acid esters: alkyl nitrates, aryl-alkyl nitrates, and bifunctional nitrates like alkyl dinitrates, hydroxy alkyl nitrates and carbonyl alkyl nitrates. We have analyzed the pattern of organic nitrates in air samples after adsorption/thermal desorption (low volume sampling-LVS) or adsorption/solvent desorption (high volume sampling-HVS) by capillary gas chromatography with electron capture (ECD) and mass spectrometric detection (MSD) using air aliquotes of 100 up to 3000 liters on column. The complexity of the organic nitrates found in air requires a group pre-separation by normal phase liquid chromatography. A detection limit per compound of 0.005 ppt(v) is achieved by our approach. We have synthesized a broad spectrum of organic nitrates as reference compounds. Air samples were taken from central Europe, the US West (Utah, Nevada, California), and the North- and South Atlantic including Antarctica. Levels and patterns of the regional and global occurrence of the various groups of C1-C12 organic nitrates including dinitrates and hydroxy nitrates and nitrates of isoprene (2-methylbutadiene) are presented. Werner G., J. Kastler, R. Looser, K. Ballschmiter: "Organic nitrates of isoprene as atmospheric trace compounds" Angewandte Chemie - International Edition (1999) 38: 1634-1637. Woidich S., O. Froescheis, O. Luxenhofer, K. Ballschmiter: "EI- and NCI-mass spectrometry of arylalkyl nitrates and their occurrence in urban air" Fresenius J. Anal. Chem. (1999) 364 : 91-99. Kastler, J; Jarman, W; Ballschmiter, K.: "Multifunctional organic nitrates as constituents in European and US urban photo-smog" Fresenius J. Anal. Chem. (2000) 368:244-249. Schneider M., K. Ballschmiter: "C3-C14 alkyl nitrates in remote South Atlantic air" Chemosphere (1999) 38: 233-244. Fischer, R G; Kastler, J; Ballschmiter, K.: "Levels and pattern of alkyl nitrates, multifunctional alkyl nitrates, and halocarbons in the air over the Atlantic Ocean" J. Geophys. Research (2000) 105:14473-14494. Fischer R.G. , R. Weller, H.-W. Jacobi, K. Ballschmiter: "Levels and patterns of volatile organic nitrates and halocarbons in the air at Neumayer Station (70°), Antarctic" Chemosphere (2002) 48:981-992

Functionalization of carbon dioxide and carbon disulfide using a stable uranium(III) alkyl complex.

PubMed

Matson, Ellen M; Forrest, William P; Fanwick, Phillip E; Bart, Suzanne C

2011-04-06

A rare uranium(III) alkyl complex, Tp*(2)U(CH(2)Ph) (2) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate), was synthesized by salt metathesis from Tp*(2)UI (1) and KCH(2)Ph and fully characterized using (1)H NMR, infrared, and electronic absorption spectroscopies as well as X-ray crystallography. This complex has a uranium-carbon distance of 2.57(2) Å, which is comparable to other uranium alkyls reported. Treating this compound with either carbon dioxide or carbon disulfide results in insertion into the uranium-carbon bond to generate Tp*(2)U(κ(2)-O(2)CCH(2)Ph) (3) and Tp*(2)U(SC(S)CH(2)Ph) (4), respectively. These species, characterized spectroscopically and by X-ray crystallography, feature new carboxylate and dithiocarboxylate ligands. Analysis by electronic absorption spectroscopy supports the trivalent oxidation state of the uranium center in both of these derivatives. Addition of trimethylsilylhalides (Me(3)SiX; X = Cl, I) to 3 results in the release of the free silyl ester, Me(3)SiOC(O)CH(2)Ph, forming the initial uranium monohalide species, Tp*(2)UX, which can then be used over multiple cycles for the functionalization of carbon dioxide. © 2011 American Chemical Society

Bis(thienothiophenyl) diketopyrrolopyrrole-based conjugated polymers with various branched alkyl side chains and their applications in thin-film transistors and polymer solar cells.

PubMed

Shin, Jicheol; Park, Gi Eun; Lee, Dae Hee; Um, Hyun Ah; Lee, Tae Wan; Cho, Min Ju; Choi, Dong Hoon

2015-02-11

New thienothiophene-flanked diketopyrrolopyrrole and thiophene-containing π-extended conjugated polymers with various branched alkyl side-chains were successfully synthesized. 2-Octyldodecyl, 2-decyltetradecyl, 2-tetradecylhexadecyl, 2-hexadecyloctadecyl, and 2-octadecyldocosyl groups were selected as the side-chain moieties and were anchored to the N-positions of the thienothiophene-flanked diketopyrrolopyrrole unit. All five polymers were found to be soluble owing to the bulkiness of the side chains. The thin-film transistor based on the 2-tetradecylhexadecyl-substituted polymer showed the highest hole mobility of 1.92 cm2 V(-1) s(-1) due to it having the smallest π-π stacking distance between the polymer chains, which was determined by grazing incidence X-ray diffraction. Bulk heterojunction polymer solar cells incorporating [6,6]-phenyl-C71-butyric acid methyl ester as the n-type molecule and the additive 1,8-diiodooctane (1 vol %) were also constructed from the synthesized polymers without thermal annealing; the device containing the 2-octyldodecyl-substituted polymer exhibited the highest power conversion efficiency of 5.8%. Although all the polymers showed similar physical properties, their device performance was clearly influenced by the sizes of the branched alkyl side-chain groups.

Structural Analysis and Application of n-Alkyl Cyanoacrylate Surgical Adhesives to the Fixation of Meshes for Hernia Repair.

PubMed

Fernández-Gutiérrez, Mar; Rodriguez-Mancheño, Marta; Pérez-Köhler, Bárbara; Pascual, Gemma; Bellón, Juan Manuel; Román, Julio San

2016-12-01

The article deals with a comparative analysis of the parameters of the polymerization in physiological conditions of three commercially available alkyl cyanoacrylates, n-butyl cyanoacrylate (GLUBRAN 2), n-hexyl cyanoacrylate (IFABOND), and n-octyl cyanoacrylate (EVOBOND), the cell behavior of the corresponding polymers and the application of these adhesives in the fixation of surgical polypropylene meshes for hernia repair in an animal model of rabbits. The results obtained demonstrate that the curing process depends on the nature of the alkyl residue of the ester group of cyanoacrylate molecules, being the heat of polymerization lower for the octyl derivative in comparison with the hexyl and butyl, and reaching a maximum temperature of 35 °C after a time of mixing with physiological fluids of 60-70 s. The cell behavior demonstrates that the three systems do not present toxicity for fibroblasts and low adhesion of cells, which is a positive result for application as tissue adhesives, especially for the fixation of abdominal polypropylene meshes for hernia repair. The animal experimentation indicates the excellent tolerance of the meshes fixed with the cyanoacrylic adhesives, during at least a period of 90 d, and guarantees a good adhesion for the application of hernia repair meshes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluoroalkyl containing salts combined with fluorinated solvents for electrolytes

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

Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan

Provided are electrochemical cells and electrolytes used to build such cells. An electrolyte may include a fluoroalkyl-substituted LiPF.sub.6 salt or a fluoroalkyl-substituted LiBF.sub.4 salt. In some embodiments, at least one fluorinated alkyl of the salt has a chain length of from 1 to 8 or, more specifically, between about 2 and 8. These fluorinated alkyl groups, in particular, relatively large fluorinated alkyl groups improve solubility of these salts in fluorinated solvents that are less flammable than, for example, conventional carbonate solvents. At the same time, the size of fluoroalkyl-substituted salts should be limited to ensure adequate concentration of the saltmore » in an electrolyte and low viscosity of the electrolyte. In some embodiments, the concentration of a fluoroalkyl-substituted salt is at least about 0.5M. Examples of fluorinated solvents include various fluorinated esters, fluorinated ethers, and fluorinated carbonates, such a 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.« less

Theoretical study on the mechanism of the gas-phase elimination kinetics of alkyl chloroformates

NASA Astrophysics Data System (ADS)

Alcázar, Jackson J.; Marquez, Edgar; Mora, José R.; Cordova-Sintjago, Tania; Chuchani, Gabriel

2016-03-01

The theoretical calculations on the mechanism of the homogeneous and unimolecular gas-phase elimination kinetics of alkyl chloroformates- ethyl chloroformate (ECF), isopropyl chloroformate (ICF), and sec-butyl chloroformate (SCF) - have been carried out by using CBS-QB3 level of theory and density functional theory (DFT) functionals CAM-B3LYP, M06, MPW1PW91, and PBE1PBE with the basis sets 6-311++G(d,p) and 6-311++G(2d,2p). The chlorofomate compounds with alkyl ester Cβ-H bond undergo thermal decomposition producing the corresponding olefin, HCl and CO2. These homogeneous eliminations are proposed to undergo two different types of mechanisms: a concerted process, or via the formation of an unstable intermediate chloroformic acid (ClCOOH), which rapidly decomposes to HCl and CO2 gas. Since both elimination mechanisms may occur through a six-membered cyclic transition state structure, it is difficult to elucidate experimentally which is the most reasonable reaction mechanism. Theoretical calculations show that the stepwise mechanism with the formation of the unstable intermediate chloroformic acid from ECF, ICF, and SCF is favoured over one-step elimination. Reasonable agreements were found between theoretical and experimental values at the CAM-B3LYP/6-311++G(d,p) level.

Direct α-alkylation of ketones with alcohols in water.

PubMed

Xu, Guoqiang; Li, Qiong; Feng, Jiange; Liu, Qiang; Zhang, Zuojun; Wang, Xicheng; Zhang, Xiaoyun; Mu, Xindong

2014-01-01

The direct α-alkylation of ketones with alcohols has emerged as a new green protocol to construct C-C bonds with H2 O as the sole byproduct. In this work, a very simple and convenient Pd/C catalytic system for the direct α-alkylation of ketones with primary alcohols in pure water is developed. Based on this catalytic system, aqueous mixtures of dilute acetone, 1-butanol, and ethanol (mimicking ABE fermentation products) can be directly transformed into C5 -C11 or longer-chain ketones and alcohols, which are precursors to fuels. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alcohols as alkylating agents in heteroarene C-H functionalization

NASA Astrophysics Data System (ADS)

Jin, Jian; MacMillan, David W. C.

2015-09-01

Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of `spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

Alcohols as alkylating agents in heteroarene C-H functionalization.

PubMed

Jin, Jian; MacMillan, David W C

2015-09-03

Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of 'spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

Glutathione Depletion Induced by c-Myc Downregulation Triggers Apoptosis on Treatment with Alkylating Agents1

PubMed Central

Biroccio, Annamaria; Benassi, Barbara; Fiorentino, Francesco; Zupi, Gabriella

2004-01-01

Abstract Here we investigate the mechanism(s) involved in the c-Myc-dependent drug response of melanoma cells. By using three M14-derived c-Myc low-expressing clones, we demonstrate that alkylating agents, cisplatin and melphalan, trigger apoptosis in the c-Myc antisense transfectants, but not in the parental line. On the contrary, topoisomerase inhibitors, adriamycin and camptothecin, induce apoptosis to the same extent regardless of c-Myc expression. Because we previously demonstrated that c-Myc downregulation decreases glutathione (GSH) content, we evaluated the role of GSH in the apoptosis induced by the different drugs. In control cells treated with one of the alkylating agents or the others, GSH depletion achieved by l-buthionine-sulfoximine preincubation opens the apoptotic pathway. The apoptosis proceeded through early Bax relocalization, cytochrome c release, and concomitant caspase-9 activation, whereas reactive oxygen species production and alteration of mitochondria membrane potential were late events. That GSH was determining in the c-Myc-dependent drug-induced apoptosis was demonstrated by altering the intracellular GSH content of the c-Myc low-expressing cells up to the level of controls. Indeed, GSH ethyl ester-mediated increase of GSH abrogated apoptosis induced by cisplatin and melphalan by inhibition of Bax/cytochrome c redistribution. The relationship among c-Myc, GSH content, and the response to alkylating agent has been also evaluated in the M14 Myc overexpressing clones as well as in the melanoma JR8 c-Myc antisense transfectants. All together, these results demonstrate that GSH plays a key role in governing c-Myc-dependent drug-induced apoptosis. PMID:15153331

Occurrence, distribution and risk of organophosphate esters in urban road dust in Beijing, China.

PubMed

Li, Wenhui; Shi, Yali; Gao, Lihong; Wu, Chuandong; Liu, Jiemin; Cai, Yaqi

2018-06-06

As a major group of plasticizers and flame-retardants, organophosphate esters (OPEs) have attracted particular attention due to their wide occurrence and potential impacts on human health and ecosystems. In the present study, the occurrence and distribution of 14 OPEs, including seven Alkyl-OPEs, three Cl-OPEs, and four Aryl-OPEs, were investigated in 65 road dust samples collected from November to December 2014 in Beijing, China. Cl-OPEs were the predominant compounds in the road dust samples, with the median concentration of 646 μg/kg, followed by the Alkyl-OPEs (median 135 μg/kg) and Aryl-OPEs (median 129 μg/kg). Tris(2-chloro-1-methylethyl) phosphate (TCPP) was the most abundant OPE with the median concentration of 384 μg/kg. In addition, OPEs levels showed significant difference (p < 0.05) in the spatial distribution. Markedly higher levels of OPEs were observed in 2nd and 3rd ring road with heavy traffic and high population density, indicating that the traffic and population were important factors for this distribution pattern. It was further supported by the analysis of OPEs in roadside soil and indoor dust in the vicinity of road dust sample sites. Finally, the average daily dose (ADD) for OPEs via inhalation, dermal absorption, and ingestion was calculated to evaluate the carcinogenic and non-carcinogenic risks to residents exposed to OPEs in the road dust. Risk assessment revealed that the risk originating from exposure to OPEs of road dust is currently low in Beijing, China. Copyright © 2018 Elsevier Ltd. All rights reserved.

'Petite' mutagenesis and mitotic crossing-over in yeast by DNA-targeted alkylating agents.

PubMed

Ferguson, L R; Turner, P M; Gourdie, T A; Valu, K K; Denny, W A

1989-12-01

Although the biological properties (cytotoxicity, mutagenicity and carcinogenicity) of alkylating agents result from their bonding interactions with DNA, such compounds generally do not show any special binding affinity for DNA. A series of acridine-linked aniline mustards of widely-varying alkylator reactivity have been designed as DNA-directed alkylating agents. We have considered whether such DNA targeting has an effect on mutagenic properties by evaluating this series of drugs in comparison with their untargeted counterparts for toxic, recombinogenic and mutagenic properties in Saccharomyces cerevisiae strain D5. The simple untargeted aniline mustards are effective inducers of mitotic crossing-over in this strain, but resemble other reported alkylators in being rather inefficient inducers of the "petite" or mitochondrial mutation in yeast. However, the majority of the DNA-targeted mustards were very efficient petite mutagens, while showing little evidence of mitotic crossing-over or other nuclear events. The 100% conversion of cells into petites and the lack of a differential between growing and non-growing cells are similar to the effects of the well characterised mitochondrial mutagen ethidium bromide. These data suggest very different modes of action between the DNA-targeted alkylators and their non-targeted counterparts.

Comparison of new nitrosoureas esters with modified steroidal nucleus for cytogenetic and antineoplastic activity.

PubMed

Hussein, A; Mioglou-Kalouptsi, E; Papageorgiou, A; Karapidaki, I; Iakovidou-Kritsi, Z; Lialiaris, T; Xrysogelou, E; Camoutsis, C; Mourelatos, D

2007-01-01

Nitrosourea is decomposed under physiological conditions to react with biological macromolecules by two mechanisms: alkylation (with proteins and nucleic acids) and carbamoylation (with proteins but not nucleic acids). It has been suggested that the alkylating action is responsible for the therapeutic effects of nitrosoureas, and that the carbamoylation activity leads to toxicity effects. In order to reduce systemic toxicity and improve specificity and distribution for cancer therapy, 2-haloethyl nitrosourea has been esterified with modified steroids, which are used as biological platforms for transporting the alkylating agent to the tumor site in a specific manner. The cytogenetic and antineoplastic effect were studied of seven newly synthesized esters of N,N-bis(2-chloroethyl)alanyl carboxyl derivatives with a modified steroidal nucleus (compounds 1-7). As a very sensitive indicator of genotoxicity the Sister Chromatid Exchange (SCE) assay was used and as a valuable marker of cytostatic activity the cell Proliferation Rate Index (PRI) in cultures of normal human lymphocytes was used. The order of magnitude of the cytogenetic activity on a molar basis (15, 30, 120 microM) of the compounds was 7>6>3>5>2>4>1. The most active compound 7 has an enlarged (seven carbon atoms) A ring modified with a lactam group (-NHCO-) with the nitrosourea moiety esterified at position 17 In the group of seven substances a correlation was observed between the magnitude of SCE response and the depression in PRI (r=-O, 65, p<0.001). According to the criterion of activity of National Cancer Institute (NCI), the order of antineoplastic activity of compounds on lymphoid L1210 leukemia is 7>6>2>5>4>3>1 and on lympocytic P388 leukemia cells is 7>2>6>5>4>3>1. The present results are in agreement with previous suggestions that the effectiveness in cytogenetic activity may well be correlated with antitumor effects [T/C: 248% for the compound 7 in 250 mg/kg b.w.; T/C: mean survival time of drug-treated animals (T) (excluding long term survivals) vs. corn-oil-treated controls (C)].

The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-01-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R + R'-OH --> - CH2-CO2-R' + R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'-OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

Hybrid nanocomposites of CdSe nanocrystals distributed in complexing thiophene-based copolymers.

PubMed

Aldakov, Dmitry; Jiu, Tonggang; Zagorska, Malgorzata; de Bettignies, Rémi; Jouneau, Pierre-Henri; Pron, Adam; Chandezon, Frédéric

2010-07-21

Two types of conjugated polymers were prepared with the goal to blend them with rod-like CdSe nanocrystals. The polymers of the first type were synthesized through copolymerization of 3-octylthiophene and 3-methylene-ethylcarboxylate-thiophene to give polythiophene with solubilizing alkyl groups and methylene ester functional groups (PE series). Post-polymerization hydrolysis of the ester type polymers yielded acid-type ones (PA series). Photoluminescence (PL) quenching in these polymers induced by their titration with nanocrystals solution was chosen as a measure of the polymer-nanocrystal interactions. PL of polyacids turned out to be more efficiently quenched as compared to the case of polymers with ester groups which was interpreted as an indication of better electronic communication between the hybrid components. Infrared (IR) spectroscopy confirmed efficient coordination of the carboxylic groups to CdSe. Voltammetric studies combined with UV-vis spectroelectrochemistry enabled the determination of energy levels alignment of the molecular composite components which turned out to be of staggered type-appropriate for photovoltaic applications. The obtained blends of polyacids with CdSe nanocrystals, when studied by transmission electron microscopy (TEM), revealed the presence of an interpenetrating network in which nanorods were homogeneously distributed within the polymer matrix without any indication of agglomerates formation both on the film surface and in the cross-section. Blends with polymers containing ester groups were less homogeneous which could be explained by weaker polymer-nanocrystals interactions. Photovoltaic cells based on these hybrid materials are also discussed.

Structural features, kinetics and SAR study of radical scavenging and antioxidant activities of phenolic and anilinic compounds

PubMed Central

2013-01-01

Background Phenolic compounds are widely distributed in plant kingdom and constitute one of the most important classes of natural and synthetic antioxidants. In the present study fifty one natural and synthetic structurally variant phenolic, enolic and anilinic compounds were examined as antioxidants and radical scavengers against DPPH, hydroxyl and peroxyl radicals. The structural diversity of the used phenolic compounds includes monophenols with substituents frequently present in natural phenols e.g. alkyl, alkoxy, ester and carboxyl groups, besides many other electron donating and withdrawing groups, in addition to polyphenols with 1–3 hydroxyl groups and aminophenols. Some common groups e.g. alkyl, carboxyl, amino and second OH groups were incorporated in ortho, meta and para positions. Results SAR study indicates that the most important structural feature of phenolic compounds required to possess good antiradical and antioxidant activities is the presence of a second hydroxyl or an amino group in o- or p-position because of their strong electron donating effect in these positions and the formation of a stable quinone-like products upon two hydrogen-atom transfer process; otherwise, the presence of a number of alkoxy (in o or p-position) and /or alkyl groups (in o, m or p-position) should be present to stabilize the resulted phenoxyl radical and reach good activity. Anilines showed also similar structural feature requirements as phenols to achieve good activities, except o-diamines which gave low activity because of the high energy of the resulted 1,2-dimine product upon the 2H-transfer process. Enols with ene-1,2-diol structure undergo the same process and give good activity. Good correlations were obtained between DPPH inhibition and inhibition of both OH and peroxyl radicals. In addition, good correlations were obtained between DPPH inhibition and antioxidant activities in sunflower oil and liver homogenate systems. Conclusions In conclusion, the structures of good anti radical and antioxidant phenols and anilines are defined. The obtained good correlations imply that measuring anti DPPH activity can be used as a simple predictive test for the anti hydroxyl and peroxyl radical, and antioxidant activities. Kinetic measurements showed that strong antioxidants with high activity have also high reaction rates indicating that factors stabilizing the phenoxyl radicals lower also the activation energy of the hydrogen transfer process. PMID:23497653

Merging domino and redox chemistry: stereoselective access to di- and trisubstituted β,γ-unsaturated acids and esters.

PubMed

Tejedor, David; Méndez-Abt, Gabriela; Cotos, Leandro; García-Tellado, Fernando

2012-03-19

Merging is the game! The coupling of a domino reaction and an internal neutral redox reaction constitutes an excellent manifold for the stereoselective synthesis of di- and trisubstituted olefins featuring a malonate unit, an ester, or a free carboxylic acid as substituents at the allylic position (see scheme; MW=microwave). The reaction utilizes simple starting materials (propargyl vinyl ethers), methanol or water as solvents, and a very simple and bench-friendly protocol. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Aldehyde C-H Arylation and Alkylation via the Combination of Nickel, Hydrogen Atom Transfer, and Photoredox Catalysis.

PubMed

Zhang, Xiaheng; MacMillan, David W C

2017-08-23

A mechanism that enables direct aldehyde C-H functionalization has been achieved via the synergistic merger of photoredox, nickel, and hydrogen atom transfer catalysis. This mild, operationally simple protocol transforms a wide variety of commercially available aldehydes, along with aryl or alkyl bromides, into the corresponding ketones in excellent yield. This C-H abstraction coupling technology has been successfully applied to the expedient synthesis of the medicinal agent haloperidol.

Isolation and characterization of Escherichia coli K-12 mutants unable to induce the adaptive response to simple alkylating agents.

PubMed Central

Jeggo, P

1979-01-01

When Esherichia coli cells are exposed to a low level of simple alkylating agents, they induce the adaptive response which renders them more resistant to the killing and the mutagenic effects of the same or other alkylating agents. This paper describes the isolation of one strain that was deficient in mutagenic adaptation and five that were deficient in both mutagenic and killing adaptation, confirming previous suggestions that killing and mutagenic adaptation are, at least to some extent, separable. These six strains have been called Ada mutants. They were more sensitive to the killing and mutagenic effects of N-methy-N'-nitro-N-nitrosoguanidine (MNNG) than the unadapted Ada+ parent. Thus, the adaptation pathway is responsible for circumventing some alkylation-induced damage even in cells that are preinduced. The increase in mutation frequency seen in Ada cells treated with MNNG was the same whether the cells were lexA+ or lexA, showing that the extra mutations found in Ada- strains do not depend upon the SOS pathway. Ada strains accumulated more O6-methyl guanine lesions than the Ada+ parent on prolonged exposure to MNNG, and this supports the idea that O6-methyl guanine is the most important lesion for MNNG-induced mutagenesis. The ada mutations have been shown to map in the 47 to 53-min region of the E. coli chromosome. PMID:383692

A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron

DOE PAGES

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

2016-05-23

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4FeCl 2. Furthermore, we prepared a series of monoalkylated salts of the type (py) 2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane thatmore » readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2Fe(N 2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.« less

Development of a drug delivery system for the treatment of periodontal disease based on bioerodible poly(ortho esters).

PubMed

Roskos, K V; Fritzinger, B K; Rao, S S; Armitage, G C; Heller, J

1995-03-01

Poly(ortho esters) prepared by the condensation of 1,2,6-hexanetriol and an alkyl orthoacetate are viscous, semisolid materials at room temperature that can be injected using a blunt needle. When tetracycline was incorporated into these materials, complete release occurred within about 24 hours, but when small amounts of Mg(OH)2 were incorporated into the polymer release could be extended to many weeks, and a loading of 0.5 wt% resulted in sustained release of about 10 days. When adhesion was tested using bovine teeth, cohesive failure of the pure polymer occurred at a force of about 392 mN cm-2 and cohesive failure of a polymer incorporating 10 wt% tetracycline and 1 wt% (Mg(OH)2 occurred at about 118 mN cm-2. The combination of injectability, dentoadhesiveness and ability to control accurately the release of incorporated antibiotics makes these materials promising candidates for bioerodible delivery systems useful in the treatment of periodontitis. Toxicological studies are currently in progress.

Effects of Different Lipophilized Ferulate Esters in Fish Oil-Enriched Milk: Partitioning, Interaction, Protein, and Lipid Oxidation.

PubMed

Qiu, Xujian; Jacobsen, Charlotte; Villeneuve, Pierre; Durand, Erwann; Sørensen, Ann-Dorit Moltke

2017-11-01

Antioxidant effects of ferulic acid and lipophilized ferulate esters were investigated in fish oil-enriched milk. Methyl ferulate (C1) and ethyl ferulate (C2) more efficiently prevented lipid oxidation than dodecyl ferulate (C12) did, followed by ferulic acid (C0). The combination of C1 or C2 with C12 could have a "synergistic" effect indicated by peroxide value, hexanal, and 1-penten-3-ol analysis results. These antioxidants also showed protein oxidation inhibition effects. The most effective antioxidants (C1 and C2) had the highest concentration in the precipitate phase but the lowest concentration in the aqueous phase, which was the opposite of the partitioning of C0. C12 had the highest concentration in the oil and emulsion phase. In particular, the interaction between ferulates esterified with short and medium alkyl chain lengths could lead to their "synergistic" effects in fish oil-enriched milk, which could be caused by the change in their partitioning or localization at the interface.

Green tea polyphenols as potent enhancers of glucocorticoid-induced mouse mammary tumor virus gene expression.

PubMed

Abe, I; Umehara, K; Morita, R; Nemoto, K; Degawa, M; Noguchi, H

2001-02-16

The effect of natural and synthetic galloyl esters on glucocorticoid-induced gene expression was evaluated by using rat fibroblast 3Y1 cells stably transfected with a luciferase reporter gene under the transcriptional regulation of the mouse mammary tumor virus promoter. The glucocorticoid-induced gene transcription was strongly suppressed by synthetic alkyl esters; n-dodecyl gallate showed the most potent inhibition (66% inhibition at 10 microM), which was far more potent than that of crude tannic acid. n-Octyl and n-cetyl gallate also showed good inhibition, while gallic acid itself was not so active, suggesting that the presence of hydrophobic side chain is important for the suppressive effect. On the other hand, surprisingly, green tea gallocatechins, (-)-epigallocatechin-3-O-gallate and theasinensin A, potently enhanced the promoter activity (182 and 247% activity at 1 microM, respectively). The regulation of the level of the glucocorticoid-induced gene expression by the antioxidative gallates is of great interest from a therapeutic point of view.

Intricate Conformational Tunneling in Carbonic Acid Monomethyl Ester.

PubMed

Linden, Michael M; Wagner, J Philipp; Bernhardt, Bastian; Bartlett, Marcus A; Allen, Wesley D; Schreiner, Peter R

2018-04-05

Disentangling internal and external effects is a key requirement for understanding conformational tunneling processes. Here we report the s- trans/ s- cis tunneling rotamerization of carbonic acid monomethyl ester (1) under matrix isolation conditions and make comparisons to its parent carbonic acid (3). The observed tunneling rate of 1 is temperature-independent in the 3-20 K range and accelerates when using argon instead of neon as the matrix material. The methyl group increases the effective half life (τ eff ) of the energetically disfavored s- trans-conformer from 3-5 h for 3 to 11-13 h for 1. Methyl group deuteration slows the rotamerization further (τ eff ≈ 35 h). CCSD(T)/cc-pVQZ//MP2/aug-cc-pVTZ computations of the tunneling probability suggest that the rate should be almost unaffected by methyl substitution or its deuteration. Thus the observed relative rates are puzzling, and they disagree with previous explanations involving fast vibrational relaxation after the tunneling event facilitated by the alkyl rotor.

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

PubMed

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

2010-09-01

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

Electrolytes including fluorinated solvents for use in electrochemical cells

DOEpatents

Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan

2015-07-07

Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include ion-supplying salts and fluorinated solvents capable of maintaining single phase solutions with the salts at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and increase safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Fluorinated salts, such as fluoroalkyl-substituted LiPF.sub.6, fluoroalkyl-substituted LiBF.sub.4 salts, linear and cyclic imide salts as well as methide salts including fluorinated alkyl groups, may be used due to their solubility in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene or, more specifically, a cyclic phosphazene and/or one or more ionic liquids.

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

PubMed

Sun, Chaode; Bittman, Robert

2004-10-29

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

Production and Use of Lipases in Bioenergy: A Review from the Feedstocks to Biodiesel Production

PubMed Central

Ribeiro, Bernardo Dias; de Castro, Aline Machado; Coelho, Maria Alice Zarur; Freire, Denise Maria Guimarães

2011-01-01

Lipases represent one of the most reported groups of enzymes for the production of biofuels. They are used for the processing of glycerides and fatty acids for biodiesel (fatty acid alkyl esters) production. This paper presents the main topics of the enzyme-based production of biodiesel, from the feedstocks to the production of enzymes and their application in esterification and transesterification reactions. Growing technologies, such as the use of whole cells as catalysts, are addressed, and as concluding remarks, the advantages, concerns, and future prospects of enzymatic biodiesel are presented. PMID:21785707

Aquivion Perfluorosulfonic Superacid as an Efficient Pickering Interfacial Catalyst for the Hydrolysis of Triglycerides.

PubMed

Shi, Hui; Fan, Zhaoyu; Hong, Bing; Pera-Titus, Marc

2017-09-11

Rational design of the surface properties of heterogeneous catalysts can boost the interfacial activity in biphasic reactions through the generation of Pickering emulsions. This concept, termed Pickering interfacial catalysis (PIC), has shown promising credentials in acid-catalyzed transesterification, ester hydrolysis, acetalization, etherification, and alkylation reactions. PIC has now been applied to the efficient, solvent-free hydrolysis of the triglyceride glyceryl trilaurate to lauric acid, catalyzed by Aquivion perfluorosulfonic superacid at mild conditions (100 °C and ambient pressure). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrodehalogenation of alkyl iodides with base-mediated hydrogenation and catalytic transfer hydrogenation: application to the asymmetric synthesis of N-protected α-methylamines.

PubMed

Mandal, Pijus K; Birtwistle, J Sanderson; McMurray, John S

2014-09-05

We report a very mild synthesis of N-protected α-methylamines from the corresponding amino acids. Carboxyl groups of amino acids are reduced to iodomethyl groups via hydroxymethyl intermediates. Reductive deiodination to methyl groups is achieved by hydrogenation or catalytic transfer hydrogenation under alkaline conditions. Basic hydrodehalogenation is selective for the iodomethyl group over hydrogenolysis-labile protecting groups, such as benzyloxycarbonyl, benzyl ester, benzyl ether, and 9-fluorenyloxymethyl, thus allowing the conversion of virtually any protected amino acid into the corresponding N-protected α-methylamine.

Hydrodehalogenation of Alkyl Iodides with Base-Mediated Hydrogenation and Catalytic Transfer Hydrogenation: Application to the Asymmetric Synthesis of N-Protected α-Methylamines

PubMed Central

2015-01-01

We report a very mild synthesis of N-protected α-methylamines from the corresponding amino acids. Carboxyl groups of amino acids are reduced to iodomethyl groups via hydroxymethyl intermediates. Reductive deiodination to methyl groups is achieved by hydrogenation or catalytic transfer hydrogenation under alkaline conditions. Basic hydrodehalogenation is selective for the iodomethyl group over hydrogenolysis-labile protecting groups, such as benzyloxycarbonyl, benzyl ester, benzyl ether, and 9-fluorenyloxymethyl, thus allowing the conversion of virtually any protected amino acid into the corresponding N-protected α-methylamine. PMID:25116734

Development of Paper, Chemical Agent Detector, 3-Way Liquid Containing Non-Mutagenic Dyes. 2. Replacement of the Blue Indicator Dye Ethyl-bis-(2,4- Dinitrophenyl Acetate (EDA)

DTIC Science & Technology

1988-06-01

Reaction MeOH, A (11) 40 7 - CH2 N2 No Reaction 0 0 cresol red (22) 8 Q12 N2 Complex Mixture bromoophenol blue (23) -I...of other analogues, e.g. cresol and thymolghthalein alkyl esters were not as succesfull since the oxidation step at the end was !ound to be more...this compound has both ortho positions blocked so the condensation reaction could occur only at the para position. Nevertheless, as the investigation

Development of a simple method for quantitation of methanesulfonic acid at low ppm level using hydrophilic interaction chromatography coupled with ESI-MS.

PubMed

Huang, Zongyun; Francis, Robert; Zha, Yan; Ruan, Joan

2015-01-01

A simple, sensitive and robust method using HILIC-ESI-MS has been developed for the determination of methane sulfonic acid (MSA) at low ppm level in order to verify the effectiveness of controlling the formation of genotoxic sulfonate esters in the downstream synthetic step, by which produces active pharmaceutical ingredient (API). Stationary phases with positively charged functional groups such as triazole and amino phases were evaluated for the retention of alkyl sulfonic acids. The MSA was quantitated at 1-10 ppm relative to the API using a Cosmosil column (triazole stationary phase) in HILIC mode and the control of MSA can be monitored effectively using the HILIC-ESI-MS methodology. In addition, to provide general guidance for the HILIC-ESI-MS method development, the retention behavior of propanesulfonic acid (PSA) in HILIC mode was investigated using a Unison UK-Amino column to have a better understanding of the HILIC separation mechanism. The results showed reasonable evidence that the combined effect of surface adsorption and ion-exchange played a dominant role for sulfonic acids when using a mobile phase within typical HILIC operation range (0.05-0.20 aqueous volume fraction) while the ion-exchange effect becomes increasingly important in a mobile phase with higher water content. The advantage of using ESI-MS detection in HILIC mode was also demonstrated by the observation that the sensitivity of PSA increased substantially with increasing acetonitrile fraction in mobile phase from 0.80 to 0.95. Copyright © 2014 Elsevier B.V. All rights reserved.

A 13C NMR study of the structure of four cinnamic acids and their methyl esters

NASA Astrophysics Data System (ADS)

Silva, A. M. S.; Alkorta, I.; Elguero, J.; Silva, V. L. M.

2001-09-01

The 13C NMR spectra, both in DMSO solution and in the solid state of four cinnamic acids (p-methoxy, p-hydroxy, p-methyl, p-chloro) and their corresponding methyl esters have been recorded. The two main results in the solid state are: (i) the only significant difference between acids and esters chemical shifts concerns the Cdbnd O group which, on average, appears at 173 ppm in the acids and 168 ppm in the esters; (ii) the signals of the ortho and meta carbons both in the acids and the esters are splitted. The two 'anomalies' disappear in DMSO solution. These observations can be rationalized using simple GIAO/B3LYP/6-31G∗ calculations.

Characteristics of sugar surfactants in stabilizing proteins during freeze-thawing and freeze-drying.

PubMed

Imamura, Koreyoshi; Murai, Katsuyuki; Korehisa, Tamayo; Shimizu, Noriyuki; Yamahira, Ryo; Matsuura, Tsutashi; Tada, Hiroko; Imanaka, Hiroyuki; Ishida, Naoyuki; Nakanishi, Kazuhiro

2014-06-01

Sugar surfactants with different alkyl chain lengths and sugar head groups were compared for their protein-stabilizing effect during freeze-thawing and freeze-drying. Six enzymes, different in terms of tolerance against inactivation because of freeze-thawing and freeze-drying, were used as model proteins. The enzyme activities that remained after freeze-thawing and freeze-drying in the presence of a sugar surfactant were measured for different types and concentrations of sugar surfactants. Sugar surfactants stabilized all of the tested enzymes both during freeze-thawing and freeze-drying, and a one or two order higher amount of added sugar surfactant was required for achieving protein stabilization during freeze-drying than for the cryoprotection. The comprehensive comparison showed that the C10-C12 esters of sucrose or trehalose were the most effective through the freeze-drying process: the remaining enzyme activities after freeze-thawing and freeze-drying increased at the sugar ester concentrations of 1-10 and 10-100 μM, respectively, and increased to a greater extent than for the other surfactants at higher concentrations. Results also indicate that, when a decent amount of sugar was also added, the protein-stabilizing effect of a small amount of sugar ester through the freeze-drying process could be enhanced. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

A monolithic lipase reactor for biodiesel production by transesterification of triacylglycerides into fatty acid methyl esters

PubMed Central

Urban, Jiri; Svec, Frantisek; Fréchet, Jean M.J.

2011-01-01

An enzymatic reactor with lipase immobilized on a monolithic polymer support has been prepared and used to catalyze the transesterification of triacylglycerides into the fatty acid methyl esters commonly used for biodiesel. A design of experiments procedure was used to optimize the monolithic reactor with variables including control of the surface polarity of the monolith via variations in the length of the hydrocarbon chain in alkyl methacrylate monomer, time of grafting of 1-vinyl-4,4-dimethylazlactone used to activate the monolith, and time used for the immobilization of porcine lipase. Optimal conditions involved the use of a poly(stearyl methacrylate-co-ethylene dimethacrylate) monolith, grafted first with vinylazlactone, then treated with lipase for 2 h to carry out the immobilization of the enzyme. Best conditions for the transesterification of glyceryl tributyrate included a temperature of 37°C and a 10 min residence time of the substrate in the bioreactor. The reactor did not lose its activity even after pumping through it a solution of substrate equaling 1,000 reactor volumes. This enzymatic reactor was also used for the transesterification of triacylglycerides from soybean oil to fatty acid methyl esters thus demonstrating the ability of the reactor to produce biodiesel. PMID:21915852

A monolithic lipase reactor for biodiesel production by transesterification of triacylglycerides into fatty acid methyl esters.

PubMed

Urban, Jiri; Svec, Frantisek; Fréchet, Jean M J

2012-02-01

An enzymatic reactor with lipase immobilized on a monolithic polymer support has been prepared and used to catalyze the transesterification of triacylglycerides into the fatty acid methyl esters commonly used for biodiesel. A design of experiments procedure was used to optimize the monolithic reactor with variables including control of the surface polarity of the monolith via variations in the length of the hydrocarbon chain in alkyl methacrylate monomer, time of grafting of 1-vinyl-4,4-dimethylazlactone used to activate the monolith, and time used for the immobilization of porcine lipase. Optimal conditions involved the use of a poly(stearyl methacrylate-co-ethylene dimethacrylate) monolith, grafted first with vinylazlactone, then treated with lipase for 2 h to carry out the immobilization of the enzyme. Best conditions for the transesterification of glyceryl tributyrate included a temperature of 37°C and a 10 min residence time of the substrate in the bioreactor. The reactor did not lose its activity even after pumping through it a solution of substrate equaling 1,000 reactor volumes. This enzymatic reactor was also used for the transesterification of triacylglycerides from soybean oil to fatty acid methyl esters thus demonstrating the ability of the reactor to produce biodiesel. Copyright © 2011 Wiley Periodicals, Inc.

Injectable hyperbranched poly(β-amino ester) hydrogels with on-demand degradation profiles to match wound healing processes† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc03913a

PubMed Central

Xu, Qian; Guo, Linru; A, Sigen; Gao, Yongsheng; Zhou, Dezhong; Greiser, Udo; Creagh-Flynn, Jack; Zhang, Hong; Dong, Yixiao; Cutlar, Lara; Wang, Fagang; Liu, Wenguang

2018-01-01

Adjusting biomaterial degradation profiles to match tissue regeneration is a challenging issue. Herein, biodegradable hyperbranched poly(β-amino ester)s (HP-PBAEs) were designed and synthesized via “A2 + B4” Michael addition polymerization, and displayed fast gelation with thiolated hyaluronic acid (HA-SH) via a “click” thiol–ene reaction. HP-PBAE/HA-SH hydrogels showed tunable degradation profiles both in vitro and in vivo using diamines with different alkyl chain lengths and poly(ethylene glycol) diacrylates with varied PEG spacers. The hydrogels with optimized degradation profiles encapsulating ADSCs were used as injectable hydrogels to treat two different types of humanized excisional wounds – acute wounds with faster healing rates and diabetic wounds with slower healing and neo-tissue formation. The fast-degrading hydrogel showed accelerated wound closure in acute wounds, while the slow-degrading hydrogel showed better wound healing for diabetic wounds. The results demonstrate that the new HP-PBAE-based hydrogel in combination with ADSCs can be used as a well-controlled biodegradable skin substitute, which demonstrates a promising approach in the treatment of various types of skin wounds. PMID:29719691

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

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4FeCl 2. Furthermore, we prepared a series of monoalkylated salts of the type (py) 2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane thatmore » readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2Fe(N 2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.« less

Alcohols as alkylating agents in heteroarene C–H functionalization

PubMed Central

Jin, Jian; MacMillan, David W. C.

2015-01-01

Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage1. One of the core principles that underlies DNA biosynthesis is the radical-mediated elimnation of H2O to deoxygenate ribonucleotides, an example of ‘spin-center shift’ (SCS)2, during which an alcohol C–O bond is cleaved, resulting in a carbon-centered radical intermediate. While SCS is a well-understood biochemical process, it is underutilized by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylations using alcohols as radical precursors. Considering traditional radical-based alkylation methods require the use of stoichiometric oxidants, elevated temperatures, or peroxides3–7, the development of a mild protocol using simple and abundant alkylating agents would have significant utility in the synthesis of diversely functionalized pharmacophores. In this manuscript, we describe the successful execution of this idea via the development of a dual catalytic alkylation of heteroarenes using alcohols as mild alkylating reagents. This method represents the first broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer (HAT) catalysis. The utility of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone. PMID:26308895

Structure and mechanism of an inverting alkylsulfatase from Pseudomonas sp. DSM6611 specific for secondary alkyl sulfates.

PubMed

Knaus, Tanja; Schober, Markus; Kepplinger, Bernhard; Faccinelli, Martin; Pitzer, Julia; Faber, Kurt; Macheroux, Peter; Wagner, Ulrike

2012-12-01

A highly enantioselective and stereoselective secondary alkylsulfatase from Pseudomonas sp. DSM6611 (Pisa1) was heterologously expressed in Escherichia coli BL21, and purified to homogeneity for kinetic and structural studies. Structure determination of Pisa1 by X-ray crystallography showed that the protein belongs to the family of metallo-β-lactamases with a conserved binuclear Zn(2+) cluster in the active site. In contrast to a closely related alkylsulfatase from Pseudomonas aeruginosa (SdsA1), Pisa1 showed a preference for secondary rather than primary alkyl sulfates, and enantioselectively hydrolyzed the (R)-enantiomer of rac-2-octyl sulfate, yielding (S)-2-octanol with inversion of absolute configuration as a result of C-O bond cleavage. In order to elucidate the mechanism of inverting sulfate ester hydrolysis, for which no counterpart in chemical catalysis exists, we designed variants of Pisa1 guided by three-dimensional structure and docking experiments. In the course of these studies, we identified an invariant histidine (His317) near the sulfate-binding site as the general acid for crucial protonation of the sulfate leaving group. Additionally, amino acid replacements in the alkyl chain-binding pocket generated an enzyme variant that lost its stereoselectivity towards rac-2-octyl sulfate. These findings are discussed in light of the potential use of this enzyme family for applications in biocatalysis. © 2012 The Authors Journal compilation © 2012 FEBS.

Functional copolymer/organo-MMT nanoarchitectures. VI. Synthesis and characterization of novel nanocomposites by interlamellar controlled/living radical copolymerization via preintercalated RAFT-agent/organoclay complexes.

PubMed

Rzayev, Zakir M O; Söylemez, A Ernur

2011-04-01

We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecylamine (ODA)-MMT organoclays, and a radical initiator. The method includes the following stages: (1) synthesis of RAFT intercalated O-MMTs by a physical or chemical interaction of the RAFT agent having two pendant carboxylic groups [S,S-bis(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate] with surface alkyl amines of O-MMT containing tertiary ammonium cation or primary amine groups through strong H-bonding and complexing/amidization reactions, respectively, and (2) utilization of these well-dispersed and intercalated RAFT ... O-MMT complexes and their amide derivatives as new modified RAFT agents in radical-initiated interlamellar controlled/living copolymerization of itaconic acid (IA)-n-butylmethacrylate (BMA) monomer pair. The structure and compositions of the synthesized RAFT ... O-MMT complexes and functional copolymer/O-MMT hybrids were confirmed by FTIR, XRD, thermal (DSC-TGA), SEM and TEM morphology analyses. It was demonstrated that the degree of interaction/exfoliation, morphology and thermal behavior of nanocomposites significantly depended on the type of organoclay and in situ interaction, as well as on the content of flexible butyl-ester linkages as a internal plasticizer. The results of the comparative analysis of the nanocomposites structure-composition-property relations show that the functional copolymer-organoclay hybrids prepared with reactive RAFT ... ODA-MMT complex and containing a combination of partially intercalated and predominantly exfoliated nano-structures exhibit relatively higher thermal stability and fine dispersed morphology. These effects were explained by in situ interfacial chemical reactions through amidization of RAFT with surface alkyl amine of MMT clay in interlamellar copolymerization. This simple and versatile method can be applied to a wide range of functional monomer/comonomer systems and mono- and bifunctional RAFT compounds for preparation new generation of nanomaterials.

Extracellular lipids of Camelina sativa: characterization of chloroform-extractable waxes from aerial and subterranean surfaces.

PubMed

Razeq, Fakhria M; Kosma, Dylan K; Rowland, Owen; Molina, Isabel

2014-10-01

Camelina sativa (L.) Crantz is an emerging low input, stress tolerant crop with seed oil composition suitable for biofuel and bioproduct production. The chemical compositions and ultrastructural features of surface waxes from C. sativa aerial cuticles, seeds, and roots were analyzed using gas chromatography and microscopy. Alkanes, primary fatty alcohols, and free fatty acids were common components of all analyzed organs. A particular feature of leaf waxes was the presence of alkyl esters of long-chain fatty acids and very long-chain fatty alcohols, ranging from C38 to C50 and dominated by C42, C44 and C46 homologues. Stem waxes were mainly composed of non-sterol pentacyclic triterpenes. Flowers accumulated significant amounts of methyl-branched iso-alkanes (C29 and C31 total carbon number) in addition to straight-chain alkanes. Seed waxes were mostly primary fatty alcohols of up to 32 carbons in length and unbranched C29 and C31 alkanes. The total amount of identified wax components extracted by rapid chloroform dipping of roots was 280μgg(-1) (fresh weight), and included alkyl hydroxycinnamates, predominantly alkyl coumarates and alkyl caffeates. This study provides qualitative and quantitative information on the waxes of C. sativa root, shoot, and seed boundary tissues, allowing the relative activities of wax biosynthetic pathways in each respective plant organ to be assessed. This detailed description of the protective surface waxes of C. sativa may provide insights into its drought-tolerant and pathogen-resistant properties, and also identifies C. sativa as a potential source of renewable high-value natural products. Copyright © 2014 Elsevier Ltd. All rights reserved.

Development of a general non-noble metal catalyst for the benign amination of alcohols with amines and ammonia.

PubMed

Cui, Xinjiang; Dai, Xingchao; Deng, Youquan; Shi, Feng

2013-03-11

The N-alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N-alkyl amines. However, as a potentially clean and economic choice for N-alkyl amine synthesis, non-noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCuFeOx catalyst was designed and prepared for the N-alkylation of ammonia or amines with alcohol or primary amines. N-alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N-heterocyclic compounds, and secondary amines could be N-alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one-pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Borate esters: Simple catalysts for the sustainable synthesis of complex amides

PubMed Central

Sabatini, Marco T.; Boulton, Lee T.; Sheppard, Tom D.

2017-01-01

Chemical reactions for the formation of amide bonds are among the most commonly used transformations in organic chemistry, yet they are often highly inefficient. A novel protocol for amidation using a simple borate ester catalyst is reported. The process presents significant improvements over other catalytic amidation methods in terms of efficiency and safety, with an unprecedented substrate scope including functionalized heterocycles and even unprotected amino acids. The method was used to access a wide range of functionalized amide derivatives, including pharmaceutically relevant targets, important synthetic intermediates, a catalyst, and a natural product. PMID:28948222

A simple synthesis of N-perfluoroacylated and N-acylated glycals of neuraminic acid with a cyclic aminic substituent at the 4α position as possible inhibitors of sialidases.

PubMed

Rota, Paola; Allevi, Pietro; Agnolin, Irene S; Mattina, Roberto; Papini, Nadia; Anastasia, Mario

2012-04-14

A simple protocol for the synthesis of N-perfluoroacylated and N-acylated glycals of neuraminic acid, with a secondary cyclic amine (morpholine or piperidine) at the 4α position, has been set-up, starting from peracetylated N-acetylneuraminic acid methyl ester that undergoes, sequentially to its direct N-transacylation followed by a C-4 amination, a β-elimination, and a selective hydrolysis of the ester functions, without affecting the sensitive perfluorinated amide. This journal is © The Royal Society of Chemistry 2012

Green polymer chemistry: The role of Candida antarctica lipase B in polymer functionalization

NASA Astrophysics Data System (ADS)

Castano Gil, Yenni Marcela

The synthesis of functional polymers with well-defined structure, end-group fidelity and physico-chemical properties useful for biomedical applications has proven challenging. Chemo-enzymatic methods are an alternative strategy to increase the diversity of functional groups in polymeric materials. Specifically, enzyme-catalyzed polymer functionalization carried out under solventless conditions is a great advancement in the design of green processes for biomedical applications, where the toxicity of solvents and catalyst residues need to be considered. Enzymes offer several distinct advantages, including high efficiency, catalyst recyclability, and mild reaction conditions. This reseach aimed to precisely functionalized polymers using two methods: enzyme-catalyzed functionalization via polymerization and chemo-enzymatic functionalization of pre-made polymers for drug delivery. In the first method, well-defined poly(caprolactone)s were generated using alkyne-based initiating systems catalyzed by CALB. Propargyl alcohol and 4-dibenzocyclooctynol (DIBO) were shown to efficiently initiate the ring opening polymerization of epsilon-caprolactone under metal free conditions and yielded polymers with Mn ~4 to 24 KDa and relatively narrow molecular mass distribution. In the second methodology, we present quantitative enzyme-catalyzed transesterification of vinyl esters and ethyl esters with poly(ethylene glycol)s (PEG)s that will serve as building blocks for dendrimer synthesis, followed by introducing a new process for the exclusive gamma-conjugation of folic acid. Specifically, fluorescein-acrylate was enzymatically conjugated with PEG. Additionally, halo-ester functionalized PEGs were successfully prepared by the transesterification of alkyl halo-esters with PEGs. 1H and 13C NMR spectroscopy, SEC and MALDI-ToF mass spectrometry confirmed the structure and purity of the products.

Construction of combustion models for rapeseed methyl ester bio-diesel fuel for internal combustion engine applications.

PubMed

Golovitchev, Valeri I; Yang, Junfeng

2009-01-01

Bio-diesel fuels are non-petroleum-based diesel fuels consisting of long chain alkyl esters produced by the transesterification of vegetable oils, that are intended for use (neat or blended with conventional fuels) in unmodified diesel engines. There have been few reports of studies proposing theoretical models for bio-diesel combustion simulations. In this study, we developed combustion models based on ones developed previously. We compiled the liquid fuel properties, and the existing detailed mechanism of methyl butanoate ester (MB, C(5)H(10)O(2)) oxidation was supplemented by sub-mechanisms for two proposed fuel constituent components, C(7)H(16) and C(7)H(8)O (and then, by mp2d, C(4)H(6)O(2) and propyne, C(3)H(4)) to represent the combustion model for rapeseed methyl ester described by the chemical formula, C(19)H(34)O(2) (or C(19)H(36)O(2)). The main fuel vapor thermal properties were taken as those of methyl palmitate C(19)H(36)O(2) in the NASA polynomial form of the Burcat database. The special global reaction was introduced to "crack" the main fuel into its constituent components. This general reaction included 309 species and 1472 reactions, including soot and NO(x) formation processes. The detailed combustion mechanism was validated using shock-tube ignition-delay data under diesel engine conditions. For constant volume and diesel engine (Volvo D12C) combustion modeling, this mechanism could be reduced to 88 species participating in 363 reactions.

Erratum to "The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase" : [Int. J. Mass Spectrom. Ion Process. 172 (1998) 25

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-02-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R+R'-OH-->-CH2-CO2-R'+R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'--OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

Experimental and modeling study of the thermal decomposition of methyl decanoate

PubMed Central

Herbinet, Olivier; Glaude, Pierre-Alexandre; Warth, Valérie; Battin-Leclerc, Frédérique

2013-01-01

The experimental study of the thermal decomposition of methyl decanoate was performed in a jet-stirred reactor at temperatures ranging from 773 to 1123 K, at residence times between 1 and 4 s, at a pressure of 800 Torr (106.6 kPa) and at high dilution in helium (fuel inlet mole fraction of 0.0218). Species leaving the reactor were analyzed by gas chromatography. Main reaction products were hydrogen, carbon oxides, small hydrocarbons from C1 to C3, large 1-olefins from 1-butene to 1-nonene, and unsaturated esters with one double bond at the end of the alkyl chain from methyl-2-propenoate to methyl-8-nonenoate. At the highest temperatures, the formation of polyunsaturated species was observed: 1,3-butadiene, 1,3-cyclopentadiene, benzene, toluene, indene, and naphthalene. These results were compared with previous ones about the pyrolysis of n-dodecane, an n-alkane of similar size. The reactivity of both molecules was found to be very close. The alkane produces more olefins while the ester yields unsaturated oxygenated compounds. A detailed kinetic model for the thermal decomposition of methyl decanoate has been generated using the version of software EXGAS which was updated to take into account the specific chemistry involved in the oxidation of methyl esters. This model contains 324 species and 3231 reactions. It provided a very good prediction of the experimental data obtained in jet-stirred reactor. The formation of the major products was analyzed. The kinetic analysis showed that the retro-ene reactions of intermediate unsaturated methyl esters are of importance in low reactivity systems. PMID:23710078

Predicting hydration Gibbs energies of alkyl-aromatics using molecular simulation: a comparison of current force fields and the development of a new parameter set for accurate solvation data.

PubMed

Garrido, Nuno M; Jorge, Miguel; Queimada, António J; Gomes, José R B; Economou, Ioannis G; Macedo, Eugénia A

2011-10-14

The Gibbs energy of hydration is an important quantity to understand the molecular behavior in aqueous systems at constant temperature and pressure. In this work we review the performance of some popular force fields, namely TraPPE, OPLS-AA and Gromos, in reproducing the experimental Gibbs energies of hydration of several alkyl-aromatic compounds--benzene, mono-, di- and tri-substituted alkylbenzenes--using molecular simulation techniques. In the second part of the paper, we report a new model that is able to improve such hydration energy predictions, based on Lennard Jones parameters from the recent TraPPE-EH force field and atomic partial charges obtained from natural population analysis of density functional theory calculations. We apply a scaling factor determined by fitting the experimental hydration energy of only two solutes, and then present a simple rule to generate atomic partial charges for different substituted alkyl-aromatics. This rule has the added advantages of eliminating the unnecessary assumption of fixed charge on every substituted carbon atom and providing a simple guideline for extrapolating the charge assignment to any multi-substituted alkyl-aromatic molecule. The point charges derived here yield excellent predictions of experimental Gibbs energies of hydration, with an overall absolute average deviation of less than 0.6 kJ mol(-1). This new parameter set can also give good predictive performance for other thermodynamic properties and liquid structural information.

A General and Selective Rhodium-Catalyzed Reduction of Amides, N-Acyl Amino Esters, and Dipeptides Using Phenylsilane.

PubMed

Das, Shoubhik; Li, Yuehui; Lu, Liang-Qiu; Junge, Kathrin; Beller, Matthias

2016-05-17

This article describes a selective reduction of functionalized amides, including N-acyl amino esters and dipeptides, to the corresponding amines using simple [Rh(acac)(cod)]. The catalyst shows excellent chemoselectivity in the presence of different sensitive functional moieties. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isolation of Biliverdin Ixa, as Its Dimethyl Ester, from Emu Eggshells

ERIC Educational Resources Information Center

Halepas, Steven; Hamchand, Randy; Lindeyer, Samuel E. D.; Bru¨ckner, Christian

2017-01-01

A laboratory experiment is described that extracts the tetrapyrrolic teal-colored biliverdin IXa, as its dimethyl ester, from commercially available emu eggshells. The extraction of ~10 mg samples of biliverdin is simple and requires two 3 h lab periods: A two-step acid digestion and liquid-liquid extraction, followed by short silica gel flash…

Deoxygenation of Unhindered Alcohols via Reductive Dealkylation of Derived Phosphate Esters

DOE PAGES

Chowdhury, Sarwat; Standaert, Robert F.

2016-09-15

Primary alcohols can be deoxygenated cleanly and in high yield by reduction of derived diphenyl phosphate esters with lithium triethylborohydride in tetrahydrofuran at room temperature. Selective deoxygenation of a primary alcohol in the presence of a secondary alcohol was demonstrated. The two-step process can be performed in one pot, making it both simple and convenient.

DNA Damage Induced by Alkylating Agents and Repair Pathways

PubMed Central

Kondo, Natsuko; Takahashi, Akihisa; Ono, Koji; Ohnishi, Takeo

2010-01-01

The cytotoxic effects of alkylating agents are strongly attenuated by cellular DNA repair processes, necessitating a clear understanding of the repair mechanisms. Simple methylating agents form adducts at N- and O-atoms. N-methylations are removed by base excision repair, AlkB homologues, or nucleotide excision repair (NER). O6-methylguanine (MeG), which can eventually become cytotoxic and mutagenic, is repaired by O6-methylguanine-DNA methyltransferase, and O6MeG:T mispairs are recognized by the mismatch repair system (MMR). MMR cannot repair the O6MeG/T mispairs, which eventually lead to double-strand breaks. Bifunctional alkylating agents form interstrand cross-links (ICLs) which are more complex and highly cytotoxic. ICLs are repaired by complex of NER factors (e.g., endnuclease xeroderma pigmentosum complementation group F-excision repair cross-complementing rodent repair deficiency complementation group 1), Fanconi anemia repair, and homologous recombination. A detailed understanding of how cells cope with DNA damage caused by alkylating agents is therefore potentially useful in clinical medicine. PMID:21113301

A process model to estimate biodiesel production costs.

PubMed

Haas, Michael J; McAloon, Andrew J; Yee, Winnie C; Foglia, Thomas A

2006-03-01

'Biodiesel' is the name given to a renewable diesel fuel that is produced from fats and oils. It consists of the simple alkyl esters of fatty acids, most typically the methyl esters. We have developed a computer model to estimate the capital and operating costs of a moderately-sized industrial biodiesel production facility. The major process operations in the plant were continuous-process vegetable oil transesterification, and ester and glycerol recovery. The model was designed using contemporary process simulation software, and current reagent, equipment and supply costs, following current production practices. Crude, degummed soybean oil was specified as the feedstock. Annual production capacity of the plant was set at 37,854,118 l (10 x 10(6)gal). Facility construction costs were calculated to be US dollar 11.3 million. The largest contributors to the equipment cost, accounting for nearly one third of expenditures, were storage tanks to contain a 25 day capacity of feedstock and product. At a value of US dollar 0.52/kg (dollar 0.236/lb) for feedstock soybean oil, a biodiesel production cost of US dollar 0.53/l (dollar 2.00/gal) was predicted. The single greatest contributor to this value was the cost of the oil feedstock, which accounted for 88% of total estimated production costs. An analysis of the dependence of production costs on the cost of the feedstock indicated a direct linear relationship between the two, with a change of US dollar 0.020/l (dollar 0.075/gal) in product cost per US dollar 0.022/kg (dollar 0.01/lb) change in oil cost. Process economics included the recovery of coproduct glycerol generated during biodiesel production, and its sale into the commercial glycerol market as an 80% w/w aqueous solution, which reduced production costs by approximately 6%. The production cost of biodiesel was found to vary inversely and linearly with variations in the market value of glycerol, increasing by US dollar 0.0022/l (dollar 0.0085/gal) for every US dollar 0.022/kg (dollar 0.01/lb) reduction in glycerol value. The model is flexible in that it can be modified to calculate the effects on capital and production costs of changes in feedstock cost, changes in the type of feedstock employed, changes in the value of the glycerol coproduct, and changes in process chemistry and technology.

Semi-catalytic reduction of secondary amides to imines and aldehydes.

PubMed

Lee, Sun-Hwa; Nikonov, Georgii I

2014-06-21

Secondary amides can be reduced by silane HSiMe2Ph into imines and aldehydes by a two-stage process involving prior conversion of amides into iminoyl chlorides followed by catalytic reduction mediated by the ruthenium complex [Cp(i-Pr3P)Ru(NCCH3)2]PF6 (1). Alkyl and aryl amides bearing halogen, ketone, and ester groups were converted with moderate to good yields under mild reaction conditions to the corresponding imines and aldehydes. This procedure does not work for substrates bearing the nitro-group and fails for heteroaromatic amides. In the case of cyano substituted amides, the cyano group is reduced to imine.

Wide bandgap OPV polymers based on pyridinonedithiophene unit with efficiency >5%

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

Schneider, Alexander M.; Lu, Luyao; Manley, Eric F.

2015-06-04

We report the properties of a new series of wide band gap photovoltaic polymers based on the N-alkyl 2-pyridone dithiophene (PDT) unit. These polymers are effective bulk heterojunction solar cell materials when blended with phenyl-C 71-butyric acid methyl ester (PC 71BM). They achieve power conversion efficiencies (up to 5.33%) high for polymers having such large bandgaps, ca. 2.0 eV (optical) and 2.5 eV (electrochemical). As a result, grazing incidence wide-angle X-ray scattering (GIWAXS) reveals strong correlations between π–π stacking distance and regularity, polymer backbone planarity, optical absorption maximum energy, and photovoltaic efficiency.

Bifunctional Alkylating Agent-Induced p53 and Nonclassical Nuclear Factor kB Responses and Cell Death are Altered by Caffeic Acid Phenethyl Ester: A Potential Role for Antioxidant/Electrophilic Response-Element Signaling

DTIC Science & Technology

2007-01-01

Methods. To establish the maximal LDH 2,3,7,8-tetrachloro- activity achievable from these cells, untreated control cells were grown dibenzo-p- dioxin to the...to modulated by AhR (Miao et al., 2005). Curcumin has been induce apoptosis. CAPE may be involved in anoikis, that is, shown to compete with dioxin ...the AhR directly binds (Miao et al., 2005). adhesion kinase (Weyant et al., 2000). Also, CAPE-induced Exposure of Hepalclc7 cells to dioxin results in

New synthetic possibilities for the preparation of liquid crystalline dicyclohexyl derivatives

NASA Astrophysics Data System (ADS)

Sasnouski, Genadz; Bezborodov, Vladimir; Dabrowski, Roman S.; Dziaduszek, Jerzy

2000-05-01

A new synthetic approach for the preparation of two- and three ring liquid crystalline compounds possessing trans,trans-dicyclohexyl moiety is proposed and realized. Recently discovered reaction of Grignard reagents with esters leading to 1-substituted cyclopropanoles in the presence of tetraisopropoxytitanium was used as a key stage. Starting from ethyl trans-4-alkylcyclohexancarboxylates the corresponding 6-(4-alkylcyclohexyl)-3-alkyl (or aryl) cyclohex-2-en-1-ones have been prepared. Their catalytic hydrogenation in the base media gave mainly saturated trans, trans-ketones which are liquid crystalline and have been used also as a promising intermediate products for the preparation of different kinds of other LC compounds.

Synthesis and anticonvulsant activities of N-benzyl (2R)-2-acetamido-3-oxysubstituted propionamide derivatives

PubMed Central

Morieux, Pierre; Stables, James P.; Kohn, Harold

2009-01-01

Lacosamide has been submitted for regulatory approval in the United States and Europe for the treatment of epilepsy. Previous synthetic methods did not permit the elaboration of the structure–activity relationship (SAR) for the 3-oxy site in lacosamide. We report an expedient five-step stereospecific synthesis for N-benzyl (2R)-2-acetamido-3-oxysubstituted propionamide analogs beginning with d-serine methyl ester. The procedure incorporated alkyl (e.g. methyl, primary, secondary, and tertiary) and aryl groups at this position. The SAR for the 3-oxy site showed maximal activity in animal seizure models for small 3-alkoxy substituents. PMID:18789868

Oleochemical industry future through biotechnology.

PubMed

Abdelmoez, Wael; Mustafa, Ahmad

2014-01-01

Lipases are the most widely used class of enzymes in organic synthesis. Enzymatic processes have been implemented in a broad range of industries as they are specific, save raw materials, energy and chemicals, environmentally friendly and fast in action compared to conventional processes. The most notable benefit is the moderate process temperature and pressure with no unwanted side reactions. In the past two decades, intensive research was carried out towards enzymatic synthesis of oleochemicals. This review has a sharp focus on the current implemented enzymatic processes for producing different oleochemicals such as fatty acids, glycerin, biodiesel, biolubricant and different alkyl esters via different processes including hydrolysis, esterification, transesterification and intraesterification.

P-Tether-Mediated, Iterative SN2'-Cuprate Alkylation Strategy to Skipped Polyol Stereotetrads: Utility of an Oxidative "Function Switch" with Phosphite-Borane Tethers.

PubMed

Markley, Jana L; Hanson, Paul R

2017-05-19

The development of a P-tether-mediated, iterative S N 2'-cuprate alkylation protocol for the formation of 1,3-skipped polyol stereotetrads is reported. This two-directional synthetic strategy builds molecular complexity from simple, readily prepared C 2 -symmetric dienediols and unites the chemistry of both temporary phosphite-borane tethers and temporary phosphate tethers-through an oxidative "function switch" of the P-tether itself-to generate intermediates that were previously inaccessible via either method alone.

A simple and sensitive fluorescent sensor for methyl parathion based on L-tyrosine methyl ester functionalized carbon dots.

PubMed

Hou, Juying; Dong, Jing; Zhu, Haishuang; Teng, Xue; Ai, Shiyun; Mang, Minglin

2015-06-15

In this paper, a simple and sensitive fluorescent sensor for methyl parathion is developed based on L-tyrosine methyl ester functionalized carbon dots (Tyr-CDs) and tyrosinase system. The carbon dots are obtained by simple hydrothermal reaction using citric acid as carbon resource and L-tyrosine methyl ester as modification reagent. The carbon dots are characterized by transmission electron microscope, high resolution transmission electron microscopy, X-ray diffraction spectrum, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The carbon dots show strong and stable photoluminescence with a quantum yield of 3.8%. Tyrosinase can catalyze the oxidation of tyrosine methyl ester on the surface of carbon dots to corresponding quinone products, which can quench the fluorescence of carbon dots. When organophosphorus pesticides (OPs) are introduced in system, they can decrease the enzyme activity, thus decrease the fluorescence quenching rate. Methyl parathion, as a model of OPs, was detected. Experimental results show that the enzyme inhibition rate is proportional to the logarithm of the methyl parathion concentration in the range 1.0×10(-10)-1.0×10(-4) M with the detection limit (S/N=3) of 4.8×10(-11) M. This determination method shows a low detection limit, wide linear range, good selectivity and high reproducibility. This sensing system has been successfully used for the analysis of cabbage, milk and fruit juice samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Spectroscopic Properties of Some Simple Esters: A Practical Application of Synthesis and Spectroscopy in the Undergraduate Organic Laboratory

ERIC Educational Resources Information Center

Brown, David P.; Durutlic, Haris; Juste, Didier

2004-01-01

Experiments are conducted for spectroscopic analysis of the allyl esters of some aromatic carboxylic acids. It is understood that these experiments allow the students to monitor the effect of hydrogen bonding on the IR stretching frequencies for the hydroxyl and carbonyl groups and also provide them with an excellent opportunity to examine the…

Chemical Kinetic Influences of Alkyl Chain Structure on the High Pressure and Temperature Oxidation of a Representative Unsaturated Biodiesel: Methyl Nonenoate.

PubMed

Fridlyand, Aleksandr; Goldsborough, S Scott; Brezinsky, Kenneth

2015-07-16

The high pressure and temperature oxidation of methyl trans-2-nonenoate, methyl trans-3-nonenoate, 1-octene, and trans-2-octene are investigated experimentally to probe the influence of the double bond position on the chemical kinetics of long esters and alkenes. Single pulse shock tube experiments are performed in the ranges p = 3.8-6.2 MPa and T = 850-1500 K, with an average reaction time of 2 ms. Gas chromatographic measurements indicate increased reactivity for trans-2-octene compared to 1-octene, whereas both methyl nonenoate isomers have reactivities similar to that of 1-octene. A difference in the yield of stable intermediates is observed for the octenes when compared to the methyl nonenoates. Chemical kinetic models are developed with the aid of the Reaction Mechanism Generator to interpret the experimental results. The models are created using two different base chemistry submodels to investigate the influence of the foundational chemistry (i.e., C0-C4), whereas Monte Carlo simulations are performed to examine the quality of agreement with the experimental results. Significant uncertainties are found in the chemistry of unsaturated esters with the double bonds located close to the ester groups. This work highlights the importance of the foundational chemistry in predictive chemical kinetics of biodiesel combustion at engine relevant conditions.

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

NASA Technical Reports Server (NTRS)

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

2001-01-01

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

Mass spectrometry of analytical derivatives. 1. Cyanide cations in the spectra of N-alkyl-N-perfluoroacyl-α-amino acids and their methyl esters

PubMed Central

Todua, Nino G.; Tretyakov, Kirill V.; Mikaia, Anzor I.

2016-01-01

The central mission for the development of the National Institute of Standards and Technology/National Institutes of Health/Environmental Protection Agency Mass Spectral Library is the acquisition of reference gas chromatography–mass spectrometry data for important compounds and their chemical modification products. The addition of reliable reference data of various derivatives of amino acids to The Library, and the study of their behavior under electron ionization conditions may be useful for their identification, structure elucidation, and a better understanding of the data obtained when the same derivatives are subjected to other ionization methods. N-Alkyl-N-perfluoroacyl derivatives of amino acids readily produce previously unreported alkylnitrilium cations of composition [HC≡N-alkyl]+. Homologous [HC≡N-aryl]+ cations are typical for corresponding N-aryl analogs. The formation of other ions characteristic for these derivatives involves oxygen rearrangement giving rise to ions [CnF2n+1–C≡N+–CnH2n+1] and [CnF2n+1–C≡N+-aryl]. The introduction of an N-benzyl substituent in a molecule favors a process producing benzylidene iminium cations. l-Threonine and l-cysteine derivatives exhibit more fragmentation pathways not typical for other α-amino acids; additionally, the Nω-amino group in l-lysine directs the dissociation process and provides structural information on the substitution at the amino functions in the molecule. PMID:26307698

Can two-dimensional gas chromatography/mass spectrometric identification of bicyclic aromatic acids in petroleum fractions help to reveal further details of aromatic hydrocarbon biotransformation pathways?

PubMed

West, Charles E; Pureveen, Jos; Scarlett, Alan G; Lengger, Sabine K; Wilde, Michael J; Korndorffer, Frans; Tegelaar, Erik W; Rowland, Steven J

2014-05-15

The identification of key acid metabolites ('signature' metabolites) has allowed significant improvements to be made in our understanding of the biodegradation of petroleum hydrocarbons, in reservoir and in contaminated natural systems, such as aquifers and seawater. On this basis, anaerobic oxidation is now more widely accepted as one viable mechanism, for instance. However, identification of metabolites in the complex acid mixtures from petroleum degradation is challenging and would benefit from use of more highly resolving analytical methods. Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GCxGC/TOFMS) with both nominal mass and accurate mass measurement was used to study the complex mixtures of aromatic acids (as methyl esters) in petroleum fractions. Numerous mono- and di-aromatic acid isomers were identified in a commercial naphthenic acids fraction from petroleum and in an acids fraction from a biodegraded petroleum. In many instances, compounds were identified by comparison of mass spectral and retention time data with those of authentic compounds. The identification of a variety of alkyl naphthalene carboxylic and alkanoic and alkyl tetralin carboxylic and alkanoic acids, plus identifications of a range of alkyl indane acids, provides further evidence for 'signature' metabolites of biodegradation of aromatic petroleum hydrocarbons. Identifications such as these now offer the prospect of better differentiation of metabolites of bacterial processes (e.g. aerobic, methanogenic, sulphate-reducing) in polar petroleum fractions. Copyright © 2014 John Wiley & Sons, Ltd.

Structural isomers of polyfluorinated di- and tri-alkylated phosphate ester surfactants present in industrial blends and in microwave popcorn bags.

PubMed

Trier, Xenia; Nielsen, Nikoline Juul; Christensen, Jan H

2011-09-01

In this study, we provide strategies for detecting and quantifying the structural isomers of polyfluorinated di- and tri-alkyl surfactants (PFAS) by mass spectrometry (MS). We specifically investigate polyfluorinated dialkylated phosphate ester surfactants (x:2/y:2 diPAPS, (F(CF(2))( x )CH(2)CH(2)O-P(O)(O)(-)-OCH(2)CH(2)(CF(2))( y )F)) and their thioether analogues (x:2/y:2 S-diPAPS, F(CF(2))( x )CH(2)CH(2)SCH(2)-C[CH(2)O)(2)P(O)(O)(-)]-CH(2)SCH(2)CH(2)(CF(2))( y )F), which are used for industrial applications, such as oil- and water-repellent coatings on paper and board. DiPAPS have been found in human blood and are metabolised to the persistent perfluoroalkyl carboxylic acids (PFCA) in rats. A microwave popcorn bag extract was analysed by ultrahigh-pressure liquid chromatography coupled to a negative electrospray ionisation-quadrupole time-of-flight MS. The extract contained S-diPAPS, diPAPS and trialkylated (triPAPS) impurities. TriPAPS were also present in industrial and synthetic diPAPS standards, and were verified with an 8:2/8:2/8:2 triPAPS standard. The eight elemental compositions (m/z's) of diPAPS in the extract represent 19 precursor ion structures, and the six S-diPAPS m/z's represent at least 13 structures. The diPAPS had [M-H](-) precursor ions of m/z 789, 889,…1,489 and the S-diPAPS of m/z 921, 1,021,…1,421, corresponding to fluorinated chains from C(6-18). Each m/z appeared as one to three chromatographic peaks of structural isomers, where, e.g. m/z 1,189 was present as 10:2/10:2, 8:2/12:2 and 6:2/14:2 diPAPS. The isomers formed different products ions, thus only half of the m/z 1,189 diPAPS concentration was measured with one precursor ion > product ion transition. In general, knowledge about structural isomers of poly-alkylated PFAS is needed for the estimation of types and amounts of perfluorinated degradation products, such as PFCA from diPAPS.

Scaffold Repurposing of Nucleosides (Adenosine Receptor Agonists): Enhanced Activity at the Human Dopamine and Norepinephrine Sodium Symporters.

PubMed

Tosh, Dilip K; Janowsky, Aaron; Eshleman, Amy J; Warnick, Eugene; Gao, Zhan-Guo; Chen, Zhoumou; Gizewski, Elizabeth; Auchampach, John A; Salvemini, Daniela; Jacobson, Kenneth A

2017-04-13

We have repurposed (N)-methanocarba adenosine derivatives (A 3 adenosine receptor (AR) agonists) to enhance radioligand binding allosterically at the human dopamine (DA) transporter (DAT) and inhibit DA uptake. We extended the structure-activity relationship of this series with small N 6 -alkyl substitution, 5'-esters, deaza modifications of adenine, and ribose restored in place of methanocarba. C2-(5-Halothien-2-yl)-ethynyl 5'-methyl 9 (MRS7292) and 5'-ethyl 10 (MRS7232) esters enhanced binding at DAT (EC 50 ∼ 35 nM) and at the norepinephrine transporter (NET). 9 and 10 were selective for DAT compared to A 3 AR in the mouse but not in humans. At DAT, the binding of two structurally dissimilar radioligands was enhanced; NET binding of only one radioligand was enhanced; SERT radioligand binding was minimally affected. 10 was more potent than cocaine at inhibiting DA uptake (IC 50 = 107 nM). Ribose analogues were weaker in DAT interaction than the corresponding bicyclics. Thus, we enhanced the neurotransmitter transporter activity of rigid nucleosides while reducing A 3 AR affinity.

Surface-segregated monolayers: a new type of ordered monolayer for surface modification of organic semiconductors.

PubMed

Wei, Qingshuo; Tajima, Keisuke; Tong, Yujin; Ye, Shen; Hashimoto, Kazuhito

2009-12-09

We report a new type of ordered monolayer for the surface modification of organic semiconductors. Fullerene derivatives with fluorocarbon chains ([6,6]-phenyl-C(61)-buryric acid 1H,1H-perfluoro-1-alkyl ester or FC(n)) spontaneously segregated as a monolayer on the surface of a [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) film during a spin-coating process from the mixture solutions, as confirmed by X-ray photoelectron spectroscopy (XPS). Ultraviolet photoelectron spectroscopy (UPS) showed the shift of ionization potentials (IPs) depending on the fluorocarbon chain length, indicating the formation of surface dipole moments. Surface-sensitive vibrational spectroscopy, sum frequency generation (SFG) revealed the ordered molecular orientations of the C(60) moiety in the surface FC(n) layers. The intensity of the SFG signals from FC(n) on the surface showed a clear odd-even effect when the length of the fluorocarbon chain was changed. This new concept of the surface-segregated monolayer provides a facile and versatile approach to modifying the surface of organic semiconductors and is applicable to various organic optoelectronic devices.

Synthesis, structural characterization and dielectric behavior of new oxime-cyclotriphosphazene derivatives

NASA Astrophysics Data System (ADS)

Koran, Kenan; Özen, Furkan; Biryan, Fatih; Görgülü, Ahmet Orhan

2016-02-01

The cyclotriphosphazene compound (2) bearing formyl groups as side groups was obtained from the reaction of 2,2-Dichloro-4,4,6,6-bis[spiro(2‧,2″-dioxy-1‧,1″-biphenylyl)]cyclotriphosphazene (1) with 4-hydroxy-3-methoxybenzaldehyde in the presence K2CO3 in tetrahydrofuran. Oxime-cyclotriphosphazene compound (3) was synthesized from the reaction of compound 2 with hydroxylamine hydrochloride in pyridine. The synthesized oxime-phosphazene compound (3) was reacted with alkyl and acyl halides. As a results, the cyclotriphosphazene compounds (1-10) bearing oxime ether and ester as side groups were obtained. The chemical structures of these compounds (1-10) were determined by elemental analysis, FT-IR, 1H, 13C and 31P NMR spectroscopic methods. Dielectric constant, dielectric loss factors and conductivity properties of cyclotriphosphazene compounds were measured over the frequency range from 100 Hz to 2 kHz at 25 °C and compared with each other. It is found that ester substituted cyclotriphosphazenes have higher dielectric constant. Our study suggests that these phosphazenes promising candidate materials in multifunctional optoelectronic devices.

Optimization of biodiesel synthesis by esterification using a fermented solid produced by Rhizopus microsporus on sugarcane bagasse.

PubMed

Botton, Vanderleia; Piovan, Leandro; Meier, Henry França; Mitchell, David Alexander; Cordova, Jesús; Krieger, Nadia

2018-04-01

A fermented solid containing lipases was produced by solid-state fermentation of Rhizopus microsporus on sugarcane bagasse enriched with urea, soybean oil, and a mineral solution. The dry fermented solid produced using R. microsporus (RMFS) was used to catalyze the synthesis of alkyl-esters by esterification in a solvent-free system containing ethanol and oleic acid (as a model system) or a mixture of fatty acids obtained from the physical hydrolysis of soybean soapstock acid oil (FA-SSAO) in subcritical water. The conversions were 93.5 and 84.1%, for oleic acid and FA-SSAO, respectively, at 48 h and 40 °C, at a molar ratio (MR) of ethanol to fatty acid of 5:1. A further increase in the MR to 10:1 improved the production of ethylic-esters, giving conversions at 48 h of 98 and 86% for oleic acid and FA-SSAO, respectively. The results obtained in this work foster further studies on scaling-up of an environmentally friendly process to produce biofuels.

Process and catalyst for carbonylating olefins

DOEpatents

Zoeller, Joseph Robert

1998-06-02

Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

Highly Functionalized 1,2–Diamino Compounds through Reductive Amination of Amino Acid-Derived β–Keto Esters

PubMed Central

Pérez-Faginas, Paula; Aranda, M. Teresa; García-López, M. Teresa; Infantes, Lourdes; Fernández-Carvajal, Asia; González-Ros, José Manuel; Ferrer-Montiel, Antonio; González-Muñiz, Rosario

2013-01-01

1,2-Diamine derivatives are valuable building blocks to heterocyclic compounds and important precursors of biologically relevant compounds. In this respect, amino acid-derived β–keto esters are a suitable starting point for the synthesis of β,γ–diamino ester derivatives through a two-step reductive amination procedure with either simple amines or α–amino esters. AcOH and NaBH3CN are the additive and reducing agents of choice. The stereoselectivity of the reaction is still an issue, due to the slow imine-enamine equilibria through which the reaction occurs, affording mixtures of diastereoisomers that can be chromatographically separated. Transformation of the β,γ–diamino esters into pyrrolidinone derivatives allows the configuration assignment of the linear compounds, and constitutes an example of their potential application in the generation of molecular diversity. PMID:23308167

Disruption of Retinol (Vitamin A) Signaling by Phthalate Esters: SAR and Mechanism Studies.

PubMed

Chen, Yanling; Reese, David H

2016-01-01

A spectrum of reproductive system anomalies (cryptorchidism, hypospadias, dysgenesis of Wolffian duct-derived tissues and prostate, and reduced sperm production) in male rats exposed in utero to phthalate esters (PEs) are thought to be caused by PE inhibition of fetal testosterone production. Recently, dibutyl and dipentyl phthalate (DBuP, DPnP) were shown to disrupt the retinol signaling pathway (RSP) in mouse pluripotent P19 embryonal carcinoma cells in vitro. The RSP regulates the synthesis and cellular levels of retinoic acid (RA), the active metabolite of retinol (vitamin A). In this new study, a total of 26 di- and mono-esters were screened to identify additional phthalate structures that disrupt the RSP and explore their mechanisms of action. The most potent PEs, those causing > 50% inhibition, contained aryl and cycloalkane groups or C4-C6 alkyl ester chains and were the same PEs reported to cause malformations in utero. They shared similar lipid solubility; logP values were between 4 and 6 and, except for PEs with butyl and phenyl groups, were stable for prolonged periods in culture. Mono- and cognate di-esters varied in ability to disrupt the RSP; e.g., DEHP was inactive but its monoester was active while DBuP was active yet its monoester was inactive. DBuP and dibenzyl phthalate both disrupted the synthesis of RA from retinol but not the ability of RA to activate gene transcription. Both PEs also disrupted the RSP in C3H10T1/2 multipotent mesenchymal stem cells. Based on this in vitro study showing that some PEs disrupt retinol signaling and previous in vivo studies that vitamin A/RA deficiency and PEs both cause strikingly similar anomalies in the male rat reproductive system, we propose that PE-mediated inhibition of testosterone and RA synthesis in utero are both causes of malformations in male rat offspring.

Enzymatic Synthesis of Glyserol-Coconut Oil Fatty Acid and Glycerol-Decanoic Acis Ester as Emulsifier and Antimicrobial Agents Using Candida rugosa Lipase EC 3.1.1.3

NASA Astrophysics Data System (ADS)

Handayani, Sri; Putri, Ayu Tanissa Tamara; Setiasih, Siswati; Hudiyono, Sumi

2018-01-01

In this research, enzymatic esterification was carried out between glycerol and fatty acid from coconut oil and decanoic acid using n-hexane as solvent. In this reaction Candida rugosa lipase was used as biocatalyst. Optimization esterification reaction was carried out for parameter of the substrate ratio. The mmol ratio between fatty acid and glycerol were used are 1:1, 1:2, 1:3, and 1: 4. The highest conversion percentage obtained at the mole ratio of 1: 4 with the value of 78.5% for the glycerol-decanoic acid ester and 55.4% for the glycerol coconut oil fatty acid ester. Esterification products were characterized by FT-IR. The FT-IR spectrum showed that the ester bond was formed as indicated by the wave number 1750-1739 cm-1. The esterification products were then examined by simple emulsion test and was proved to be an emulsifier. The glycerol-coconut oil fatty acid ester produced higher stability emulsion compare with glycerol decanoic ester. The antimicrobial activity assay using disc diffusion method showed that both glycerol-coconut oil fatty acid ester and glycerol-decanoic ester had the ability inhibiting the growth of Propionibacterium acnes and Staphylococcus epidermidis. Glycerol-decanoic ester shows higher antimicrobial activity than glycerol-coconut oil fatty acid ester.

Chemical and physical analyses of wax ester properties

PubMed Central

Patel, Sejal; Nelson, Dennis R.; Gibbs, Allen G.

2001-01-01

Wax esters are major constituents of the surface lipids in many terrestrial arthropods, but their study is complicated by their diversity. We developed a procedure for quantifying isomers in mixtures of straight-chain saturated and unsaturated wax esters having the same molecular weights, using single-ion monitoring of the total ion current data from gas chromatography-mass spectrometry. We examined the biological consequences of structural differences by measuring the melting temperatures, Tm, of >60 synthetic wax esters, containing 26–48 carbon atoms. Compounds containing saturated alcohol and acid moieties melted at 38–73°C. The main factor affecting Tm was the total chain length of the wax ester, but the placement of the ester bond also affected Tm. Insertion of a double bond into either the alcohol or acid moiety decreased Tm by ∼30°C. Simple mixtures of wax esters with n-alkanes melted several °C lower than predicted from the melting points of the component lipids. Our results indicate that the wax esters of primary alcohols that are most typically found on the cuticle of terrestrial arthropods occur in a solid state under physiological conditions, thereby conferring greater waterproofing. Wax esters of secondary alcohols, which occur on melanopline grasshoppers, melted >60°C below primary esters of the same molecular weight and reduced Tm of the total surface lipids to environmental values. PMID:15455064

Development of l-Tyrosine-Based Enzyme-Responsive Amphiphilic Poly(ester-urethane) Nanocarriers for Multiple Drug Delivery to Cancer Cells.

PubMed

Aluri, Rajendra; Jayakannan, Manickam

2017-01-09

New classes of enzymatic-biodegradable amphiphilic poly(ester-urethane)s were designed and developed from l-tyrosine amino acid resources and their self-assembled nanoparticles were employed as multiple drug delivery vehicles in cancer therapy. The amine and carboxylic acid functional groups in l-tyrosine were converted into dual functional ester-urethane monomers and they were subjected to solvent free melt polycondensation with hydrophilic polyethylene glycols to produce comb-type poly(ester-urethane)s. The phenolic unit in the l-tyrosine was anchored with hydrophobic alkyl side chain to bring appropriate amphiphilicity in the polymer geometry to self-assemble them as stable nanoscaffolds in aqueous medium. The topology of the polymer was found to play a major role on the glass transition, crystallinity, and viscoelastic rheological properties of l-tyrosine poly(ester-urethane)s. The amphiphilic polymers were self-assembled as 200 ± 10 nm nanoparticles and they exhibited excellent encapsulation capabilities for anticancer drugs such as doxorubicin (DOX) and camptothecin (CPT). In vitro drug release studies revealed that the drug-loaded l-tyrosine nanoparticles were stable at extracellular conditions and they underwent enzymatic-biodegradation exclusively at the intracellular level to release the drugs. Cytotoxicity studies in the cervical cancer (HeLa) and normal WT-MEFs cell lines revealed that the nascent l-tyrosine nanoparticles were nontoxic, whereas the CPT and DOX drug-loaded polymer nanoparticles exhibited excellent cell killing in cancer cells. Confocal microscopic imaging confirmed the cellular internalization of drug-loaded nanoparticles. The drugs were taken up by the cells much higher quantity while delivering them from l-tyrosine nanoparticle platform compared to their free state. Flow cytometry analysis showed that the DOX-loaded polymer nanoscaffolds internalized the drugs 8-10× higher compared to free DOX. Both the synthesis of new classes of poly(ester-urethane)s via melt polycondensation approach and the enzyme-responsive drug delivery concept were accomplished for the first time. Thus, the present investigation is expected to open up new opportunities for l-tyrosine polymeric materials in biomaterial and thermoplastic applications.

Regioselective and stereospecific acylation across oxirane- and silyloxy systems as a novel strategy to the synthesis of enantiomerically pure mono-, di- and triglycerides.

PubMed

Stamatov, Stephan D; Stawinski, Jacek

2007-12-07

A trifluoroacetate-catalyzed opening of the oxirane ring of glycidyl derivatives bearing allylic acyl or alkyl functionalities with trifluoroacetic anhydride (TFAA), provides an efficient entry to configurationally homogeneous 1(3)-acyl- or 1(3)-O-alkyl-sn-glycerols. Selective introduction of tert-butyldimethylsilyl- (TBDMS), or triisopropylsilyl- (TIPS) transient protections at the terminal sites within these key intermediates secures 1(3)-acyl- or 1(3)-O-alkyl-3(1)-O-TBDMS (or TIPS)-sn-glycerols as general bifunctional precursors to 1,2(2,3)-diacyl-, 1(3)-O-alkyl-2-acyl- and 1,3-diacyl-sn-glycerols and hence triester isosters. Incorporation of a requisite acyl residue at the central carbon of the silylated synthons with a subsequent Et(3)N.3HF-promoted, direct trichloroacetylation across the siloxy system by trichloroacetic anhydride (TCAA), followed by cleavage of the trichloroacetyl group, affords the respective 1,2(2,3)-diacyl- or 1(3)-O-alkyl-2-acyl-sn-glycerols. Alternatively, a reaction sequence involving: (i) attachment of a trichloroacetyl fragment at the stereogenic C2-centre of the monosilylated glycerides; (ii) replacement of the silyl moiety by a short- or long-chain carboxylic acid residue by means of the acylating agent: tetra-n-butylammonium bromide (TBABr)-carboxylic acid anhydride (CAA)-trimethylsilyl bromide (TMSBr); and (iii) removal of the trichloroacetyl replacement, provides pure 1,3-diacyl-sn-glycerols. The TBABr-CAA-TMSBr reagent system allows also a one-step conversion of 1,2-diacylglycerol silyl ethers into homochiral triglycerides with predefined asymmetry and degree of unsaturation. These compounds can also be accessed via a two-step one-pot approach where the trichloroacetyl derivatives of 1,2(2,3)- or 1,3-diacyl-sn-glycerols serve as triester building blocks for establishing the third ester bond at preselected C3(1)- or C2-positions within the glycerol skeleton at the very last synthetic stage. In all instances, the target compounds were produced under mild conditions, in high enantiomeric purity, and in practically quantitative yields.

Intramolecular Hydroamination of Unbiased and Functionalized Primary Aminoalkenes Catalyzed by a Rhodium Aminophosphine Complex

PubMed Central

Julian, Lisa D.; Hartwig, John F.

2010-01-01

We report a rhodium catalyst that exhibits high reactivity for the hydroamination of primary aminoalkenes that are unbiased toward cyclization and that possess functional groups that would not be tolerated in hydroaminations catalyzed by more electrophilic systems. This catalyst contains an unusual diaminophosphine ligand that binds to rhodium in a κ3-P,O,P mode. The reactions catalyzed by this complex typically proceed at mild temperatures (room temperature to 70 °C), occur with primary aminoalkenes lacking substituents on the alkyl chain that bias the system toward cyclization, occur with primary aminoalkenes containing chloride, ester, ether, enolizable ketone, nitrile, and unprotected alcohol functionality, and occur with primary aminoalkenes containing internal olefins. Mechanistic data imply that these reactions occur with a turnover-limiting step that is different from that of reactions catalyzed by late transition metal complexes of Pd, Pt, and Ir. This change in the turnover-limiting step and resulting high activity of the catalyst stem from favorable relative rates for protonolysis of the M-C bond to release the hydroamination product vs reversion of the aminoalkyl intermediate to regenerate the acyclic precursor. Probes for the origin of the reactivity of the rhodium complex of L1 imply that the aminophosphine groups lead to these favorable rates by effects beyond steric demands and simple electron donation to the metal center. PMID:20839807

Antibacterial characteristics of newly developed amphiphilic lipids and DNA-lipid complexes against bacteria.

PubMed

Inoue, Y; Fukushima, T; Hayakawa, T; Takeuchi, H; Kaminishi, H; Miyazaki, K; Okahata, Y

2003-05-01

The purpose of this study was to investigate the antibacterial activity of newly developed amphiphilic lipids and DNA/lipid complexes against two types of oral bacteria and two types of hospital infection bacteria. Nine amphiphilic lipids were quantitatively prepared from the reaction of n-alkyl alcohol, alpha-amino acids, and p-toluenesulfonic acid. Nine DNA-lipid complexes were prepared by the simple mixing of DNA and amphiphilic lipids. The DNA-lipid complexes were insoluble in water. The antibacterial activity of lipids and DNA-lipid complexes against Porphyromonas gingivalis, Streptococcus mutans, Staphylococcus aureus, and Pseudomonas aeruginosa were evaluated by the disk-diffusion method. Seven artificial lipids showed antibacterial behavior; in particular, the lipids prepared from n-decyl alcohol and glycine and from n-decyl alcohol and L-alanine showed antibacterial activity against the four bacterial strains used in this study. On the other hand, the lipids of glutamic acid derivatives did not show any antibacterial activity against the four bacteria strains except for the lipid with an n-octyl group. Five DNA-lipid complexes also had an antibacterial effect. The complex prepared from DNA and glycine decyl ester p-toluenesulfonic acid salt exhibited antibacterial activity against the four types of bacteria strains. In this study it was found that lipids and DNA-lipid complexes with a mono-decyl group or a mono-dodecyl group have more favorable antibacterial activity. Copyright 2003 Wiley Periodicals, Inc.

Reactions of a Ruthenium Complex with Substituted N-Propargyl Pyrroles.

PubMed

Chia, Pi-Yeh; Huang, Shou-Ling; Liu, Yi-Hong; Lin, Ying-Chih

2016-04-05

In an investigation into the chemical reactions of N-propargyl pyrroles 1 a-c, containing aldehyde, keto, and ester groups on the pyrrole ring, with [Ru]-Cl ([Ru]=Cp(PPh3 )2 Ru; Cp=C5 H5 ), an aldehyde group in the pyrrole ring is found to play a crucial role in stimulating the cyclization reaction. The reaction of 1 a, containing an aldehyde group, with [Ru]-Cl in the presence of NH4 PF6 yields the vinylidene complex 2 a, which further reacts with allyl amine to give the carbene complex 6 a with a pyrrolizine group. However, if 1 a is first reacted with allyl amine to yield the iminenyne 8 a, then the reaction of 8 a with [Ru]-Cl in the presence of NH4 PF6 yields the ruthenium complex 9 a, containing a cationic pyrrolopyrazinium group, which has been fully characterized by XRD analysis. These results can be adequately explained by coordination of the triple bond of the propargyl group to the ruthenium metal center first, followed by two processes, that is, formation of a vinylidene intermediate or direct nucleophilic attack. Additionally, the deprotonation of 2 a by R4 NOH yields the neutral acetylide complex 3 a. In the presence of NH4 PF6 , the attempted alkylation of 3 a resulted in the formation the Fischer-type amino-carbene complex 5 a as a result of the presence of NH3, which served as a nucleophile. With KPF6, the alkylation of 3 a with ethyl and benzyl bromoacetates afforded the disubstituted vinylidene complexes 10 a and 11 a, containing ester groups, which underwent deprotonation reactions to give the furyl complexes 12 a and 13 a, respectively. For 13 a, containing an O-benzyl group, subsequent 1,3-migration of the benzyl group was observed to yield product 14 a with a lactone unit. Similar reactivity was not observed for the corresponding N-propargyl pyrroles 1 b and 1 c, which contained keto and ester groups, respectively, on the pyrrole ring. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Autoignition Studies of Diesel Alternative Biofuels

NASA Astrophysics Data System (ADS)

Wang, Weijing

The autoignition of biofuel compounds that offer potential as diesel fuel alternatives was studied under high-pressure engine-like conditions using the shock tube technique. Ignition delay times were determined in reflected shock experiments using measured pressure and electronically-excited OH emission. Measurements were made at conditions ranging from 650 to 1350 K, pressures from 6 to 50 atm, and for fuel/air/diluent mixtures at equivalence ratios from 0.5 to 2. The wide range of temperatures examined provides observation of autoignition in three reactivity regimes, including the negative temperature coefficient (NTC) regime which is characteristic of fuels containing alkyl functionalities. Compounds studied include biodiesel-related compounds and real biodiesel fuels, dimethyl ether, and 3-methylheptane which is representative of compounds found in synthetic diesel fuels produced using the Fischer-Tropsch and hydrotreatment processes. Biodiesel compounds studied include biodiesel surrogates, methyl decanoate, methyl-5-decenoate, and methyl-9-decenoate; compounds found in large quantities in biodiesels, methyl palmitate, methyl stearate, methyl oleate, and methyl linoleate; and soy-based and animal fat based methyl ester biodiesels. Comparison of biodiesel compounds illustrates the influence of molecular structure (e.g., chain length, double bonds, and ester functionality) on reactivity. For methyl decanoate, the effect of high pressure exhaust gas recirculation (EGR) conditions relevant to internal combustion engines was also determined. Results showed that the first-order influence of EGR by displacing fuel and O2 to decrease radical branching. Measurements were compared to kinetic modeling results from models available in the literature providing varying degrees of model validation. Reaction flux analyses were also carried out to further examine the kinetic differences in different temperature regimes for fuel compounds. For example, reaction flux analyses illustrates the importance of the long alkyl chain in controlling the overall reactivity of methyl ester biodiesel compounds and the subtle role the ester group has on inhibiting low-temperature reactivity as well as the influence of branching on reactivity for lightly branched alkanes. This thesis work provides a rich database of kinetic information for biofuel-related compounds at conditions relevant to real engine operations, offering quantitative kinetic targets for the development and evaluation of future kinetic models for important alternative fuel compounds. The results quantify the reactivity variability of biodiesel alternatives and illustrate that at temperature greater than 900 to 1000 K fuel structure has little influence on reactivity, as fuel fragmentation results in an intermediate pool that is largely the same for the fuels studied. On the other hand at temperature lower than 900 K, where fuel-specific low-temperature chemistry plays a role, different fuel structures can result in vast differences in reactivity, up to factors of three or more in ignition delay.

Influence of DNA Repair on Nonlinear Dose-Responses for Mutation

PubMed Central

Johnson, George E.

2013-01-01

Recent evidence has challenged the default assumption that all DNA-reactive alkylating agents exhibit a linear dose-response. Emerging evidence suggests that the model alkylating agents methyl- and ethylmethanesulfonate and methylnitrosourea (MNU) and ethylnitrosourea observe a nonlinear dose-response with a no observed genotoxic effect level (NOGEL). Follow-up mechanistic studies are essential to understand the mechanism of cellular tolerance and biological relevance of such NOGELs. MNU is one of the most mutagenic simple alkylators. Therefore, understanding the mechanism of mutation induction, following low-dose MNU treatment, sets precedence for weaker mutagenic alkylating agents. Here, we tested MNU at 10-fold lower concentrations than a previous study and report a NOGEL of 0.0075 µg/ml (72.8nM) in human lymphoblastoid cells, quantified through the hypoxanthine (guanine) phosphoribosyltransferase assay (OECD 476). Mechanistic studies reveal that the NOGEL is dependent upon repair of O6-methylguanine (O6MeG) by the suicide enzyme O6MeG-DNA methyltransferase (MGMT). Inactivation of MGMT sensitizes cells to MNU-induced mutagenesis and shifts the NOGEL to the left on the dose axis. PMID:23288051

Influence of DNA repair on nonlinear dose-responses for mutation.

PubMed

Thomas, Adam D; Jenkins, Gareth J S; Kaina, Bernd; Bodger, Owen G; Tomaszowski, Karl-Heinz; Lewis, Paul D; Doak, Shareen H; Johnson, George E

2013-03-01

Recent evidence has challenged the default assumption that all DNA-reactive alkylating agents exhibit a linear dose-response. Emerging evidence suggests that the model alkylating agents methyl- and ethylmethanesulfonate and methylnitrosourea (MNU) and ethylnitrosourea observe a nonlinear dose-response with a no observed genotoxic effect level (NOGEL). Follow-up mechanistic studies are essential to understand the mechanism of cellular tolerance and biological relevance of such NOGELs. MNU is one of the most mutagenic simple alkylators. Therefore, understanding the mechanism of mutation induction, following low-dose MNU treatment, sets precedence for weaker mutagenic alkylating agents. Here, we tested MNU at 10-fold lower concentrations than a previous study and report a NOGEL of 0.0075 µg/ml (72.8nM) in human lymphoblastoid cells, quantified through the hypoxanthine (guanine) phosphoribosyltransferase assay (OECD 476). Mechanistic studies reveal that the NOGEL is dependent upon repair of O(6)-methylguanine (O(6)MeG) by the suicide enzyme O(6)MeG-DNA methyltransferase (MGMT). Inactivation of MGMT sensitizes cells to MNU-induced mutagenesis and shifts the NOGEL to the left on the dose axis.

[Determination of fatty acid esters of chloropropanediols in diet samples by gas chromatography-mass spectrometry coupled with solid-supported liquid-liquid extraction].

PubMed

Gao, Jie; Liu, Qing; Han, Feng; Miao, Hong; Zhao, Yunfeng; Wu, Yongning

2014-05-01

To establish a method for the determination of fatty acid esters of 3-monochloropropane-1, 2-diol (3-MCPD) and 2-monochloropropane-1, 3-diol (2-MCPD) in diet samples by gas chromatography-mass spectrometry (GC-MS) with solid-supported liquid-liquid extraction (SLE). Diet samples were ultrasonically extracted by hexane, followed by ester cleavage reaction with sodium methylate in methanol, and then purified by solid-supported liquid-liquid extraction. (SLE) using diatomaceous earth as the sorbent. After derivatization with heptafluorobutyrylimidazole, the analytes were detected by GC-MS and quantified by the deuterated internal standards. The limits of detection (LODs) of 3-MCPD esters and 2-MCPD esters in different diet samples were 0.002 - 0.005 mg/kg and 0.002 - 0.006 mg/kg. The average recoveries of 3-MCPD esters and 2-MCPD esters at the spiking levels of 0.05 and 0.1 mg/kg in the diet samples were in the range of 65.9% - 104.2% and 75.4% - 118.0%, respectively, with the relative standard deviations in the range of 2.2% - 14.2% and 0.8% - .13.9%. The method is simple, accurate and rugged for the determination of fatty acid esters of 3-MCPD and 2-MCPD in diet samples.

Synthesis of non-cytotoxic poly(ester-amine) dendrimers as potential solubility enhancers for drugs: methotrexate as a case study.

PubMed

Soto-Castro, Delia; Cruz-Morales, Jorge A; Ramírez Apan, María Teresa; Guadarrama, Patricia

2010-11-09

This study describes the synthesis of two new families of dendrimers based on the esterification of N-alkylated 3-amine-1-propanol with two different cores, adipic acid (1st and 2nd generations) and ethylenediamine (generation 1.5), both with carboxylic acid end groups, offering a wide variety of further modifications at the periphery. According to the cytotoxic evaluation of the dendrimers and their possible degradation products within cell lines, these materials could be considered as innocuous. In preliminary studies, the synthesized dendrimers proved to be potential enhancers of solubility of highly hydrophobic drugs, like methotrexate, widely used in chemotherapy.

Benzoyl radicals from (hetero)aromatic aldehydes. Decatungstate photocatalyzed synthesis of substituted aromatic ketones.

PubMed

Ravelli, Davide; Zema, Michele; Mella, Mariella; Fagnoni, Maurizio; Albini, Angelo

2010-09-21

Benzoyl radicals are generated directly from (hetero)aromatic aldehydes upon tetrabutylammonium decatungstate ((n-Bu(4)N)(4)W(10)O(32)), TBADT) photocatalysis under mild conditions. In the presence of alpha,beta-unsaturated esters, ketones and nitriles radical conjugate addition ensues and gives the corresponding beta-functionalized aryl alkyl ketones in moderate to good yields (stereoselectively in the case of 3-methylene-2-norbornanone). Due to the mild reaction conditions the presence of various functional groups on the aromatic ring is tolerated (e.g. methyl, methoxy, chloro). The method can be applied to hetero-aromatic aldehydes whether electron-rich (e.g. thiophene-2-carbaldehyde) or electron-poor (e.g. pyridine-3-carbaldehyde).

Towards a fragment-based approach in gelator design: halogen effects leading to thixotropic, mouldable and self-healing systems in aryl-triazolyl amino acid-based gelators!

PubMed

Srivastava, Bhartendu K; Manheri, Muraleedharan K

2017-04-18

A simple replacement of a H atom by Br transformed non-gelating aryl triazolyl amino acid benzyl ester into a versatile gelator, which formed shape-persistent, self-healing and mouldable gels. The 'bromo-aryl benzyl ester' fragment was then transplanted into another framework, which resulted in similar solvent preference and gelation efficiency.

Dynamics of adsorption in micellar and non micellar solutions of derivatives of lysosomotropic substances.

PubMed

Dopierala, Katarzyna; Prochaska, Krystyna

2010-04-22

Dynamics of adsorption in micellar and non micellar solutions of derivatives of lysosomotropic substances was studied. The following compounds were considered in our research work: alkyl N,N-dimethyl-alaninates methobromides (DMALM-n), alkyl N,N-dimethylglycinates methobromides (DMGM-n), fatty acids N,N-dimethylaminoethylesters methobromides (DMM-n), fatty acids N,N-dimethylaminopropylesters methobromides (DMPM-n), fatty acids 1-dimethylamino-2-propyl methobromides (DMP(2)M-n), and derivatives of aminoesters with double alkyl chains (M(2)M-n). The examined compounds show interesting biological properties which can be useful, especially in medicine. The exact mechanism of interaction of such compounds with biological membrane is not fully known. However, it is supposed that the presence of micelles has an important role in biological systems. In this paper we show the results of dynamic surface tension measurements in solutions containing the investigated compounds at concentrations above and below cmc. Moreover, we analyzed the influence of the chemical structure of molecules on the diameters of the micelles formed in the solutions. It was found that adsorption dynamics for the studied compounds is strongly affected by the chemical structure of the considered derivatives, especially by the presence of the ester bond, linearity of the molecule, as well as its hydrophobicity. The obtained results show that the structure of the bromide M(2)M-n with two short hydrocarbon chains favors a faster and more efficient adsorption of the molecules at the air/water interface, compared with compounds having one long alkyl chain. Moreover, the double chained derivatives of the M(2)M-n type do not form typical spherical micelles but bilayer structures probably exist in these solutions. The micelles present in the solutions influence the dynamics of adsorption drastically. Moreover, the obtained results indicated that the compounds with especially high biological activity form rather small aggregates. Copyright 2010 Elsevier B.V. All rights reserved.

Chemistry of anti-AIDS and anticancer compounds

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

Yan, S.

1992-01-01

Several types of prodrugs of 2[prime], 3[prime]-dideoxynucleosides were designed and synthesized for evaluation as anti-AIDS drugs. These prodrugs include 5[prime]-O-acyl-2[prime], 3[prime]-dideoxynucleosides, in which the acyl groups are derived from both aromatic and aliphatic acids, [alpha]-amino acids, diacylglycerol carbonic acids, and diacylglycerol carbamic acids. By applying the pyridium-dihydropyridine redox delivery system to deliver 2[prime], 3[prime]-dideoxynucleosides to the central nervous system, 1,4-dihydropyridine-2[prime], 3[prime]-dideoxy-inosine and -adenosine compounds were synthesized. 5[prime]-Esters of 2[prime], 3[prime]-dideoxyinosine and 2[prime], 3[prime]-dideoxyadenosine were evaluated for their activity against the HIV-1 virus and for delivery to the central nervous system (CNS). The isomerization, hydrolysis, and oxidation of alkyl 1,4-dihydro-N-methylpyridine-3-carboxylates weremore » studied by [sup 1]H and [sup 13]C NMR spectroscopy. Three intermediates, 1,4-dihydro-N-methylpyridine-3-carboxylic acid, alkyl (methyl or isopropyl) 1,6-dihydro-N-methylpyridine-3-carboxylate, and 1,6-dihydro-N-methylpyridine-3-carboxylic acid, were observed by [sup 1]H and [sup 13]C NMR spectroscopy, and their percentages in solution were determined. The structures of the 1,6-dihydropyridine intermediates were confirmed by comparison of the NMR spectra with those of an authentic model compound, methyl N-(4-chlorobenzyl)-1,6-dihydropyridine-3-carboxylate. The rate of hydrolysis of alkyl 1,4-dihydro-N-methylpyridine-3-carboxylates depends on the steric bulk of the O-alkyl group. A new type of 1,4-dihydropyridine drug delivery system with a three-carbon spacer group, 9-[2,3-di-O-acetyl-5-O-[3-(1,4-dihydro-N-methylpyridine-3-carboxamido)propionyl]-[beta]-D-arabinofuranosyl]adenine was designed, synthesized, and evaluated to deliver ara-ADA to the CNS for treatment of herpes encephalitis.« less

Selective Oxidative Esterification from Two Different Alcohols via Photoredox Catalysis.

PubMed

Yi, Hong; Hu, Xia; Bian, Changliang; Lei, Aiwen

2017-01-10

Esters functionalities are important building blocks that are extensively used in the chemical industry and academic laboratories. Direct oxidative esterification from easy-available alcohols to esters would be a much more appealing approach, especially using O 2 as terminal oxidant. Inputting external energy by photocatalysis for dioxygen activation, a mild and simple method for ester synthesis from two different alcohols has been achieved in this work. This reaction is performed under neutral conditions using O 2 as the terminal oxidant. A variety of primary alcohols, especially long chain alcohols and secondary alcohols are tolerated in this system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Merging photoredox and nickel catalysis: decarboxylative cross-coupling of carboxylic acids with vinyl halides.

PubMed

Noble, Adam; McCarver, Stefan J; MacMillan, David W C

2015-01-21

Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of α-oxy and α-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions.

Diacyltransferase Activity and Chain Length Specificity of Mycobacterium tuberculosis PapA5 in the Synthesis of Alkyl β-Diol Lipids

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

Touchette, Megan H.; Bommineni, Gopal R.; Delle Bovi, Richard J.

Although classified as Gram-positive bacteria, Corynebacterineae possess an asymmetric outer membrane that imparts structural and thereby physiological similarity to more distantly related Gram-negative bacteria. Like lipopolysaccharide in Gram-negative bacteria, lipids in the outer membrane of Corynebacterineae have been associated with the virulence of pathogenic species such as Mycobacterium tuberculosis (Mtb). For example, Mtb strains that lack long, branched-chain alkyl esters known as dimycocerosates (DIMs) are significantly attenuated in model infections. The resultant interest in the biosynthetic pathway of these unusual virulence factors has led to the elucidation of many of the steps leading to the final esterification of the alkylmore » beta-diol, phthiocerol, with branched-chain fatty acids know as mycocerosates. PapA5 is an acyltransferase implicated in these final reactions. We here show that PapA5 is indeed the terminal enzyme in DIM biosynthesis by demonstrating its dual esterification activity and chain-length preference using synthetic alkyl beta-diol substrate analogues. Applying these analogues to a series of PapA5 mutants, we also revise a model for the substrate binding within PapA5. Finally, we demonstrate that the Mtb Ser/Thr kinase PknB modifies PapA5 on three Thr residues, including two (T196, T198) located on an unresolved loop. These results clarify the DIM biosynthetic pathway and suggest possible mechanisms by which DIM biosynthesis may be regulated by the post-translational modification of PapA5.« less

Synthesis and Anticancer Activity of 2-(Alkyl-, Alkaryl-, Aryl-, Hetaryl-)-[1,2,4]triazolo[1,5-c]quinazolines

PubMed Central

Kovalenko, Sergiy I.; Antypenko, Lyudmyla M.; Bilyi, Andriy K.; Kholodnyak, Sergiy V.; Karpenko, Olexandr V.; Antypenko, Olexii M.; Mykhaylova, Natalya S.; Los, Tetyana I.; Kolomoets, Olexandra S.

2013-01-01

The combinatorial library of novel potential anticancer agents, namely, 2-(alkyl-, alkaryl-, aryl-, hetaryl-)[1,2,4]triazolo[1,5-c]quinazolines, was synthesized by the heterocyclization of the alkyl-, alkaryl-, aryl-, hetarylcarboxylic acid (3H-quinazoline-4-ylidene)hydrazides by oxidative heterocyclization of the 4-(arylidenehydrazino)quinazolines using bromine, and by the heterocyclization of N-(2-cyanophenyl)formimidic acid ethyl ester. The optimal method for synthesis of the s-triazolo[1,5-c]quinazolines appeared to be cyclocondensation of the corresponding carboxylic acid (3H-quinazoline-4-ylidene)hydrazides. The compounds’ structures were established by 1H, 13C NMR, LC- and EI-MS analysis. The in vitro screening of anticancer activity determined the most active compound to be 3,4,5-trimethoxy-N′-[quinazolin-4(3H)-ylidene]benzohydrazide (3.20) in micromolar concentrations with the GI50 level (MG_MID, GI50 is 2.29). Thus, the cancer cell lines whose growth is greatly inhibited by compound 3.20 are: non-small cell lung cancer (NCI-H522, GI50=0.34), CNS (SF-295, GI50=0.95), ovarian (OVCAR-3, GI50=0.33), prostate (PC-3, GI50=0.56), and breast cancer (MCF7, GI50=0.52), leukemia (K-562, GI50=0.41; SR, GI50=0.29), and melanoma (MDA-MB-435, GI50=0.31; SK-MEL-5, GI50=0.74; UACC-62, GI50=0.32). SAR-analysis is also discussed. PMID:23833709

Anti-tumor activities of lipids and lipid analogues and their development as potential anticancer drugs.

PubMed

Murray, Michael; Hraiki, Adam; Bebawy, Mary; Pazderka, Curtis; Rawling, Tristan

2015-06-01

Lipids have the potential for development as anticancer agents. Endogenous membrane lipids, such as ceramides and certain saturated fatty acids, have been found to modulate the viability of tumor cells. In addition, many tumors over-express cyclooxygenase, lipoxygenase or cytochrome P450 enzymes that mediate the biotransformation of ω-6 polyunsaturated fatty acids (PUFAs) to potent eicosanoid regulators of tumor cell proliferation and cell death. In contrast, several analogous products from the biotransformation of ω-3 PUFAs impair particular tumorigenic pathways. For example, the ω-3 17,18-epoxide of eicosapentaenoic acid activates anti-proliferative and proapoptotic signaling cascades in tumor cells and the lipoxygenase-derived resolvins are effective inhibitors of inflammatory pathways that may drive tumor expansion. However, the development of potential anti-cancer drugs based on these molecules is complex, with in vivo stability a major issue. Nevertheless, recent successes with the antitumor alkyl phospholipids, which are synthetic analogues of naturally-occurring membrane phospholipid esters, have provided the impetus for development of further molecules. The alkyl phospholipids have been tested against a range of cancers and show considerable activity against skin cancers and certain leukemias. Very recently, it has been shown that combination strategies, in which alkyl phospholipids are used in conjunction with established anticancer agents, are promising new therapeutic approaches. In future, the evaluation of new lipid-based molecules in single-agent and combination treatments may also be assessed. This could provide a range of important treatment options in the management of advanced and metastatic cancer. Copyright © 2015 Elsevier Inc. All rights reserved.

Membrane-destabilizing activity of pH-responsive cationic lysine-based surfactants: role of charge position and alkyl chain length.

PubMed

Nogueira, Daniele Rubert; Mitjans, Montserrat; Morán, M Carmen; Pérez, Lourdes; Vinardell, M Pilar

2012-09-01

Many strategies for treating diseases require the delivery of drugs into the cell cytoplasm following internalization within endosomal vesicles. Thus, compounds triggered by low pH to disrupt membranes and release endosomal contents into the cytosol are of particular interest. Here, we report novel cationic lysine-based surfactants (hydrochloride salts of N(ε)- and N(α)-acyl lysine methyl ester) that differ in the position of the positive charge and the length of the alkyl chain. Amino acid-based surfactants could be promising novel biomaterials in drug delivery systems, given their biocompatible properties and low cytotoxic potential. We examined their ability to disrupt the cell membrane in a range of pH values, concentrations and incubation times, using a standard hemolysis assay as a model of endosomal membranes. Furthermore, we addressed the mechanism of surfactant-mediated membrane destabilization, including the effects of each surfactant on erythrocyte morphology as a function of pH. We found that only surfactants with the positive charge on the α-amino group of lysine showed pH-sensitive hemolytic activity and improved kinetics within the endosomal pH range, indicating that the positive charge position is critical for pH-responsive behavior. Moreover, our results showed that an increase in the alkyl chain length from 14 to 16 carbon atoms was associated with a lower ability to disrupt cell membranes. Knowledge on modulating surfactant-lipid bilayer interactions may help us to develop more efficient biocompatible amino acid-based drug delivery devices.

Fluoroester Co-Solvents for Low-Temperature Li+ Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar; Prakash, G. K. Surya; Smith, Kiah; Bhalla, Pooja

2009-01-01

Electrolytes comprising LiPF6 dissolved in alkyl carbonate/fluoroester mixtures have been found to afford improved low-temperature performance and greater high-temperature resilience in rechargeable lithium-ion electrochemical cells. These and other electrolytes comprising lithium salts dissolved mixtures of esters have been studied in continuing research directed toward extending the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. The purpose of the present focus on high-temperature resilience in addition to low-temperature performance is to address issues posed by the flammability of the esters and, at temperatures near the upper end (about 55 C) of their intended operating temperature range, by their high chemical reactivity. As used here, high-temperature resilience signifies, loosely, a desired combination of low flammability of an electrolyte mixture and the ability of a cell that contains the mixture to sustain a relatively small loss of reversible charge/discharge capacity during storage in the fully charged condition at high temperature. The selection of fluoroesters for study as candidate electrolyte solvent components to increase high-temperature resilience was prompted in part by the observation that like other halogenated compounds, fluoroesters have low flammability. The fluoroesters investigated in this study include trifluoroethyl butyrate (TFEB), ethyl trifluoroacetate (ETFA), trifluoroethyl acetate (TFEA), and methyl pentafluoropropionate (MPFP). Solvent mixtures were prepared by mixing these fluoroesters with two other esters: ethylene carbonate (EC) and ethyl methyl carbonate (EMC).

Abiotic Condensation Synthesis of Glyceride Lipids and Wax Esters Under Simulated Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Rushdi, Ahmed I.; Simoneit, Bernd R. T.

2006-04-01

Precursor compounds for abiotic proto cellular membranes are necessary for the origin of life. Amphipathic compounds such as fatty acids and acyl glycerols are important candidates for micelle/bilayer/vesicle formation. Two sets of experiments were conducted to study dehydration reactions of model lipid precursors in aqueous media to form acyl polyols and wax esters, and to evaluate the stability and reactions of the products at elevated temperatures. In the first set, mixtures of n-nonadecanoic acid and ethylene glycol in water, with and without oxalic acid, were heated at discrete temperatures from 150 ∘C to 300 ∘C for 72 h. The products were typically alkyl alkanoates, ethylene glycolyl alkanoates, ethylene glycolyl bis-alkanoates and alkanols. The condensation products had maximum yields between 150 ∘C and 250 ∘C, and were detectable and thus stable under hydrothermal conditions to temperatures < 300 ∘C. In the second set of experiments, mixtures of n-heptanoic acid and glycerol were heated using the same experimental conditions, with and without oxalic acid, between 100 ∘C and 250 ∘C. The main condensation products were two isomers each of monoacylglycerols and diacylglycerols at all temperatures, as well as minor amounts of the fatty acid anhydride and methyl ester. The yield of glyceryl monoheptanoates generally increased with increasing temperature and glyceryl diheptanoates decreased noticeably with increasing temperature. The results indicate that condensation reactions and abiotic synthesis of organic lipid compounds under hydrothermal conditions occur easily, provided precursor concentrations are sufficiently high.

Determination of free and esterified carotenoid composition in rose hip fruit by HPLC-DAD-APCI(+)-MS.

PubMed

Zhong, Lijie; Gustavsson, Karl-Erik; Oredsson, Stina; Głąb, Bartosz; Yilmaz, Jenny Lindberg; Olsson, Marie E

2016-11-01

Rose hip fruit, which contains high concentration of carotenoids is commonly used for different food products in Europe and it is considered to have medical properties. In this study, a simple, rapid and efficient HPLC-DAD-APCI(+)-MS method was developed and applied to identify and quantify the carotenoids in rose hip fruit of four rose species, including both unsaponified and saponified extract. In the unsaponified extract 23 carotenoid esters were detected, in which either rubixanthin ester or violaxanthin ester was the dominant component of the ester composition. In the saponified extract 21 carotenoids, including 11 xanthophylls and 10 carotenes were detected. This is the first time the total carotenoid composition, including the carotenoid esters in rose hip fruit were identified and quantified. This work reveals the potential of rose hip fruit to be utilized as a healthy dietary material and give chemical information for the possible future development in the pharmacology field. Copyright © 2016 Elsevier Ltd. All rights reserved.

Density of Jatropha curcas Seed Oil and its Methyl Esters: Measurement and Estimations

NASA Astrophysics Data System (ADS)

Veny, Harumi; Baroutian, Saeid; Aroua, Mohamed Kheireddine; Hasan, Masitah; Raman, Abdul Aziz; Sulaiman, Nik Meriam Nik

2009-04-01

Density data as a function of temperature have been measured for Jatropha curcas seed oil, as well as biodiesel jatropha methyl esters at temperatures from above their melting points to 90 ° C. The data obtained were used to validate the method proposed by Spencer and Danner using a modified Rackett equation. The experimental and estimated density values using the modified Rackett equation gave almost identical values with average absolute percent deviations less than 0.03% for the jatropha oil and 0.04% for the jatropha methyl esters. The Janarthanan empirical equation was also employed to predict jatropha biodiesel densities. This equation performed equally well with average absolute percent deviations within 0.05%. Two simple linear equations for densities of jatropha oil and its methyl esters are also proposed in this study.

Retention behaviour of polyunsaturated fatty acid methyl esters on porous graphitic carbon.

PubMed

Gaudin, Karen; Hanai, Toshihiko; Chaminade, Pierre; Baillet, Arlette

2007-07-20

Retention with porous graphitic carbon was investigated with 25 structures of fatty acid methyl esters (FAMEs) with two different mobile phases: CH(3)CN:CHCl(3) 60:40 (v/v) and CH(3)OH:CHCl(3) 60:40 (v/v) with both 0.1% triethylamine (TEA) and an equimolar amount of HCOOH. Preliminary results showed that the use of TEA/HCOOH led to the response increase of saturated FAMEs with evaporative light scattering detection. No increase was observed for unsaturated one. These modifiers may slightly reduce the retention of FAMEs but did not significantly modify the separation factor with porous graphitic carbon. Thermodynamic parameters were calculated for each structure using Van't Hoff plot measured over the temperature range from 10 to 50 degrees C, with the both mobile phase conditions. All the studied compounds were found linked by the same retention mechanism on porous graphitic carbon. Quantitative in silico analysis of the retention using a molecular mechanics calculation demonstrated a good correlation between the retention factors and the molecular interaction energy values (r>0.93). Especially the Van der Waals energy was predominant, and the contribution of electrostatic energy was negligible for the quantitative analysis of the retention. The results indicate that Van der Waals force, hydrophobic interaction, is predominant for the retention of FAMEs on this packing material. The relative retention for highly unsaturated homologues can be changed by the selection of the weak solvent CH(3)CN or CH(3)OH. Then isomers differing only in the position of the carbon double bond on the alkyl chain can be separated and their behaviour is summarised as the closer the carbon double bonds to the FAME polar head, the more the retention decreases. Finally, the more important the number of carbon double bonds in the alkyl chain is, the smaller the retention is.

The Rheological Properties of Lipid Monolayers Modulate the Incorporation of l-Ascorbic Acid Alkyl Esters.

PubMed

Díaz, Yenisleidy de Las Mercedes Zulueta; Mottola, Milagro; Vico, Raquel V; Wilke, Natalia; Fanani, María Laura

2016-01-19

In this work, we tested the hypothesis that the incorporation of amphiphilic drugs into lipid membranes may be regulated by their rheological properties. For this purpose, two members of the l-ascorbic acid alkyl esters family (ASCn) were selected, ASC16 and ASC14, which have different rheological properties when organized at the air/water interface. They are lipophilic forms of vitamin C used in topical pharmacological preparations. The effect of the phase state of the host lipid membranes on ASCn incorporation was explored using Langmuir monolayers. Films of pure lipids with known phase states have been selected, showing liquid-expanded, liquid-condensed, and solid phases as well as pure cholesterol films in liquid-ordered state. We also tested ternary and quaternary mixed films that mimic the properties of cholesterol containing membranes and of the stratum corneum. The compressibility and shear properties of those monolayers were assessed in order to define its phase character. We found that the length of the acyl chain of the ASCn compounds induces differential changes in the rheological properties of the host membrane and subtly regulates the kinetics and extent of the penetration process. The capacity for ASCn uptake was found to depend on the phase state of the host film. The increase in surface pressure resultant after amphiphile incorporation appears to be a function of the capacity of the host membrane to incorporate such amphiphile as well as the rheological response of the film. Hence, monolayers that show a solid phase state responded with a larger surface pressure increase to the incorporation of a comparable amount of amphiphile than liquid-expanded ones. The cholesterol-containing films, including the mixture that mimics stratum corneum, allowed a very scarce ASCn uptake independently of the membrane diffusional properties. This suggests an important contribution of Cho on the maintenance of the barrier function of stratum corneum.

Assessment of the skin sensitising potency of the lower alkyl methacrylate esters.

PubMed

Kimber, Ian; Pemberton, Mark A

2014-10-01

There is continued interest in, and imperatives for, the classification of contact allergens according to their relative skin sensitising potency. However, achieving that end can prove problematic, not least when there is an apparent lack of concordance between experimental assessments of potency and the prevalence allergic contact dermatitis as judged by clinical experience. For the purpose of exploring this issue, and illustrating the important considerations that are required to reach sound judgements about potency categorisation, the lower alkyl methacrylate esters (LAM) have been employed here as a case study. Although the sensitising potential of methyl methacrylate (MMA) has been reviewed previously, there is available new information that is relevant for assessment of skin sensitising potency. Moreover, for the purposes of this article, analyses have been extended to include also other LAM for which relevant data are available: ethyl methacrylate (EMA), n-butyl methacrylate (nBMA), isobutyl methacrylate (iBMA), and 2-ethylhexyl methacrylate (EHMA). In addressing the skin sensitising activity of these chemicals and in drawing conclusions regarding relative potency, a number of sources of information has been considered, including estimates of potency derived from local lymph node assay (LLNA) data, the results of guinea pig assays, and data derived from in silico methods and from recently developed in vitro approaches. Moreover, clinical experience of skin sensitisation of humans by LAM has also been evaluated. The conclusion drawn is that MMA and other LAM are contact allergens, but that none of these chemicals has any more than weak skin sensitising potency. We have also explored here the possible bases for this modest sensitising activity. Finally, the nature of exposure to LAM has been reviewed briefly and on the basis of that information, together with an understanding of skin sensitising potency, a risk assessment has been prepared. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

Merging Photoredox and Nickel Catalysis: Decarboxylative Cross-Coupling of Carboxylic Acids with Vinyl Halides

PubMed Central

2015-01-01

Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of α-oxy and α-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions. PMID:25521443

Determination of the content of fatty acid methyl esters (FAME) in biodiesel samples obtained by esterification using 1H-NMR spectroscopy.

PubMed

Mello, Vinicius M; Oliveira, Flavia C C; Fraga, William G; do Nascimento, Claudia J; Suarez, Paulo A Z

2008-11-01

Three different calibration curves based on (1)H-NMR spectroscopy (300 MHz) were used for quantifying the reaction yield during biodiesel synthesis by esterification of fatty acids mixtures and methanol. For this purpose, the integrated intensities of the hydrogens of the ester methoxy group (3.67 ppm) were correlated with the areas related to the various protons of the alkyl chain (olefinic hydrogens: 5.30-5.46 ppm; aliphatic: 2.67-2.78 ppm, 2.30 ppm, 1.96-2.12 ppm, 1.56-1.68 ppm, 1.22-1.42 ppm, 0.98 ppm, and 0.84-0.92 ppm). The first curve was obtained using the peaks relating the olefinic hydrogens, a second with the parafinic protons and the third curve using the integrated intensities of all the hydrogens. A total of 35 samples were examined: 25 samples to build the three different calibration curves and ten samples to serve as external validation samples. The results showed no statistical differences among the three methods, and all presented prediction errors less than 2.45% with a co-efficient of variation (CV) of 4.66%. 2008 John Wiley & Sons, Ltd.

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

Penning, T.D.

The enone, 2,2-diemthyl-3a..beta.., 6a..beta..-dihydro-4H-cyclopenta-1,3-dioxol-4-one, has been synthesized in six steps from cyclopentadiene, resolved using sulfoximine chemistry, and converted into (-)-prostaglandin E/sub 2/ methyl ester in three steps. Introduction of the optically pure omega side-chain using a conjugate addition of a stabilized organocopper reagent, followed by direct alkylation of the enolate with the ..cap alpha.. side-chain allylic iodide in the presence of hexamethylphosphoramide, afforded a trans, vicinally disubstituted cyclopentanone. Deprotection of the C-15 alcohol, followed by aluminum amalgam reduction of the C-10/oxygen bond, provided (-)-PGE/sub 2/ methyl ester in 47% overall yield from the enone. In an extension of previously describedmore » work, 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide, prepared from l-ephedrine and thiophosphoryl chloride, was used to determine the enantiomeric excess of chiral alcohols in conjunction with /sup 31/P NMR. Chiral primary and secondary alcohols added quantitatively to the phospholidine to give diastereomers which could be analyzed by /sup 31/P NMR and HPLC. A number of other phosphorus heterocycles were also explored as potential chiral derivatizing reagents.« less

Final Report - Low Temperature Combustion Chemistry And Fuel Component Interactions

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

Wooldridge, Margaret

Recent research into combustion chemistry has shown that reactions at “low temperatures” (700 – 1100 K) have a dramatic influence on ignition and combustion of fuels in virtually every practical combustion system. A powerful class of laboratory-scale experimental facilities that can focus on fuel chemistry in this temperature range is the rapid compression facility (RCF), which has proven to be a versatile tool to examine the details of fuel chemistry in this important regime. An RCF was used in this project to advance our understanding of low temperature chemistry of important fuel compounds. We show how factors including fuel molecularmore » structure, the presence of unsaturated C=C bonds, and the presence of alkyl ester groups influence fuel auto-ignition and produce variable amounts of negative temperature coefficient behavior of fuel ignition. We report new discoveries of synergistic ignition interactions between alkane and alcohol fuels, with both experimental and kinetic modeling studies of these complex interactions. The results of this project quantify the effects of molecular structure on combustion chemistry including carbon bond saturation, through low temperature experimental studies of esters, alkanes, alkenes, and alcohols.« less

Combinations of fluorinated solvents with imide salts or methide salts for electrolytes

DOEpatents

Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan; Lei, Norman; Guerrero-Zavala, Guillermo; Kwong, Kristie W

2015-11-10

Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include imide salts and/or methide salts as well as fluorinated solvents capable of maintaining single phase solutions at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and improve safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Linear and cyclic imide salts, such as LiN(SO.sub.2CF.sub.2CF.sub.3).sub.2, and LiN(SO.sub.2CF.sub.3).sub.2, as well as methide salts, such as LiC(SO.sub.2CF.sub.3).sub.3 and LiC(SO.sub.2CF.sub.2CF.sub.3).sub.3, may be used in these electrolytes. Fluorinated alkyl groups enhance solubility of these salts in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene, and/or one or more ionic liquids.

Skin delivery of antioxidant surfactants based on gallic acid and hydroxytyrosol.

PubMed

Alonso, Cristina; Lucas, Ricardo; Barba, Clara; Marti, Meritxell; Rubio, Laia; Comelles, Francesc; Morales, Juan Carlos; Coderch, Luisa; Parra, José Luís

2015-07-01

The aim of this study has been to investigate the dermal absorption profile of the antioxidant compounds gallic acid and hydroxytyrosol as well as their derivatives, hexanoate (hexyl gallate and hydroxytyrosol hexanoate) and octanoate (octyl gallate and octanoate derivative) alkyl esters (antioxidant surfactants). Previously, the scavenging capacity of these compounds, expressed as efficient dose ED50, has also determined. The percutaneous absorption of these compounds was obtained by an in vitro methodology using porcine skin biopsies on Franz static diffusion cells. The antiradical activity of compounds was determined using the 1,1-diphenyl-2-picrylhydrazyl free radical method. The percutaneous penetration results show the presence of antioxidants in all layers of the skin. The content of the cutaneously absorbed compound is higher for the antioxidant surfactants (ester derivatives). This particular behaviour could be due to the higher hydrophobicity of these compounds and the presence of surface activity in the antioxidant surfactants. These new antioxidant surfactants display optimum properties, which may be useful in the preparation of emulsified systems in cosmetic and pharmaceutical formulations because of their suitable surface activity and because they can protect the skin from oxidative damage. © 2015 Royal Pharmaceutical Society.

Guggenheim's rule and the enthalpy of vaporization of simple and polar fluids, molten salts, and room temperature ionic liquids.

PubMed

Weiss, Volker C

2010-07-22

One of Guggenheim's many corresponding-states rules for simple fluids implies that the molar enthalpy of vaporization (determined at the temperature at which the pressure reaches 1/50th of its critical value, which approximately coincides with the normal boiling point) divided by the critical temperature has a value of roughly 5.2R, where R is the universal gas constant. For more complex fluids, such as strongly polar and ionic fluids, one must expect deviations from Guggenheim's rule. Such a deviation has far-reaching consequences for other empirical rules related to the vaporization of fluids, namely Guldberg's rule and Trouton's rule. We evaluate these characteristic quantities for simple fluids, polar fluids, hydrogen-bonding fluids, simple inorganic molten salts, and room temperature ionic liquids (RTILs). For the ionic fluids, the critical parameters are not accessible to direct experimental observation; therefore, suitable extrapolation schemes have to be applied. For the RTILs [1-n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides, where the alkyl chain is ethyl, butyl, hexyl, or octyl], the critical temperature is estimated by extrapolating the surface tension to zero using Guggenheim's and Eotvos' rules; the critical density is obtained using the linear-diameter rule. It is shown that the RTILs adhere to Guggenheim's master curve for the reduced surface tension of simple and moderately polar fluids, but that they deviate significantly from his rule for the reduced enthalpy of vaporization of simple fluids. Consequences for evaluating the Trouton constant of RTILs, the value of which has been discussed controversially in the literature, are indicated.

Comparative reactivity of different types of stable cyclic and acyclic mono- and diamino carbenes with simple organic substrates.

PubMed

Martin, David; Canac, Yves; Lavallo, Vincent; Bertrand, Guy

2014-04-02

A series of stable carbenes, featuring a broad range of electronic properties, were reacted with simple organic substrates. The N,N-dimesityl imidazolylidene (NHC) does not react with isocyanides, whereas anti-Bredt di(amino)carbene (pyr-NHC), cyclic (alkyl)(amino)carbene (CAAC), acyclic di(amino)carbene (ADAC), and acyclic (alkyl)(amino)carbene (AAAC) give rise to the corresponding ketenimines. NHCs are known to promote the benzoin condensation, and we found that the CAAC, pyr-NHC, and ADAC react with benzaldehyde to give the ketone tautomer of the Breslow intermediate, whereas the AAAC first gives the corresponding epoxide and ultimately the Breslow intermediate, which can be isolated. Addition of excess benzaldehyde to the latter does not lead to benzoin but to a stable 1,3-dioxolane. Depending on the electronic properties of carbenes, different products are also obtained with methyl acrylate as a substrate. The critical role of the carbene electrophilicity on the outcome of reactions is discussed.

Rh-Catalyzed Annulations of N-Methoxybenzamides and Ketenimines: Sterically and Electronically Controlled Synthesis of Isoquinolinones and Isoindolinones.

PubMed

Zhou, Xiaorong; Zhang, Zhiyin; Zhao, Hongyang; Lu, Ping; Wang, Yanguang

2017-04-07

Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides are reported. The outcome of reactions is dependent on the structure of ketenimines. The β-alkyl-substituted ketenimines furnish 3-iminoisoquinolin-1(2H)-ones in a formal [4 + 2] annulation manner, while the β-ester substituted ketenimines afford 3-aminoisoindolin-1-ones in a formal [4 + 1] annulation manner. The synthesized [4 + 2] products undergo an intramolecular Cu-catalyzed C-N coupling to be converted to benzo[4,5]imidazo[1,2-b]isoquinolin-11-ones, which can be directly prepared from ketenimines and N-methoxybenzamides by a one-pot Rh-catalyzed annulation/Cu-catalyzed C-N coupling sequence.

Sensitization by heat treatment of Escherichia coli K-12 cells to hydrophobic antibacterial compounds.

PubMed Central

Tsuchido, T; Takano, M

1988-01-01

The sensitivities of intact and heat-injured cells of Escherichia coli K-12 to several antibacterial compounds were measured by the prolongation of growth delay. Cells exposed to sublethal heat became more sensitive to various hydrophobic compounds, such as medium-chain fatty acids, alkyl esters of p-hydroxybenzoic acid, and some kinds of antibiotics or dyes, than unheated cells; but there was a smaller or no increase in sensitivity to short-chain fatty acids, chloramphenicol, and vancomycin. The destruction by heat of a permeability barrier of the outer membrane may have sensitized the cells to hydrophobic compounds. The sensitization was much lower for a strain defective in lipopolysaccharide, which is important as a barrier against hydrophobic compounds. PMID:3075437

Metal-free carbonylations by photoredox catalysis.

PubMed

Majek, Michal; Jacobi von Wangelin, Axel

2015-02-09

The synthesis of benzoates from aryl electrophiles and carbon monoxide is a prime example of a transition-metal-catalyzed carbonylation reaction which is widely applied in research and industrial processes. Such reactions proceed in the presence of Pd or Ni catalysts, suitable ligands, and stoichiometric bases. We have developed an alternative procedure that is free of any metal, ligand, and base. The method involves a redox reaction driven by visible light and catalyzed by eosin Y which affords alkyl benzoates from arene diazonium salts, carbon monoxide, and alcohols under mild conditions. Tertiary esters can also be prepared in high yields. DFT calculations and radical trapping experiments support a catalytic photoredox pathway without the requirement for sacrificial redox partners. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Generation and exploitation of acyclic azomethine imines in chiral Brønsted acid catalysis

NASA Astrophysics Data System (ADS)

Hashimoto, Takuya; Kimura, Hidenori; Kawamata, Yu; Maruoka, Keiji

2011-08-01

Successful implementation of a catalytic asymmetric synthesis strategy to produce enantiomerically enriched compounds requires the adoption of suitable prochiral substrates. The combination of an azomethine imine electrophile with various nucleophiles could give straightforward access to a number of synthetically useful chiral hydrazines, but is used rarely. Here we report the exploitation of acyclic azomethine imines as a new type of prochiral electrophile. They can be generated in situ by the condensation of N‧-benzylbenzoylhydrazide with a variety of aldehydes in the presence of a catalytic amount of an axially chiral dicarboxylic acid. By trapping these electrophiles with alkyl diazoacetate or (diazomethyl)phosphonate nucleophiles, we produced a diverse array of chiral α-diazo-β-hydrazino esters and phosphonates with excellent enantioselectivities.

Novel double prodrugs of the iron chelator N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED): Synthesis, characterization, and investigation of activation by chemical hydrolysis and oxidation.

PubMed

Thiele, Nikki A; Abboud, Khalil A; Sloan, Kenneth B

2016-08-08

The development of iron chelators suitable for the chronic treatment of diseases where iron accumulation and subsequent oxidative stress are implicated in disease pathogenesis is an active area of research. The clinical use of the strong chelator N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED) and its alkyl ester prodrugs has been hindered by poor oral bioavailability and lack of conversion to the parent chelator, respectively. Here, we present novel double prodrugs of HBED that have the carboxylate and phenolate donors of HBED masked with carboxylate esters and boronic acids/esters, respectively. These double prodrugs were successfully synthesized as free bases (7a-f) or as dimesylate salts (8a-c,e), and were characterized by (1)H, (13)C, and (11)B NMR; MP; MS; and elemental analysis. The crystal structure of 8a was solved. Three of the double prodrugs (8a-c) were selected for further investigation into their abilities to convert to HBED by stepwise hydrolysis and H2O2 oxidation. The serial hydrolysis of the pinacol and methyl esters of N,N'-bis(2-boronic acid pinacol ester benzyl)ethylenediamine-N,N'-diacetic acid methyl ester dimesylate (8a) was verified by LC-MS. The macro half-lives for the hydrolyses of 8a-c, measured by UV, ranged from 3.8 to 26.3 h at 37 °C in pH 7.5 phosphate buffer containing 50% MeOH. 9, the product of hydrolysis of 8a-c and the intermediate in the conversion pathway, showed little-to-no affinity for iron or copper in UV competition experiments. 9 underwent a serial oxidative deboronation by H2O2 in N-methylmorpholine buffer to generate HBED (k = 10.3 M(-1) min(-1)). The requirement of this second step, oxidation, before conversion to the active chelator is complete may confer site specificity when only localized iron chelation is needed. Overall, these results provide proof of principle for the activation of the double prodrugs by chemical hydrolysis and H2O2 oxidation, and merit further investigation into the protective capabilities of the prodrugs against H2O2-induced cell death. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Simple route for nano-hydroxyapatite properties expansion.

PubMed

Rojas, L; Olmedo, H; García-Piñeres, A J; Silveira, C; Tasic, L; Fraga, F; Montero, M L

2015-10-20

Simple surface modification of nano-hydroxyapatite, through acid-basic reactions, allows expanding the properties of this material. Introduction of organic groups such as hydrophobic alkyl chains, carboxylic acid, and amide or amine basic groups on the hydroxyapatite surface systematically change the polarity, surface area, and reactivity of hydroxyapatite without modifying its phase. Physical and chemical properties of the new derivative particles were analyzed. The biocompatibility of modified Nano-Hap on Raw 264.7 cells was also assessed.

A protocol for the production of gliadin-cyanoacrylate nanoparticles for hydrophilic coating

USDA-ARS?s Scientific Manuscript database

This article presents a protocol for the production of protein-based nanoparticles that change the hydrophobic surface to hydrophilic by a simple spray coating. These nanoparticles are produced by the polymerization reaction of alkyl cyanoacrylate on the surface of cereal protein (gliadin) molecules...

AN EFFICIENT AQUEOUS N-HETEROCYCLIZATION OF ANILINE DERIVATIVES: MICROWAVE-ASSISTED SYNTHESIS OF N-ARYL AZACYCLOALKANES

EPA Science Inventory

N-aryl azacycloalkanes, an important class of building blocks in natural product and pharmaceuticals, are synthesized via an efficient and simple eco-friendly protocol that involves double N-alkylation of aniline derivatives. The reaction is accelerated by exposure to microwaves ...

SOLVENT-FREE PREPARATION OF IONIC LIQUIDS USING A HOUSEHOLD MICROWAVE OVEN

EPA Science Inventory

An efficient solventless protocol for the preparation of a wide variety of ionic liquids is described which requires a simple exposure of admixed 1-methylimidazole and alkyl halides to microwave irradiation in open glass containers. The details of this clean process using a commo...

Dual function catalysts. Dehydrogenation and asymmetric intramolecular Diels-Alder cycloaddition of N-hydroxy formate esters and hydroxamic acids: evidence for a ruthenium-acylnitroso intermediate.

PubMed

Chow, Chun P; Shea, Kenneth J

2005-03-23

The chiral ruthenium salen complex, 13b, functions as an efficient catalyst for the sequential oxidation and asymmetric Diels-Alder cycloaddition of hydroxamic acids and N-hydroxy formate esters. This result provides evidence for the formation of a ruthenium-nitroso formate (acyl nitroso) intermediate. The Diels-Alder precursors are prepared from simple building blocks, and the cycloadducts, bridged oxazinolactams, can serve as useful intermediates in organic synthesis.

Efficient synthesis of (+/-)-4-methyloctanoic acid, aggregation pheromone of rhinoceros beetles of the genus Oryctes (Coleoptera: Dynastidae, Scarabaeidae).

PubMed

Ragoussis, Valentine; Giannikopoulos, Alexandros; Skoka, Efthymia; Grivas, Panagiotis

2007-06-27

(+/-)-4-Methyloctanoic acid and its ethyl ester are aggregation pheromones of many rhinoceros beetles of the genus Oryctes and are investigated for the control of these pests by olfactory trapping. A simple, economical, and high-yield (>50%) synthesis of (+/-)-4-methyloctanoic acid and its ethyl ester is presented starting from n-hexanal. The key step in this sequence is an orthoester Claisen rearrangement for the elongation of the carbon chain by two.

Enantioselective Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds.

PubMed

Hari, Durga Prasad; Waser, Jerome

2017-06-28

Enantioselective catalytic methods allowing the addition of both a nucleophile and an electrophile onto diazo compounds give a fast access into important building blocks. Herein, we report the highly enantioselective oxyalkynylation of diazo compounds using ethynylbenziodoxol-(on)e reagents and a simple copper bisoxazoline catalyst. The obtained α-benzoyloxy propargylic esters are useful building blocks, which are difficult to synthesize in enantiopure form using other methods. The obtained products could be efficiently transformed into vicinal diols and α-hydroxy propargylic esters without loss in enantiopurity.

Extreme oxatriquinanes and a record C-O bond length

NASA Astrophysics Data System (ADS)

Gunbas, Gorkem; Hafezi, Nema; Sheppard, William L.; Olmstead, Marilyn M.; Stoyanova, Irini V.; Tham, Fook S.; Meyer, Matthew P.; Mascal, Mark

2012-12-01

Oxatriquinanes are fused, tricyclic oxonium ions that are known to have exceptional stability compared to simple alkyl oxonium salts. C-O bonds in ethers are generally ˜1.43 Å in length, but oxatriquinane has been found to have C-O bond lengths of 1.54 Å. A search of the Cambridge Structural Database turned up no bona fide C-O bond length exceeding this value. Computational modelling of oxatriquinane alongside other alkyl oxonium ions indicated that the electronic consequences of molecular strain were primarily responsible for the observed bond elongation. We also show that substitution of the oxatriquinane ring system with alkyl groups of increasing steric demand pushes the C-O bond to unheard of distances, culminating in a tert-butyl derivative at a predicted 1.60 Å. Chemical synthesis and an X-ray crystallographic study of these compounds validated the results of the modelling work and, finally, an extraordinary 1.622 Å C-O bond was observed in 1,4,7-tri-tert-butyloxatriquinane.

Tandem catalysis for the production of alkyl lactates from ketohexoses at moderate temperatures

DOE PAGES

Orazov, Marat; Davis, Mark E.

2015-09-08

Retro-aldol reactions have been implicated as the limiting steps in catalytic routes to convert biomass-derived hexoses and pentoses into valuable C2, C3, and C4 products such as glycolic acid, lactic acid, 2-hydroxy-3-butenoic acid, 2,4-dihydroxybutanoic acid, and alkyl esters thereof. Due to a lack of efficient retro-aldol catalysts, most previous investigations of catalytic pathways involving these reactions were conducted at high temperatures (≥160 °C). Here, we report moderate-temperature (around 100 °C) retro-aldol reactions of various hexoses in aqueous and alcoholic media with catalysts traditionally known for their capacity to catalyze 1,2-intramolecular carbon shift (1,2-CS) reactions of aldoses, i.e., various molybdenum oxidemore » and molybdate species, nickel(II) diamine complexes, alkali-exchanged stannosilicate molecular sieves, and amorphous TiO2–SiO2 coprecipitates. Solid Lewis acid cocatalysts that are known to catalyze 1,2-intramolecular hydride shift (1,2-HS) reactions that enable the formation of α-hydroxy carboxylic acids from tetroses, trioses, and glycolaldehyde, but cannot readily catalyze retro-aldol reactions of hexoses and pentoses at these moderate temperatures, are shown to be compatible with the aforementioned retro-aldol catalysts. The combination of a distinct retro-aldol catalyst with a 1,2-HS catalyst enables lactic acid and alkyl lactate formation from ketohexoses at moderate temperatures (around 100 °C), with yields comparable to best-reported chemocatalytic examples at high temperature conditions (≥160 °C). The use of moderate temperatures enables numerous desirable features such as lower pressure and significantly less catalyst deactivation.« less

Reactions of singly-reduced ethylene carbonate in lithium battery electrolytes: a molecular dynamics simulation study using the ReaxFF.

PubMed

Bedrov, Dmitry; Smith, Grant D; van Duin, Adri C T

2012-03-22

We have conducted quantum chemistry calculations and gas- and solution-phase reactive molecular dynamics simulation studies of reactions involving the ethylene carbonate (EC) radical anion EC(-) using the reactive force field ReaxFF. Our studies reveal that the substantial barrier for transition from the closed (cyclic) form, denoted c-EC(-), of the radical anion to the linear (open) form, denoted o-EC(-), results in a relatively long lifetime of the c-EC(-) allowing this compound to react with other singly reduced alkyl carbonates. Using ReaxFF, we systematically investigate the fate of both c-EC(-) and o-EC(-) in the gas phase and EC solution. In the gas phase and EC solutions with a relatively low concentration of Li(+)/x-EC(-) (where x = o or c), radical termination reactions between radical pairs to form either dilithium butylene dicarbonate (CH(2)CH(2)OCO(2)Li)(2) (by reacting two Li(+)/o-EC(-)) or ester-carbonate compound (by reacting Li(+)/o-EC(-) with Li(+)/c-EC(-)) are observed. At higher concentrations of Li(+)/x-EC(-) in solution, we observe the formation of diradicals which subsequently lead to formation of longer alkyl carbonates oligomers through reaction with other radicals or, in some cases, formation of (CH(2)OCO(2)Li)(2) through elimination of C(2)H(4). We conclude that the local ionic concentration is important in determining the fate of x-EC(-) and that the reaction of c-EC(-) with o-EC(-) may compete with the formation of various alkyl carbonates from o-EC(-)/o-EC(-) reactions. © 2012 American Chemical Society

Occurrence of myo-inositol and alkyl-substituted polysaccharide in the prey-trapping mucilage of Drosera capensis

NASA Astrophysics Data System (ADS)

Kokubun, Tetsuo

2017-10-01

The chemical composition of the exudate mucilage droplets of the carnivorous plant Drosera capensis was investigated using nuclear magnetic resonance spectroscopy. The mucilage was found to contain beside a very large molecular weight polysaccharide a significant amount of myo-inositol. It appears that myo-inositol escaped detection due to the commonly applied methodology on the chemical analysis of plant mucilage, such as dialysis, precipitation of polysaccharide component with alcohol, acid hydrolysis and detection of the resultant monosaccharide (aldose) units. The possible functions of myo-inositol in the mucilage droplets and the fate after being washed off from the leaf tentacles are proposed. On the polysaccharide component, the presence of methyl ester and alkyl chain-like moieties could be confirmed. These lipophilic moieties may provide the prey-trapping mucilage with the unique adhesive property onto the hydrophobic insect body parts, as well as onto the nature's well-known superhydrophobic surfaces such as the leaves of the sacred lotus plants. A re-evaluation of the mineral components of the mucilage, reported 40 years ago, is presented from the viewpoints of the current result and plants' natural habitat. A case for re-examination of the well-studied plant mucilaginous materials is made in light of the new findings.

Induction of sister chromatid exchanges and cell division delays in human lymphocytes by the anti-tumour agent homo-aza-steroidal ester of p-bis(2-chloroethyl)aminophenoxy acetic acid.

PubMed

Tselepi, M R; Demopoulos, N A; Catsoulacos, P

1989-09-01

3 beta-Hydroxy-13 alpha-amino-13,17-seco-5 alpha-androstan-17-oic-13,17-lactam-p-bis(2-chloroethyl) aminophenoxyacetate (NSC 294859) is a new modified steroidal alkylating agent. This compound was given by i.p. administration to mice bearing different types of tumour. It was found to exhibit good activity in L1210 and P388 leukaemias with maintenance of activity against advanced tumours. The treatment of colon 26 tumour and B16 melanoma resulted in positive antineoplastic activity. The drug was not shown to be active in a melphalan-resistant P388 line. In this study, NSC 294859 was found to be effective in causing statistically significant increases in sister-chromatid exchange (SCE) rates and cell division delays. The alkylating agent component, p-bis-(2-chloroethyl)aminophenoxy acetic acid, was shown to be less effective than the parent compound, while the modified steroid component, 3 beta-hydroxy-13 alpha-amino-13,17-seco-5 alpha-androstan-17-oic-13,17-lactam, showed no effect. There were no statistically significant differences among donors regarding the induction of SCEs and replication indices (RIs) for the compounds tested.

Degradation of brominated flame retardant in computer housing plastic by supercritical fluids.

PubMed

Wang, Yanmin; Zhang, Fu-Shen

2012-02-29

The degradation process of brominated flame retardant (BFR) and BFR-containing waste computer housing plastic in various supercritical fluids (water, methanol, isopropanol and acetone) was investigated. The results showed that the debromination and degradation efficiencies, final products were greatly affected by the solvent type. Among the four tested solvents, isopropanol was the most suitable solvent for the recovery of oil from BFR-containing plastic for its (1) excellent debromination effectiveness (debromination efficiency 95.7%), (2) high oil production (60.0%) and (3) mild temperature and pressure requirements. However, in this case, the removed bromine mostly existed in the oil. Introduction of KOH into the sc-isopropanol could capture almost all the inorganic bromine from the oil thus bromine-free oil could be obtained. Furthermore, KOH could enhance the depolymerization of the plastic. The obtained oil mainly consisted of single- and duplicate-ringed aromatic compounds in a carbon range of C9-C17, which had alkyl substituents or aliphatic bridges, such as butyl-benzene, (3-methylbutyl)-benzene, 1,1'-(1,3-propanediyl)bis benzene. Phenol, alkyl phenols and esters were the major oxygen-containing compounds in the oil. This study provides an efficient approach for debromination and simultaneous recovering valuable chemicals from BFR-containing plastic in e-waste. Copyright © 2011 Elsevier B.V. All rights reserved.

A study of the antibacterial activity of L-phenylalanine and L-tyrosine esters in relation to their CMCs and their interactions with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC as model membrane.

PubMed

Joondan, Nausheen; Jhaumeer-Laulloo, Sabina; Caumul, Prakashanand

2014-01-01

Cationic amino acid-based surfactants are known to interact with the lipid bilayer of cell membranes resulting in depolarization, lysis and cell death through a disruption of the membrane topology. A range of cationic surfactant analogues derived from L-Phenylalanine (C1-C20) and L-Tyrosine (C8-C14) esters have been synthesized and screened for their antibacterial activity. The esters were more active against gram positive than gram negative bacteria. The activity increased with increasing chain length, exhibiting a cut-off effect at C12 for gram positive and C8/C10 for gram negative bacteria. The cut-off effect for gram negative bacteria was observed at a lower alkyl chain length. The CMC was correlated with the MIC, inferring that micellar activity contribute to the cut-off effect in antibacterial activity. The interaction of the cationic surfactants with the phospholipid vesicles (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC) in the presence of 1-anilino-8-naphthalene sulfonate (ANS) and 1,6-diphenyl-1,3,5-hexatriene (DPH) as fluorescence probes showed that an increase in ionic interaction causes an increase in antibacterial activity. Increase in hydrophobic interaction increases the antibacterial activity only to a certain chain length, attributing to the cut-off effect. Therefore, both electrostatic and hydrophobic interactions, involving the polar and nonpolar moieties are of paramount importance for the bactericidal properties. Copyright © 2014 Elsevier GmbH. All rights reserved.

Sequential Diels–Alder/[3,3]-sigmatropic rearrangement reactions of β-nitrostyrene with 3-methyl-1,3-pentadiene

PubMed Central

Pipic, Alma; Zeller, Matthias; Tsetsakos, Panagiota

2013-01-01

Summary The tin(IV)-catalyzed reaction of β-nitrostyrene with (E)-3-methyl-1,3-pentadiene in toluene afforded two major nitronic ester cycloadducts in 27% and 29% yield that arise from the reaction at the less substituted diene double bond. Also present were four cycloadducts from the reaction at the higher substituted diene double bond, two of which were the formal cycloadducts of (Z)-3-methyl-1,3-pentadiene. A Friedel–Crafts alkylation product from the reaction of the diene, β-nitrostyrene, and toluene was also obtained in 10% yield. The tin(IV)-catalyzed reaction of β-nitrostyrene with (Z)-3-methyl-1,3-pentadiene in dichloromethane afforded four nitronic ester cycloadducts all derived from the reaction at the higher substituted double bond. One cycloadduct was isolated in 45% yield and two others are formal adducts of the E-isomer of the diene. The product formation in these reactions is consistent with a stepwise mechanism involving a zwitterionic intermediate. The initially isolated nitronic ester cycloadducts underwent tin(IV)-catalyzed interconversion, presumably via zwitterion intermediates. Cycloadducts derived from the reaction at the less substituted double bond of (E)-3-methyl-1,3-pentadiene underwent a [3,3]-sigmatropic rearrangement on heating to afford 4-nitrocyclohexenes. Cycloadducts derived from the reaction at the higher substituted diene double bond of either diene failed to undergo a thermal rearrangement. Rates and success of the rearrangement are consistent with a concerted mechanism possessing a dipolar transition state. An initial assessment of substituent effects on the rearrangement process is presented. PMID:24204426

Abiotic condensation synthesis of glyceride lipids and wax esters under simulated hydrothermal conditions.

PubMed

Rushdi, Ahmed I; Simoneit, Bernd R T

2006-04-01

Precursor compounds for abiotic proto cellular membranes are necessary for the origin of life. Amphipathic compounds such as fatty acids and acyl glycerols are important candidates for micelle/bilayer/vesicle formation. Two sets of experiments were conducted to study dehydration reactions of model lipid precursors in aqueous media to form acyl polyols and wax esters, and to evaluate the stability and reactions of the products at elevated temperatures. In the first set, mixtures of n-nonadecanoic acid and ethylene glycol in water, with and without oxalic acid, were heated at discrete temperatures from 150 ( composite function)C to 300 ( composite function)C for 72 h. The products were typically alkyl alkanoates, ethylene glycolyl alkanoates, ethylene glycolyl bis-alkanoates and alkanols. The condensation products had maximum yields between 150 ( composite function)C and 250 ( composite function)C, and were detectable and thus stable under hydrothermal conditions to temperatures < 300 ( composite function)C. In the second set of experiments, mixtures of n-heptanoic acid and glycerol were heated using the same experimental conditions, with and without oxalic acid, between 100 ( composite function)C and 250 ( composite function)C. The main condensation products were two isomers each of monoacylglycerols and diacylglycerols at all temperatures, as well as minor amounts of the fatty acid anhydride and methyl ester. The yield of glyceryl monoheptanoates generally increased with increasing temperature and glyceryl diheptanoates decreased noticeably with increasing temperature. The results indicate that condensation reactions and abiotic synthesis of organic lipid compounds under hydrothermal conditions occur easily, provided precursor concentrations are sufficiently high.

Isomerization of 1-O-indol-3-ylacetyl-beta-D-glucose. Enzymatic hydrolysis of 1-O, 4-O, and 6-O-indol-3-ylacetyl-beta-D-glucose and the enzymatic synthesis of indole-3-acetyl glycerol by a hormone metabolizing complex

NASA Technical Reports Server (NTRS)

Kowalczyk, S.; Bandurski, R. S.

1990-01-01

The first compound in the series of reactions leading to the ester conjugates of indole-3-acetic acid (IAA) in kernels of Zea mays sweet corn is the acyl alkyl acetal, 1-O-indol-3-ylacetyl-beta-D-glucose (1-O-IAGlu). The enzyme catalyzing the synthesis of this compound is UDP-glucose:indol-3-ylacetate glucosyl-transferase (IAGlu synthase). The IAA moiety of the high energy compound 1-O-IAGlu may be enzymatically transferred to myo-inositol or to glycerol or the 1-O-IAGlu may be enzymatically hydrolyzed. Alternatively, nonenzymatic acyl migration may occur to yield the 2-O, 4-O, and 6-O esters of IAA and glucose. The 4-O and 6-O esters may then be enzymatically hydrolyzed to yield free IAA and glucose. This work reports new enzymatic activities, the transfer of IAA from 1-O-IAGlu to glycerol, and the enzyme-catalyzed hydrolysis of 4-O and 6-O-IAGlu. Data is also presented on the rate of non-enzymatic acyl migration of IAA from the 1-O to the 4-O and 6-O positions of glucose. We also report that enzymes catalyzing the synthesis of 1-O-IAGlu and the hydrolysis of 1-O, 4-O, and 6-O-IAGlu fractionate as a hormone metabolizing complex. The association of synthetic and hydrolytic capabilities in enzymes which cofractionate may have physiological significance.

Concerning a new classification of tricyanides

NASA Technical Reports Server (NTRS)

Krafft, F.; Vonhansen, A.

1979-01-01

A new classification series of tricyanides is presented. Several tricyanides are synthesized by a simple method from aluminum chloride, benzonitrile, and a respective alkyl or phenyl chloride, purified by recrystallization and distillation, and then analyzed. Structural formulae are suggested, and molecular weights, melting points, and boiling points are determined for each.

The Two Faces of Sulfinates: Illustrating Umpolung Reactivity

ERIC Educational Resources Information Center

Tapia-Pineda, Adabelia; Perez-Arrieta, Carlos; Silva-Cuevas, Carolina; Paleo, Ehecatl; Lujan-Montelongo, J. Armando

2016-01-01

A simple, microscale experiment was developed with the aim of demonstrating the concept of umpolung in synthetic organic chemistry. Starting from a common alkyl sulfinate, students perform a polarity inversion by performing a Grignard-based sulfoxide synthesis and a Mannich-type formamide synthesis. The products are purified without chromatography…

Development of an HPLC Method with an ODS Column to Determine Low Levels of Aspartame Diastereomers in Aspartame

PubMed Central

Ohtsuki, Takashi; Nakamura, Ryoichiro; Kubo, Satoru; Otabe, Akira; Oobayashi, Yoko; Suzuki, Shoko; Yoshida, Mika; Yoshida, Mitsuya; Tatebe, Chiye; Sato, Kyoko; Akiyama, Hiroshi

2016-01-01

α-L-Aspartyl-D-phenylalanine methyl ester (L, D-APM) and α-D-aspartyl-L-phenylalanine methyl ester (D, L-APM) are diastereomers of aspartame (N-L-α-Aspartyl-L-phenylalanine-1-methyl ester, L, L-APM). The Joint FAO/WHO Expert Committee on Food Additives has set 0.04 wt% as the maximum permitted level of the sum of L, D-APM and D, L-APM in commercially available L, L-APM. In this study, we developed and validated a simple high-performance liquid chromatography (HPLC) method using an ODS column to determine L, D-APM and D, L-APM in L, L-APM. The limits of detection and quantification, respectively, of L, D-APM and D, L-APM were found to be 0.0012 wt% and 0.004 wt%. This method gave excellent accuracy, repeatability, and reproducibility in a recovery test performed on five different days. Moreover, the method was successfully applied to the determination of these diastereomers in commercial L, L-APM samples. Thus, the developed method is a simple, useful, and practical tool for determining L, D-APM and D, L-APM levels in L, L-APM. PMID:27015640

Development of an HPLC Method with an ODS Column to Determine Low Levels of Aspartame Diastereomers in Aspartame.

PubMed

Ohtsuki, Takashi; Nakamura, Ryoichiro; Kubo, Satoru; Otabe, Akira; Oobayashi, Yoko; Suzuki, Shoko; Yoshida, Mika; Yoshida, Mitsuya; Tatebe, Chiye; Sato, Kyoko; Akiyama, Hiroshi

2016-01-01

α-L-Aspartyl-D-phenylalanine methyl ester (L, D-APM) and α-D-aspartyl-L-phenylalanine methyl ester (D, L-APM) are diastereomers of aspartame (N-L-α-Aspartyl-L-phenylalanine-1-methyl ester, L, L-APM). The Joint FAO/WHO Expert Committee on Food Additives has set 0.04 wt% as the maximum permitted level of the sum of L, D-APM and D, L-APM in commercially available L, L-APM. In this study, we developed and validated a simple high-performance liquid chromatography (HPLC) method using an ODS column to determine L, D-APM and D, L-APM in L, L-APM. The limits of detection and quantification, respectively, of L, D-APM and D, L-APM were found to be 0.0012 wt% and 0.004 wt%. This method gave excellent accuracy, repeatability, and reproducibility in a recovery test performed on five different days. Moreover, the method was successfully applied to the determination of these diastereomers in commercial L, L-APM samples. Thus, the developed method is a simple, useful, and practical tool for determining L, D-APM and D, L-APM levels in L, L-APM.

A simple protocol for NMR analysis of the enantiomeric purity of chiral hydroxylamines.

PubMed

Tickell, David A; Mahon, Mary F; Bull, Steven D; James, Tony D

2013-02-15

A practically simple three-component chiral derivatization protocol for determining the enantiopurity of chiral hydroxylamines by (1)H NMR spectroscopic analysis is described, involving their treatment with 2-formylphenylboronic acid and enantiopure BINOL to afford a mixture of diastereomeric nitrono-boronate esters whose ratio is an accurate reflection of the enantiopurity of the parent hydroxylamine.

Rapid discrimination of extracts of Chinese propolis and poplar buds by FT-IR and 2D IR correlation spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Yan-Wen; Sun, Su-Qin; Zhao, Jing; Li, Yi; Zhou, Qun

2008-07-01

The extract of Chinese propolis (ECP) has recently been adulterated with that of poplar buds (EPB), because most of ECP is derived from the poplar plant, and ECP and EPB have almost identical chemical compositions. It is very difficult to differentiate them by using the chromatographic methods such as high performance liquid chromatography (HPLC) and gas chromatography (GC). Therefore, how to effectively discriminate these two mixtures is a problem to be solved urgently. In this paper, a rapid method for discriminating ECP and EPB was established by the Fourier transform infrared (FT-IR) spectra combined with the two-dimensional infrared correlation (2D IR) analysis. Forty-three ECP and five EPB samples collected from different areas of China were analyzed by the FT-IR spectroscopy. All the ECP and EPB samples tested show similar IR spectral profiles. The significant differences between ECP and EPB appear in the region of 3000-2800 cm -1 of the spectra. Based on such differences, the two species were successfully classified with the soft independent modeling of class analogy (SIMCA) pattern recognition technique. Furthermore, these differences were well validated by a series of temperature-dependent dynamic FT-IR spectra and the corresponding 2D IR plots. The results indicate that the differences in these two natural products are caused by the amounts of long-chain alkyl compounds (including long-chain alkanes, long-chain alkyl esters and long chain alkyl alcohols) in them, rather than the flavonoid compounds, generally recognized as the bioactive substances of propolis. There are much more long-chain alkyl compounds in ECP than those in EPB, and the carbon atoms of the compounds in ECP remain in an order Z-shaped array, but those in EPB are disorder. It suggests that FT-IR and 2D IR spectroscopy can provide a valuable method for the rapid differentiation of similar natural products, ECP and EPB. The IR spectra could directly reflect the integrated chemical compositions of complicated mixtures, and it may be available for use in further chromatographic analysis.

Molecular Characterization of Cryoconite Organic Matter from the Athabasca Glacier, Canadian Rocky Mountains

NASA Astrophysics Data System (ADS)

Xu, Y.; Simpson, M. J.; Eyles, N.; Simpson, A.; Baer, A. J.

2009-05-01

Cryoconite is a dark-colored, dust-like material found on the surfaces of glaciers. Cryoconite holes, which are produced by accelerated ice melt due to more solar radiation absorption by cryoconite than bare ice, act as habitats for microbial life and biologically mediated chemical reactions on otherwise relatively inert glacier surfaces. Cryoconite holes may behave as bacterial shelters during "Snowball Earth" events postulated for the Neoproterozoic Earth. In this study organic matter (OM) biomarkers and a host of one- and two-dimensional NMR techniques were used to characterize cryoconite organic matter (COM) collected from the Athabasca Glacier in the Canadian Rocky Mountains. Solvent extracts contain large quantities of fatty acids, n-alkanols, n- alkanes, wax esters and sterols. A large contribution of C23 and C25 relative to C29 and C31 n-alkanes ([C23/(C23+C29)] = 0.51) suggests that allochthonous COM is derived mainly from lower order plants such as mosses and lichens. This is confirmed by the absence of lignin-derived phenols, a biomarker of terrestrial vascular plants, after copper (II) oxidation in extracts and NMR analyses of COM. Solution-state 1H NMR reveals prominent peptide/protein structures which are characteristic of microbial inputs, while solid-state 13C CP/MAS NMR analysis shows a very high alkyl/O-alkyl ratio (2.16), suggesting that COM is unique compared to organic matter found in nearby soils which have alkyl/O-alkyl ratio of ~0.39. Our NMR results suggest that COM is dominated by microbial-derived compounds, which is also confirmed by phospholipid fatty acid results (6,950µg/gOC) which show significant microbial contributions to COM primarily from bacteria and minor microeukaryotes. Both biomarker and NMR data suggest that COM likely supports active microbial communities on the Athabasca Glacier. Given that such material is incorporated within the glacier in the accumulation zone or flushed by meltwaters into subglacial environments, reworked COM may provide nutrient sources for active microbial communities found within and under glaciers.

Controlled conjugated backbone twisting for an increased open-circuit voltage while having a high short-circuit current in poly(hexylthiophene) derivatives.

PubMed

Ko, Sangwon; Hoke, Eric T; Pandey, Laxman; Hong, Sanghyun; Mondal, Rajib; Risko, Chad; Yi, Yuanping; Noriega, Rodrigo; McGehee, Michael D; Brédas, Jean-Luc; Salleo, Alberto; Bao, Zhenan

2012-03-21

Conjugated polymers with nearly planar backbones have been the most commonly investigated materials for organic-based electronic devices. More twisted polymer backbones have been shown to achieve larger open-circuit voltages in solar cells, though with decreased short-circuit current densities. We systematically impose twists within a family of poly(hexylthiophene)s and examine their influence on the performance of polymer:fullerene bulk heterojunction (BHJ) solar cells. A simple chemical modification concerning the number and placement of alkyl side chains along the conjugated backbone is used to control the degree of backbone twisting. Density functional theory calculations were carried out on a series of oligothiophene structures to provide insights on how the sterically induced twisting influences the geometric, electronic, and optical properties. Grazing incidence X-ray scattering measurements were performed to investigate how the thin-film packing structure was affected. The open-circuit voltage and charge-transfer state energy of the polymer:fullerene BHJ solar cells increased substantially with the degree of twist induced within the conjugated backbone--due to an increase in the polymer ionization potential--while the short-circuit current decreased as a result of a larger optical gap and lower hole mobility. A controlled, moderate degree of twist along the poly(3,4-dihexyl-2,2':5',2''-terthiophene) (PDHTT) conjugated backbone led to a 19% enhancement in the open-circuit voltage (0.735 V) vs poly(3-hexylthiophene)-based devices, while similar short-circuit current densities, fill factors, and hole-carrier mobilities were maintained. These factors resulted in a power conversion efficiency of 4.2% for a PDHTT:[6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM) blend solar cell without thermal annealing. This simple approach reveals a molecular design avenue to increase open-circuit voltage while retaining the short-circuit current.

Mineral oil metal working fluids (MWFs)-development of practical criteria for mist sampling.

PubMed

Simpson, A T; Groves, J A; Unwin, J; Piney, M

2000-05-01

Not all mineral oil metalworking fluids (MWFs) in common use form stable airborne mists which can be sampled quantitatively onto a filter. This much has been known for some time but no simple method of identifying oils too volatile for customary filter sampling has been developed. Past work was reviewed and experiments were done to select simple criteria which would enable such oils to be identified. The sampling efficiency for a range of commercial mineral oil MWF were assessed by drawing clean air through spiked filters at 2 l. min(-1) for periods up to 6 h before analysis. The physical properties of MWF are governed by their composition and kinematic viscosity was found to be the most practical and easily available index of the potential for sample loss from the filter. Oils with viscosities greater that 18 cSt (at 40 degrees C) lost less than 5% of their weight, whereas those with viscosities less than 18 cSt gave losses up to 71%. The losses from the MWF were mostly aliphatic hydrocarbons (C(10)-C(18)), but additives such as alkyl benzenes, esters, phenols and terpene odorants were also lost. The main recommendation to arise from the work is that filter sampling can be performed on mineral oils with viscosities of 18 cSt (at 40 degrees C) or more with little evaporative losses from the filter. However, sampling oils with viscosities less than 18 cSt will produce results which may significantly underestimate the true value. Over a quarter of UK mineral oil MWFs are formulated from mineral oils with viscosities less than 18 cSt (at 40 degrees C). The problem of exposure under-estimation and inappropriate exposure sampling could be widespread. Further work is being done on measurement of mixed phase mineral oil mist exposure.

Synthesis and biological screening by novel hybrid fluorocarbon hydrocarbon compounds for use as artificial blood substitutes

NASA Technical Reports Server (NTRS)

Moacanin, J.; Scherer, K.; Toronto, A.; Lawson, D.; Terranova, T.; Yavrouian, A.; Astle, L.; Harvey, S.; Kaaelble, D. H.

1979-01-01

A series of hybrid fluorochemicals of general structure R(1)R(2)R(3)CR(4) was prepared where the R(i)'s (i=1,2,3) is a saturated fluoroalkyl group of formula C sub N F sub 2n+1, and R(4) is an alkyl group C sub n H sub 2n+1 or a related moiety containing amino, ether, or ester functions but no CF bonds. Compounds of this class containing approximately eight to twenty carbons total have physical properties suitable for use as the oxygen carrying phase of fluorochemical emulsion artificial blood. The chemical synthesis, and physical and biological testing of pure single isomers of the proposed artificial blood candidate compounds are included. Significant results are given.

Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

PubMed

Souillart, Laetitia; Cramer, Nicolai

2014-09-01

The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tandem cyclopropanation with dibromomethane under Grignard conditions.

PubMed

Brunner, Gerhard; Eberhard, Laura; Oetiker, Jürg; Schröder, Fridtjof

2008-10-03

Tertiary Grignard reagents and dibromomethane efficiently cyclopropanate allylic (and certain homoallylic) magnesium and lithium alcoholates at ambient temperature in ether solvents. Lithium (homo)allyl alcoholates are directly cyclopropanated with magnesium and CH2Br2 under Barbier conditions at higher temperatures. The reaction rates depend on the substitution pattern of the (homo)allylic alcoholates and on the counterion with lithium giving best results. Good to excellent syn-selectivities are obtained from alpha-substituted substrates, which are in accord with a staggered Houk model. In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl carboxylates or vinyloxiranes. Using this methodology, numerous fragrance ingredients and their precursors were efficiently converted to the corresponding cyclopropyl carbinols.

Removal of the endocrine disrupter butyl benzyl phthalate from the environment

PubMed Central

Karlovsky, Petr

2010-01-01

Butyl benzyl phthalate (BBP), an aryl alkyl ester of 1,2-benzene dicarboxylic acid, is extensively used in vinyl tiles and as a plasticizer in PVC in many commonly used products. BBP, which readily leaches from these products, is one of the most important environmental contaminants, and the increased awareness of its adverse effects on human health has led to a dramatic increase in research aimed at removing BBP from the environment via bioremediation. This review highlights recent progress in the degradation of BBP by pure and mixed bacterial cultures, fungi, and in sludge, sediment, and wastewater. Sonochemical degradation, a unique abiotic remediation technique, and photocatalytic degradation are also discussed. The degradation pathways for BBP are described, and future research directions are considered. PMID:20396882

One-step synthesis of carbohydrate esters as antibacterial and antifungal agents.

PubMed

AlFindee, Madher N; Zhang, Qian; Subedi, Yagya Prasad; Shrestha, Jaya P; Kawasaki, Yukie; Grilley, Michelle; Takemoto, Jon Y; Chang, Cheng-Wei Tom

2018-02-01

Carbohydrate esters are biodegradable, and the degraded adducts are naturally occurring carbohydrates and fatty acids which are environmentally friendly and non-toxic to human. A simple one-step regioselective acylation of mono-carbohydrates has been developed that leads to the synthesis of a wide range of carbohydrate esters. Screening of these acylated carbohydrates revealed that several compounds were active against a panel of bacteria and fungi, including Staphylococcus aureus, methicillin-resistant S. aureus (MRSA), Candida albicans, Cryptococcus neoformans, Aspergillus flavus and Fusarium graminearum. Unlike prior studies on carbohydrate esters that focus only on antibacterial applications, our compounds are found to be active against both bacteria and fungi. Furthermore, the synthetic methodology is suitable to scale-up production for a variety of acylated carbohydrates. The identified lead compound, MAN014, can be used as an antimicrobial in applications such as food processing and preservation and for treatment of bacterial and fungal diseases in animals and plants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Making sense of enthalpy of vaporization trends for ionic liquids: new experimental and simulation data show a simple linear relationship and help reconcile previous data.

PubMed

Verevkin, Sergey P; Zaitsau, Dzmitry H; Emel'yanenko, Vladimir N; Yermalayeu, Andrei V; Schick, Christoph; Liu, Hongjun; Maginn, Edward J; Bulut, Safak; Krossing, Ingo; Kalb, Roland

2013-05-30

Vaporization enthalpy of an ionic liquid (IL) is a key physical property for applications of ILs as thermofluids and also is useful in developing liquid state theories and validating intermolecular potential functions used in molecular modeling of these liquids. Compilation of the data for a homologous series of 1-alkyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([C(n)mim][NTf2]) ILs has revealed an embarrassing disarray of literature results. New experimental data, based on the concurring results from quartz crystal microbalance, thermogravimetric analyses, and molecular dynamics simulation have revealed a clear linear dependence of IL vaporization enthalpies on the chain length of the alkyl group on the cation. Ambiguity of the procedure for extrapolation of vaporization enthalpies to the reference temperature 298 K was found to be a major source of the discrepancies among previous data sets. Two simple methods for temperature adjustment of vaporization enthalpies have been suggested. Resulting vaporization enthalpies obey group additivity, although the values of the additivity parameters for ILs are different from those for molecular compounds.

Synthesis and Characterization of Fatty Acid/Amino Acid Self-Assemblies

PubMed Central

Gajowy, Joanna; Bolikal, Durgadas; Kohn, Joachim; El Fray, Miroslawa

2014-01-01

In this paper, we discuss the synthesis and self-assembling behavior of new copolymers derived from fatty acid/amino acid components, namely dimers of linoleic acid (DLA) and tyrosine derived diphenols containing alkyl ester pendent chains, designated as “R” (DTR). Specific pendent chains were ethyl (E) and hexyl (H). These poly(aliphatic/aromatic-ester-amide)s were further reacted with poly(ethylene glycol) (PEG) and poly(ethylene glycol methyl ether) of different molecular masses, thus resulting in ABA type (hydrophilic-hydrophobic-hydrophilic) triblock copolymers. We used Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies to evaluate the chemical structure of the final materials. The molecular masses were estimated by gel permeation chromatography (GPC) measurements. The self-organization of these new polymeric systems into micellar/nanospheric structures in aqueous environment was evaluated using ultraviolet/visible (UV-VIS) spectroscopy, dynamic light scattering (DLS) and transmission electron microscopy (TEM). The polymers were found to spontaneously self-assemble into nanoparticles with sizes in the range 196–239 nm and critical micelle concentration (CMC) of 0.125–0.250 mg/mL. The results are quite promising and these materials are capable of self-organizing into well-defined micelles/nanospheres encapsulating bioactive molecules, e.g., vitamins or antibacterial peptides for antibacterial coatings on medical devices. PMID:25347356

Transesterification of waste cooking oil by an organic solvent-tolerant alkaline lipase from Streptomyces sp. CS273.

PubMed

Mander, Poonam; Yoo, Hah-Young; Kim, Seung Wook; Choi, Yun Hee; Cho, Seung Sik; Yoo, Jin Cheol

2014-02-01

The aim of this present study was to produce a microbial enzyme that can potentially be utilized for the enzymatic transesterification of waste cooking oil. To that end, an extracellular lipase was isolated and purified from the culture broth of Streptomyces sp. CS273. The molecular mass of purified lipase was estimated to be 36.55 kDa by SDS PAGE. The optimum lipolytic activity was obtained at alkaline pH 8.0 to 8.5 and temperature 40 °C, while the enzyme was stable in the pH range 7.0 ∼ 9.0 and at temperature ≤40 °C. The lipase showed highest hydrolytic activity towards p-nitrophenyl myristate (C14). The lipase activity was enhanced by several salts and detergents including NaCl, MnSo₄, and deoxy cholic acid, while phenylmethylsulfonyl fluoride at concentration 10 mM inhibited the activity. The lipase showed tolerance towards different organic solvents including ethanol and methanol which are commonly used in transesterification reactions to displace alcohol from triglycerides (ester) contained in renewable resources to yield fatty acid alkyl esters known as biodiesel. Applicability of the lipase in transesterification of waste cooking oil was confirmed by gas chromatography mass spectrometry analysis.

Forensic identification of spilled biodiesel and its blends with petroleum oil based on fingerprinting information.

PubMed

Yang, Zeyu; Hollebone, Bruce P; Wang, Zhendi; Yang, Chun; Brown, Carl; Landriault, Mike

2013-06-01

A case study is presented for the forensic identification of several spilled biodiesels and its blends with petroleum oil using integrated forensic oil fingerprinting techniques. The integrated fingerprinting techniques combined SPE with GC/MS for obtaining individual petroleum hydrocarbons (aliphatic hydrocarbons, polyaromatic hydrocarbons and their alkylated derivatives and biomarkers), and biodiesel hydrocarbons (fatty acid methyl esters, free fatty acids, glycerol, monoacylglycerides, and free sterols). HPLC equipped with evaporative scattering laser detector was also used for identifying the compounds that conventional GC/MS could not finish. The three environmental samples (E1, E2, and E3) and one suspected source sample (S2) were dominant with vegetable oil with high acid values and low concentration of fatty acid methyl ester. The suspected source sample S2 was responsible for the three spilled samples although E1 was slightly contaminated by petroleum oil with light hydrocarbons. The suspected source sample S1 exhibited with the high content of glycerol, low content of glycerides, and high polarity, indicating its difference from the other samples. These samples may be the separated byproducts in producing biodiesel. Canola oil source is the most possible feedstock for the three environmental samples and the suspected source sample S2. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

World-Wide Indoor Exposure to Polyfluoroalkyl Phosphate Esters (PAPs) and other PFASs in Household Dust.

PubMed

Eriksson, Ulrika; Kärrman, Anna

2015-12-15

Human exposure to perfluorooctanoic acid (PFOA) and other per- and polyfluoroalkyl substances (PFASs) is ongoing and in some cases increasing, despite efforts made to reduce emissions. The role of precursor compounds such as polyfluorinated phosphate esters (PAPs) has received increasing attention, but there are knowledge gaps regarding their occurrence and impact on human exposure. In this study, mono-, di-, and triPAPs, perfluorinated alkyl acids (PFAAs), saturated, and unsaturated fluorotelomer carboxylic acids (FTCA/FTUCAs), perfluoroalkane sulfonamides, and sulfonamidethanols (FOSA/FOSEs), and one fluorotelomer sulfonic acid (FTSA)) were compared in household dust samples from Canada, the Faroe Islands, Sweden, Greece, Spain, Nepal, Japan, and Australia. Mono-, di-, and triPAPs, including several diPAP homologues, were frequently detected in dust from all countries, revealing an ubiquitous spread in private households from diverse geographic areas, with significant differences between countries. The median levels of monoPAPs and diPAPs ranged from 3.7 ng/g to 1 023 ng/g and 3.6 ng/g to 692 ng/g, respectively, with the lowest levels found in Nepal and the highest in Japan. The levels of PAPs exceeded those of the other PFAS classes. These findings reveal the importance of PAPs as a source of PFAS exposure worldwide.

Orally administered glycidol and its fatty acid esters as well as 3-MCPD fatty acid esters are metabolized to 3-MCPD in the F344 rat.

PubMed

Onami, Saeko; Cho, Young-Man; Toyoda, Takeshi; Akagi, Jun-ichi; Fujiwara, Satoshi; Ochiai, Ryosuke; Tsujino, Kazushige; Nishikawa, Akiyoshi; Ogawa, Kumiko

2015-12-01

IARC has classified glycidol and 3-monochloropropane-1,2-diol (3-MCPD) as group 2A and 2B, respectively. Their esters are generated in foodstuffs during processing and there are concerns that they may be hydrolyzed to the carcinogenic forms in vivo. Thus, we conducted two studies. In the first, we administered glycidol and 3-MCPD and associated esters (glycidol oleate: GO, glycidol linoleate: GL, 3-MCPD dipalmitate: CDP, 3-MCPD monopalmitate: CMP, 3-MCPD dioleate: CDO) to male F344 rats by single oral gavage. After 30 min, 3-MCPD was detected in serum from all groups. Glycidol was detected in serum from the rats given glycidol or GL and CDP and CDO in serum from rats given these compounds. In the second, we examined if metabolism occurs on simple reaction with rat intestinal contents (gastric, duodenal and cecal contents) from male F344 gpt delta rats. Newly produced 3-MCPD was detected in all gut contents incubated with the three 3-MCPD fatty acid esters and in gastric and duodenal contents incubated with glycidol and in duodenal and cecal contents incubated with GO. Although our observation was performed at 1 time point, the results showed that not only 3-MCPD esters but also glycidol and glycidol esters are metabolized into 3-MCPD in the rat. Copyright © 2015 Elsevier Inc. All rights reserved.

Biochemical analysis of human milk treated with sodium dodecyl sulfate, an alkyl sulfate microbicide that inactivates human immunodeficiency virus type 1.

PubMed

Hartmann, Sandra Urdaneta; Wigdahl, Brian; Neely, Elizabeth B; Berlin, Cheston M; Schengrund, Cara-Lynne; Lin, Hung-Mo; Howett, Mary K

2006-02-01

Reduction of transmission of human immunodeficiency virus type 1 (HIV-1) through human milk is needed. Alkyl sulfates such as sodium dodecyl sulfate (SDS) are microbicidal against HIV-1 at low concentrations, have little to no toxicity, and are inexpensive. The authors have reported that treatment of HIV-1-infected human milk with < or = 1% (10 mg/mL) SDS for 10 minutes inactivates cell-free and cell-associated virus. The SDS can be removed with a commercially available resin after treatment without recovery of viral infectivity. In this article, the authors report results of selective biochemical analyses (ie, protein, immunoglobulins, lipids, cells, and electrolytes) of human milk subjected to SDS treatment and removal. The SDS treatment or removal had no significant effects on the milk components studied. Therefore, the use of alkyl sulfate microbicides to treat milk from HIV-1-positive women may be a simple, practical, and nutritionally sound way to prevent or reduce transmission of HIV-1 while still feeding with mother's own milk.

Characterization and cytotoxicity evaluation of biocompatible amino acid esters used to convert salicylic acid into ionic liquids.

PubMed

Moshikur, Rahman Md; Chowdhury, Md Raihan; Wakabayashi, Rie; Tahara, Yoshiro; Moniruzzaman, Muhammad; Goto, Masahiro

2018-07-30

The technological utility of active pharmaceutical ingredients (APIs) is greatly enhanced when they are transformed into ionic liquids (ILs). API-ILs have better solubility, thermal stability, and the efficacy in topical delivery than solid or crystalline drugs. However, toxicological issue of API-ILs is the main challenge for their application in drug delivery. To address this issue, 11 amino acid esters (AAEs) were synthesized and investigated as biocompatible counter cations for the poorly water-soluble drug salicylic acid (Sal) to form Sal-ILs. The AAEs were characterized using 1 H and 13 C NMR, FTIR, elemental, and thermogravimetric analyses. The cytotoxicities of the AAE cations, Sal-ILs, and free Sal were investigated using mammalian cell lines (L929 and HeLa). The toxicities of the AAE cations greatly increased with inclusion of long alkyl chains, sulfur, and aromatic rings in the side groups of the cations. Ethyl esters of alanine, aspartic acid, and proline were selected as a low cytotoxic AAE. The cytotoxicities of the Sal-ILs drastically increased compared with the AAEs on incorporation of Sal into the cations, and were comparable to that of free Sal. Interestingly, the water miscibilities of the Sal-ILs were higher than that of free Sal, and the Sal-ILs were miscible with water at any ratio. A skin permeation study showed that the Sal-ILs penetrated through skin faster than the Sal sodium salt. These results suggest that AAEs could be used in biomedical applications to eliminate the use of traditional toxic solvents for transdermal delivery of poorly water-soluble drugs. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of water on foaming properties of diglycerol fatty acid ester-oil systems.

PubMed

Shrestha, Lok Kumar; Shrestha, Rekha Goswami; Solans, Conxita; Aramaki, Kenji

2007-06-19

We have studied the effect of added water on the nonaqueous foaming properties of diglycerol fatty acid ester nonionic surfactant systems. Diglycerol monomyristate (designated as DGM) could not foam in nonpolar oils squalane and hexadecane at normal room temperature. Nevertheless, addition of a small amount of water induces a dramatic change in foaming properties. Both the foamability and foam stability increases with the amount of added water within the studied concentration range. Phase behavior study showed that in the dilute regions there is dispersion of solid surfactant in the aforementioned oils in the DGM systems. The particle size of the dispersed solid phase was found to be several tens of microns in the water free system, and hence it tends to coagulate and precipitate. In the case of shorter alkyl chain length, diglycerol monolaurate (DGL) surfactant-oil systems, dispersion of lamellar liquid crystal (Lalpha) is observed at room temperature, and the poor foaming properties were attributed to the large particle size of the liquid crystal. In both the DGL and DGM-oil systems, we observed a tendency of the particle size to decrease with the increasing concentration of added water. At higher temperature, the solid surfactant transforms to lamellar liquid crystal phase, and foaming is improved in the DGM/squalane system. Foams are stable for several minutes. Judging from the foaming test and particle size distribution data it can be concluded that the poor foaming in the diglycerol fatty acid esters-oil systems may possibly be due to bigger particle size, which causes precipitation. Addition of water results in the dispersion of smaller particles and improves the foaming behavior.

Highly Enantioselective Rhodium-Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram.

PubMed

Huang, Linwei; Zhu, Jinbin; Jiao, Guangjun; Wang, Zheng; Yu, Xingxin; Deng, Wei-Ping; Tang, Wenjun

2016-03-24

Highly enantioselective additions of arylboroxines to simple aryl ketones have been achieved for the first time with a Rh/(R,R,R,R)-WingPhos catalyst, thus providing a range of chiral diaryl alkyl carbinols with excellent ee values and yields. (R,R,R,R)-WingPhos has been proven to be crucial for the high reactivity and enantioselectivity. The method has enabled a new, concise, and enantioselective synthesis of the antidepressant drug escitalopram. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, docking study and relaxant effect of 2-alkyl and 2-naphthylchromones on rat aorta and guinea-pig trachea through phosphodiesterase inhibition.

PubMed

Rodríguez-Ramos, Fernando; Navarrete, Andrés; González-Andrade, Martín; Alarcón, Carlos; Aguilera-Cruz, Alejandro; Reyes-Ramírez, Adelfo

2013-10-01

Chromone (4), which form the base structure of various flavonoids isolated as natural products, is capable of relaxing smooth muscle. This is relevant to the treatment of high blood pressure, asthma and chronic obstructive pulmonary disease. The former disorder involves the contraction of vascular smooth muscle (VSM), and the latter two bronchoconstriction of airway smooth muscle (ASM). One of the principal mechanisms by which flavonoids relax muscle tissue is the inhibition of phosphodiesterases (PDEs), present in both VSM and ASM. Therefore, a study was designed to analyze the structure-activity relationship of chromone derivatives in vaso- and bronchorelaxation through the inhibition of PDE. Docking studies showed that these chromones bind at the catalytic site of PDEs. Consequently, we synthesized analogs of chromones substituted at position C-2 with alkyl and naphthyl groups. These compounds were synthesized from 2-hydroxyacetophenone and acyl chlorides in the presence of DBU and pyridine, modifying the methodology reported for the synthesis of 3-acylchromones by changing the reaction temperature from 80 to 30°C and using methylene chloride as solvent, yielding the corresponding phenolic esters 10a-10h. These compounds were cyclized with an equivalent of DBU, pyridine as solvent, and heated at reflux temperature, yielding the chromones 11a-11h. Evaluation of the vasorelaxant effect of 4, 11a-11h on rat aorta demonstrated that potency decreases with branched alkyl groups. Whereas the EC50 of compound 11d (substituted by an n-hexyl group) was 8.64±0.39 μM, that of 11f (substituted by an isobutyl group) was 14.58±0.64 μM. Contrarily, the effectiveness of the compound is directly proportional to the length of the alkyl chain, as evidenced by the increase in maximal effect of compound 11c versus 11d (66% versus 100%) and 11e versus 11f (60% versus 96%). With an aromatic group like naphthyl as the C-2 substituent, the effectiveness was only 43%. All compounds tested on guinea pig trachea showed less than 55% effectiveness. Compounds 4, 11a-11h were evaluated as PDE inhibitors in vitro, with 11d showing the greatest effect (73%), corroborating the importance of a long alkyl chain, which inhibits the decomposition of cGMP. Docking studies showed that the compound 11d was selective for the inhibition of PDE-5. Copyright © 2013 Elsevier Inc. All rights reserved.

Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes

PubMed Central

2015-01-01

We report a set of rare copper-catalyzed reactions of alkanes with simple amides, sulfonamides, and imides (i.e., benzamides, tosylamides, carbamates, and phthalimide) to form the corresponding N-alkyl products. The reactions lead to functionalization at secondary C–H bonds over tertiary C–H bonds and even occur at primary C–H bonds. [(phen)Cu(phth)] (1-phth) and [(phen)Cu(phth)2] (1-phth2), which are potential intermediates in the reaction, have been isolated and fully characterized. The stoichiometric reactions of 1-phth and 1-phth2 with alkanes, alkyl radicals, and radical probes were investigated to elucidate the mechanism of the amidation. The catalytic and stoichiometric reactions require both copper and tBuOOtBu for the generation of N-alkyl product. Neither 1-phth nor 1-phth2 reacted with excess cyclohexane at 100 °C without tBuOOtBu. However, the reactions of 1-phth and 1-phth2 with tBuOOtBu afforded N-cyclohexylphthalimide (Cy-phth), N-methylphthalimide, and tert-butoxycyclohexane (Cy-OtBu) in approximate ratios of 70:20:30, respectively. Reactions with radical traps support the intermediacy of a tert-butoxy radical, which forms an alkyl radical intermediate. The intermediacy of an alkyl radical was evidenced by the catalytic reaction of cyclohexane with benzamide in the presence of CBr4, which formed exclusively bromocyclohexane. Furthermore, stoichiometric reactions of [(phen)Cu(phth)2] with tBuOOtBu and (Ph(Me)2CO)2 at 100 °C without cyclohexane afforded N-methylphthalimide (Me-phth) from β-Me scission of the alkoxy radicals to form a methyl radical. Separate reactions of cyclohexane and d12-cyclohexane with benzamide showed that the turnover-limiting step in the catalytic reaction is the C–H cleavage of cyclohexane by a tert-butoxy radical. These mechanistic data imply that the tert-butoxy radical reacts with the C–H bonds of alkanes, and the subsequent alkyl radical combines with 1-phth2 to form the corresponding N-alkyl imide product. PMID:24405209

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

PubMed

Moradi, Ali Varasteh

2017-01-01

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

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

PubMed

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

2016-11-09

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

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

A multi-purpose tool for food inspection: Simultaneous determination of various classes of preservatives and biogenic amines in meat and fish products by LC-MS.

PubMed

Molognoni, Luciano; Daguer, Heitor; de Sá Ploêncio, Leandro Antunes; De Dea Lindner, Juliano

2018-02-01

This paper describes an innovative fast and multipurpose method for the chemical inspection of meat and fish products by liquid chromatography-tandem mass spectrometry. Solid-liquid extraction and low temperature partitioning were applied to 17 analytes, which included large bacteriocins (3.5kDa) and small molecules (organic acids, heterocyclic compounds, polyene macrolides, alkyl esters of the p-hydroxybenzoic acid, aromatic, and aliphatic biogenic amines and polyamines). Chromatographic separation was achieved in 10min, using stationary phase of di-isopropyl-3-aminopropyl silane bound to hydroxylated silica. Method validation was in accordance to Commission Decision 657/2002/CE. Linear ranges were among 1.25-10.0mgkg -1 (natamycin and parabens), 2.50-10.0mgkg -1 (sorbate and nisin), 25.0-200mgkg -1 (biogenic amines, hexamethylenetetramine, benzoic and lactic acids), and 50.0-400mgkg -1 (citric acid). Expanded measurement uncertainty (U) was estimated by single laboratory validation combined to modeling in two calculation approaches: internal (U = 5%) and external standardization (U = 24%). Method applicability was checked on 89 real samples among raw, cooked, dry fermented and cured products, yielding acceptable recoveries. Many regulatory issues were revealed, corroborating the need for enhancement of the current analytical methods. This simple execution method dispenses the use of additional procedures of extraction and, therefore, reduces costs over time. It is suitable for routine analysis as a screening or confirmatory tool for both qualitative and quantitative results, replacing many time consuming analytical procedures. Copyright © 2017 Elsevier B.V. All rights reserved.

Photoresponsive liquid crystalline epoxy networks with shape memory behavior and dynamic ester bonds

DOE PAGES

Rios, Orlando; Chen, Jihua; Li, Yuzhan; ...

2016-06-01

Functional polymers are intelligent materials that can respond to a variety of external stimuli. However, these materials have not yet found widespread real world applications because of the difficulties in fabrication and the limited number of functional building blocks that can be incorporated into a material. Here, we demonstrate a simple route to incorporate three functional building blocks (azobenzene chromophores, liquid crystals, and dynamic covalent bonds) into an epoxy-based liquid crystalline network (LCN), in which an azobenzene-based epoxy monomer is polymerized with an aliphatic dicarboxylic acid to create exchangeable ester bonds that can be thermally activated. Lastly, all three functionalmore » building blocks exhibited good compatibility, and the resulting materials exhibits various photomechanical, shape memory, and self-healing properties because of the azobenzene molecules, liquid crystals, and dynamic ester bonds, respectively.« less

Chemical Makeup and Hydrophilic Behavior of Graphene Oxide Nanoribbons after Low-Temperature Fluorination.

PubMed

Romero Aburto, Rebeca; Alemany, Lawrence B; Weldeghiorghis, Thomas K; Ozden, Sehmus; Peng, Zhiwei; Lherbier, Aurélien; Botello Méndez, Andrés Rafael; Tiwary, Chandra Sekhar; Taha-Tijerina, Jaime; Yan, Zheng; Tabata, Mika; Charlier, Jean-Christophe; Tour, James M; Ajayan, Pulickel M

2015-07-28

Here we investigated the fluorination of graphene oxide nanoribbons (GONRs) using H2 and F2 gases at low temperature, below 200 °C, with the purpose of elucidating their structure and predicting a fluorination mechanism. The importance of this study is the understanding of how fluorine functional groups are incorporated in complex structures, such as GONRs, as a function of temperature. The insight provided herein can potentially help engineer application-oriented materials for several research and industrial sectors. Direct (13)C pulse magic angle spinning (MAS) nuclear magnetic resonance (NMR) confirmed the presence of epoxy, hydroxyl, ester and ketone carbonyl, tertiary alkyl fluorides, as well as graphitic sp(2)-hybridized carbon. Moreover, (19)F-(13)C cross-polarization MAS NMR with (1)H and (19)F decoupling confirmed the presence of secondary alkyl fluoride (CF2) groups in the fluorinated graphene oxide nanoribbon (FGONR) structures fluorinated above 50 °C. First-principles density functional theory calculations gained insight into the atomic arrangement of the most dominant chemical groups. The fluorinated GONRs present atomic fluorine percentages in the range of 6-35. Interestingly, the FGONRs synthesized up to 100 °C, with 6-19% of atomic fluorine, exhibit colloidal similar stability in aqueous environments when compared to GONRs. This colloidal stability is important because it is not common for materials with up to 19% fluorine to have a high degree of hydrophilicity.

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

PubMed

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

2018-05-22

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

Inhaled Treprostinil-Prodrug Lipid Nanoparticle Formulations Provide Long-Acting Pulmonary Vasodilation.

PubMed

Leifer, Franziska G; Konicek, Donna M; Chen, Kuan-Ju; Plaunt, Adam J; Salvail, Dany; Laurent, Charles E; Corboz, Michel R; Li, Zhili; Chapman, Richard W; Perkins, Walter R; S Malinin, Vladimir

2018-05-23

Treprostinil (TRE), a prostanoid analogue approved in the USA for the treatment of pulmonary arterial hypertension, requires continuous infusion or multiple dosing sessions per day for inhaled and oral routes of administration due to its short half-life. The inhaled drug is known to induce adverse systemic and local effects including headache, nausea, cough, and throat irritation which may be due at least in part to transiently high drug concentrations in the lungs and plasma immediately following administration [1]. To ameliorate these side effects and reduce dosing frequency we designed an inhaled slow-release TRE formulation. TRE was chemically modified to be an alkyl prodrug (TPD) which was then packaged into a lipid nanoparticle (LNP) carrier. Preclinical screening in a rat model of hypoxia-induced pulmonary vasoconstriction led to selection of a 16-carbon alkyl ester derivative of TRE. The TPD-LNP demonstrated approximately 10-fold lower TRE plasma C max compared to inhaled TRE solution while maintaining an extended vasodilatory effect. The favorable PK profile is attributed to gradual dissociation of TPD from the LNP and subsequent conversion to TRE. Together, this sustained presentation of TRE to the lungs and plasma is consistent with a once- or twice-daily dosing schedule in the absence of high C max -associated adverse events which could provide patients with an improved treprostinil therapy. © Georg Thieme Verlag KG Stuttgart · New York.

Acidity and complex formation studies of 3-(adenine-9-yl)-propionic and 3-(thymine-1-yl)-propionic acids in ethanol-water media

NASA Astrophysics Data System (ADS)

Hammud, Hassan H.; El Shazly, Shawky; Sonji, Ghassan; Sonji, Nada; Bouhadir, Kamal H.

2015-05-01

The ligands 3-(adenine-9-yl)propionic acid (AA) and 3-(thymine-1-yl)propionic acid (TA) were prepared by N9-alkylation of adenine and N1-alkylation of thymine with ethylacrylate in presence of a base catalyst, followed by acid hydrolysis of the formed ethyl esters to give the corresponding propionic acid derivatives. The products were characterized by spectral methods (FTIR, 1H NMR and 13C NMR), which confirm their structures. The dissociation constants of ligands, were potentiometrically determined in 0.3 M KCl at 20-50 °C temperature range. The work was extended to study complexation behavior of AA and TA with various biologically important divalent metal ions (Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Mn2+ and Pb2+) in 50% v/v water-ethanol medium at four different temperatures, keeping ionic strength constant (0.3 M KCl). The order of the stability constants of the formed complexes decreases in the sequence Cu2+ > Pb2+ > Zn2+ > Ni2+ > Co2+ > Mn2+ > Cd2+ for both ligands. The effect of temperature was also studied and the corresponding thermodynamic functions (ΔG, ΔH, ΔS) were derived and discussed. The formation of metal complexes has been found to be spontaneous, and the stability constants were dependant markedly on the basicity of the ligands.

Efficient synthesis, structural characterization and anti-microbial activity of chiral aryl boronate esters of 1,2-O-isopropylidene-α-D-xylofuranose.

PubMed

Trivedi, Rajiv; Rami Reddy, E; Kiran Kumar, Ch; Sridhar, B; Pranay Kumar, K; Srinivasa Rao, M

2011-07-01

A simple and efficient synthetic approach toward a series of chiral aryl boronate esters, starting from D-xylose, as anti-microbial agents, is described herein. Minimum inhibitory concentration and zone of inhibition revealed that these derivatives exhibit potent anti-bacterial and anti-fungal properties. Herein, we report the first anti-microbial activity of this class of compounds. All products have been characterized by NMR ((1)H, (13)C and (11)B), IR, elemental and mass spectral study. Copyright © 2011 Elsevier Ltd. All rights reserved.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer

NASA Astrophysics Data System (ADS)

Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.

2016-11-01

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

PubMed

Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R

2016-11-10

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.

Decomposition of food lipids by ionizing radiation

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

Nawar, W.W.

1973-01-01

A number of animal and vegetable fats as well as model systems of triglycerides were used in a study to examine the effects of irradiation on the lipid fraction of foods. More than one hundred compounds were identified as radiolytic products. These include a series of hydrocarbons, aldehydes, esters, free acids, ethane- and propanediol diesters, propenediol diesters, diglycerides, triglycerides, ketones, glyceryl ether diesters, and 2-alkyl cyclobutanones. Reaction mechanism are proposed to explain the formation of the decomposition products. Bascially, these compounds result via the formation of free radicals according to preferential cleavages in the vicinity of the carbonyl groups. Sincemore » some of these compounds are unique to radiation effects, a method was developed to detect irradiation treatment in foods. Variables affecting the radiolytic pattern are discussed, and a comparison between thermolytic and radiolytic effects is presented. (GE)« less

Hydrozirconation of lithium alkynylselenolate anions. Generation and reactions of alpha-zirconated vinyl selenide intermediates

PubMed

Dabdoub; Begnini; Guerrero; Baroni

2000-01-14

Lithium alkynylselenolate anions react completely with 1.0 equiv of Cp(2)Zr(H)Cl in THF at room temperature to give exclusively the alpha-zirconated vinylselenolate intermediates 23-27, which by treatment with an alkyl halide afforded the alpha-zirconated vinyl alkylselenide intermediates 29-33. Reaction of 29-33 with butyltellurenyl bromide results in the formation of ketene telluro(seleno) acetals 35-39 with total control of the regio- and stereochemistry. The synthetic utility of the ketene telluro(seleno) acetals obtained here was demonstrated by reaction of 36 with butyllithium. This promotes the exclusive and stereospecific removal of the tellurium moiety and enables formation of the corresponding selenium-containing allylic alcohol of type 44, alpha-(alkylseleno)-alpha,beta-unsaturated aldehyde 45, ester 46, or carboxylic acid 47, after reaction with different types of electrophiles.

Synthesis of γ-Phosphate-Labeled and Doubly Labeled Adenosine Triphosphate Analogs.

PubMed

Hacker, Stephan M; Welter, Moritz; Marx, Andreas

2015-03-09

This unit describes the synthesis of γ-phosphate-labeled and doubly labeled adenosine triphosphate (ATP) analogs and their characterization using the phosphodiesterase I from Crotalus adamanteus (snake venom phosphodiesterase; SVPD). In the key step of the synthesis, ATP or an ATP analog, bearing a linker containing a trifluoroacetamide group attached to the nucleoside, are modified with an azide-containing linker at the terminal phosphate using an alkylation reaction. Subsequently, different labels are introduced to the linkers by transformation of one functional group to an amine and coupling to an N-hydroxysuccinimide ester. Specifically, the Staudinger reaction of the azide is employed as a straightforward means to obtain an amine in the presence of various labels. Furthermore, the fluorescence characteristics of a fluorogenic, doubly labeled ATP analog are investigated following enzymatic cleavage by SVPD. Copyright © 2015 John Wiley & Sons, Inc.

[Derivatives of lupinin and epilupinin as ligands of various cholinesterases].

PubMed

Basova, N E; Kormilitsyn, B N; Rozengart, E V; Saakov, V S; Suvorov, A A

2012-01-01

Literature data have been summarized on interaction of cholinesterases of some mammals and arthropods with a group of isomer derivatives of alkaloid lupini and its epimer epilupinin. As substrates of cholinesterases of several mammals there are studied 8 acetates containing in their molecules the chinolysidin bicycle with different structure of N-alkyl radical, which showed certain elements of specificity of action. For 2 isomer esters that are derivatives of the protonated base of the lupinin and epilupinin structures, differences in their substrate characteristics were revealed. The polyenzyme analysis if anticholinesterase efficiency was performed for 30 organophosphorus inhibitors that are dialkoxyphosphorus derivatives of lupinin and epilupinin; as a result, quite a few peculiarities of their action depending on their structure were revealed. Several tested compounds turned out to act as specific inhibitors of cholinesterases of some mammals and arthropods.

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

DOEpatents

Lin, YuPo J; St. Martin, Edward J

2013-08-13

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

Cross-reactions among parabens, para-phenylenediamine, and benzocaine: a retrospective analysis of patch testing.

PubMed

Turchin, Irina; Moreau, Linda; Warshaw, Erin; Sasseville, Denis

2006-12-01

Parabens are alkyl ester derivatives of para-hydroxybenzoic acid and are the most commonly used preservatives in the cosmetic industry. Cross-reactions with para-amino compounds, namely, benzocaine and para-phenylenediamine (PPD), have been reported but are thought to be extremely rare. To evaluate the rate of cross-reactivity between parabens, PPD, and benzocaine in a population of patients patch-tested in a hospital-based contact dermatitis clinic. A retrospective analysis of 4,368 patients consecutively patch-tested between July 1989 and June 2005. Our study demonstrated that the rate of cross-reactions to parabens in PPD- and benzocaine-positive patients combined is 2%. This cross-reaction rate is significant in the tested population but still falls within the previously reported rates of sensitivity to parabens in the general population (0 to 3.5%).

A Remarkably Simple Class of Imidazolium-Based Lipids and Their Biological Properties.

PubMed

Wang, Da; Richter, Christian; Rühling, Andreas; Drücker, Patrick; Siegmund, Daniel; Metzler-Nolte, Nils; Glorius, Frank; Galla, Hans-Joachim

2015-10-19

A series of imidazolium salts bearing two alkyl chains in the backbone of the imidazolium core were synthesized, resembling the structure of lipids. Their antibacterial activity and cytotoxicity were evaluated using Gram-positive and Gram-negative bacteria and eukaryotic cell lines including tumor cells. It is shown that the length of alkyl chains in the backbone is vital for the antibiofilm activities of these lipid-mimicking components. In addition to their biological activity, their surface activity and their membrane interactions are shown by film balance and quartz crystal microbalance (QCM) measurements. The structure-activity relationship indicates that the distinctive chemical structure contributes considerably to the biological activities of this novel class of lipids. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal- and additive-free photoinduced borylation of haloarenes.

PubMed

Mfuh, Adelphe M; Schneider, Brett D; Cruces, Westley; Larionov, Oleg V

2017-03-01

Boronic acids and esters have critical roles in the areas of synthetic organic chemistry, molecular sensors, materials science, drug discovery, and catalysis. Many of the current applications of boronic acids and esters require materials with very low levels of transition metal contamination. Most of the current methods for the synthesis of boronic acids, however, require transition metal catalysts and ligands that must be removed via additional purification procedures. This protocol describes a simple, metal- and additive-free method of conversion of haloarenes directly to boronic acids and esters. This photoinduced borylation protocol does not require expensive and toxic metal catalysts or ligands, and it produces innocuous and easy-to-remove by-products. Furthermore, the reaction can be carried out on multigram scales in common-grade solvents without the need for reaction mixtures to be deoxygenated. The setup and purification steps are typically accomplished within 1-3 h. The reactions can be run overnight, and the protocol can be completed within 13-16 h. Two representative procedures that are described in this protocol provide details for preparation of a boronic acid (3-cyanopheylboronic acid) and a boronic ester (1,4-benzenediboronic acid bis(pinacol)ester). We also discuss additional details of the method that will be helpful in the application of the protocol to other haloarene substrates.

Effects of 7-O substitutions on estrogenic and anti-estrogenic activities of daidzein analogues in MCF-7 breast cancer cells

USDA-ARS?s Scientific Manuscript database

Daidzein (1) is a natural estrogenic isoflavone. We report here that 1 can be transformed into an antiestrogenic ligand by simple alkyl substitutions of the 7-hydroxyl hydrogen. To test the effect of such structural modifications on the hormonal activities of the resulting compounds, a series of dai...

Shifting from Ziegler-Natta to Philips-type catalyst? A simple and safe access to reduced titanium systems for ethylene polymerization.

PubMed

Popoff, Nicolas; Espinas, Jeff; Gouré, Eric; Boyron, Olivier; Le Roux, Erwan; Basset, Jean-Marie; Gauvin, Régis M; De Mallmann, Aimery; Taoufik, Mostafa

2011-12-01

Silica-supported titanium(IV) chloride is readily reduced by Mashima and co-workers' reagent (1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene) to afford materials active in ethylene polymerisation without need of aluminum alkyl cocatalyst. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new simple phthalimide-based fluorescent probe for highly selective cysteine and bioimaging for living cells

NASA Astrophysics Data System (ADS)

Shen, Youming; Zhang, Xiangyang; Zhang, Youyu; Zhang, Chunxiang; Jin, Junling; Li, Haitao

2017-10-01

A new turn-on phthalimide fluorescent probe has designed and synthesized for sensing cysteine (Cys) based on excited state intramolecular proton transfer (ESIPT) process. It is consisted of a 3-hydroxyphthalimide derivative moiety as the fluorophore and an acrylic ester group as a recognition receptor. The acrylic ester acts as an ESIPT blocking agent. Upon addition of cystein, intermolecular nucleophilic attack of cysteine on acrylic ester releases the fluorescent 3-hydroxyphthalimide derivative, thereby enabling the ESIPT process and leading to enhancement of fluorescence. The probe displays high sensitivity, excellent selectivity and with large Stokes shift toward cysteine. The linear interval range of the fluorescence titration ranged from 0 to 1.0 × 10- 5 M and detection limit is low (6 × 10- 8 M). In addition, the probe could be used for bio-imaging in living cells.

Synthesis, spectroscopic and electrochemical characterization of secnidazole esters

NASA Astrophysics Data System (ADS)

Shahid, Hafiz Abdullah; Jahangir, Sajid; Hanif, Muddasir; Xiong, Tianrou; Muhammad, Haji; Wahid, Sana; Yousuf, Sammer; Qureshi, Naseem

2017-12-01

We report a low-cost, less toxic to environment and simple method for the esterification of secnidazole. This is first comprehensive structural characterization of novel secnidazole esters by the spectroscopic and electrochemical methods. The important EIMS fragmentation analysis showed unique contribution of heteroatom bonds explained by the fragmentation patterns. These peaks originate from the loss of single electron, loss of HCN, M-O, M-NO, M-NO2, M-C7H10N3O3, and M-C8H10N3O4. The comparison of 13C NMR predicted values with the experimental values showed that ChemBioDraw Ultra 14.0 has advantage of predicting aromatic (sp2) carbons, while MestReNova 6.1 predicts sp3 hybrid carbons more accurately. The electrochemical properties indicated an irreversible oxidation process and reversible reduction process in these ester molecules similar to the parent secnidazole.

Lyotropic liquid crystal behaviour of azelate and succinate monoester surfactants based on fragrance alcohols.

PubMed

Marchal, Frédéric; Nardello-Rataj, Véronique; Chailloux, Nelly; Aubry, Jean-Marie; Tiddy, Gordon J T

2008-05-01

Azelaic acid was used as a starting material for the preparation of new monoester surfactants based on fragrance alcohols. Sodium monocitronellyl azelate (citroC(9)Na) and sodium monomenthyl azelate (menC(9)Na) were synthesized and their aqueous phase behaviour was studied. For comparison, monoesters derived from succinic anhydride, i.e. sodium monocitronellyl succinate (citroC(4)Na) and sodium monomenthyl succinate (menC(4)Na), were also prepared as well as sodium monodecyl succinate (C(10)C(4)Na) and sodium monodecyl azelate (C(10)C(9)Na) in order to study the effect of the position of the ester function inside the hydrophobic tail and of branching and unsaturation respectively. Liquid crystal structures were examined by optical polarising microscopy and schematic partial binary phase diagrams (surfactant+water, 0-100 wt%, 10-90 degrees C) of the surfactants were established. Succinate surfactants behave as longer alkyl chain surfactants than their azelate counterparts, meaning that these last ones probably adopt a more folded conformation, with the ester function more frequently present at the micelle surface. This conformation would result in a rougher micelle surface, making it slightly less easy for micelles to pack in liquid crystalline phases. It was also shown that the tendency to adopt a more folded conformation and to form smaller micelles is ranked in this order: monomenthyl>monocitronellyl>monodecyl.

The rhizobacterium Arthrobacter agilis produces dimethylhexadecylamine, a compound that inhibits growth of phytopathogenic fungi in vitro.

PubMed

Velázquez-Becerra, Crisanto; Macías-Rodríguez, Lourdes I; López-Bucio, José; Flores-Cortez, Idolina; Santoyo, Gustavo; Hernández-Soberano, Christian; Valencia-Cantero, Eduardo

2013-12-01

Plant diseases caused by fungal pathogens such as Botrytis cinerea and the oomycete Phytophthora cinnamomi affect agricultural production worldwide. Control of these pests can be done by the use of fungicides such as captan, which may have deleterious effects on human health. This study demonstrates that the rhizobacterium Arthrobacter agilis UMCV2 produces volatile organic compounds that inhibit the growth of B. cinerea in vitro. A single compound from the volatile blends, namely dimethylhexadecylamine (DMHDA), could inhibit the growth of both B. cinerea and P. cinnamomi when supplied to the growth medium in low concentrations. DMHDA also inhibited the growth of beneficial fungi Trichoderma virens and Trichoderma atroviride but at much higher concentrations. DMHDA-related aminolipids containing 4, 8, 10, 12, and 14 carbons in the alkyl chain were tested for their inhibitory effect on the growth of the pathogens. The results show that the most active compound from those tested was dimethyldodecylamine. This effect correlates with a decrease in the number of membrane lipids present in the mycelium of the pathogen including eicosanoic acid, (Z)-9-hexadecenoic acid, methyl ester, and (Z)-9-octadecenoic acid, methyl ester. Strawberry leaflets treated with DMHDA were not injured by the compound. These data indicate that DMHDA and related compounds, which can be produced by microorganisms may effectively inhibit the proliferation of certain plant pathogens.

Fate of phthalate esters in municipal wastewater treatment plant and their environmental impact.

PubMed

Kong, Minghao; Song, Yonghui; Zhang, Yizhang; Liu, Ruixia; Wei, Jian; Zheng, Lei

2016-01-01

The fate and distribution of six phthalate esters (PAEs) in a municipal wastewater treatment plant (WWTP) employing an anaerobic/anoxic/oxic (A(2)/O) process were investigated. The process achieved relatively high removal efficiencies of PAEs in the range 55-97%. It illustrated that biotransformation and sludge-adsorption were major elimination pathways by analyzing the mass balance and flux of PAEs. About 83% of ∑PAEs was entirely removed by A(2)/O bioreactors indicating biotransformation is the dominant removal mechanism. PAEs with shorter alkyl chain length and higher water solubility were more biodegradable. Less than 6% of ∑PAEs were removed by excess sludge adsorption. The sludge-adsorption capacity of PAE depends on its hydrophobicity. The levels and fluxes of PAEs were analyzed by monitoring different sites of the receiving river of the WWTP effluent to clarify the potential impact of discharge. Daily flux of PAEs upstream and downstream of the discharging point were 113 kg·d(-1) and 205 kg·d(-1), respectively, which were higher than the effluent devotion value of 6.67 kg·d(-1). It suggested that the emissions from the WWTP appeared to be less than those from the other possible sources, such as potential untreated discharge and surface runoff. Improvement of wastewater collection efficiencies is necessary to eliminate the PAE load in the urban river.

Partition thermodynamics of ionic surfactants between phosphatidylcholine vesicle and water phases

NASA Astrophysics Data System (ADS)

Chu, Shin-Chi; Hung, Chia-Hui; Wang, Shun-Cheng; Tsao, Heng-Kwong

2003-08-01

The partition of ionic surfactants (sodium alkyl sulfate and alkyl trimethyl ammonium bromide) between phosphatidylcholine vesicles and aqueous phase is investigated by simple conductometry under different temperatures. The experimental results can be well represented by the proposed regular solution theory and the thermodynamic parameters satisfy the thermodynamic consistency. The deviation from ideal partition is manifested through the effective interaction energy between lipid and surfactant wb, which is O(kT) large. It is found that wb rises as the alkyl chain is decreased for a specified head group. This is attributed to significant mismatch of chain lengths between surfactant and lipid molecules. The partition coefficient K declines with increasing temperature. The energy barrier from bilayer to aqueous phase, Δμ/kT∝ln K, is in the range of 16-26 kJ/mol. As the alkyl chain length is decreased for a given head group, Δμ is lowered by 1.3-1.5 kJ/mol per methylene group. Two independent analyses are employed to confirm this result. Using the thermodynamic parameters determined from experiments, the internal energy, entropy, and free energy of the partition process can be derived. Partition is essentially driven by the internal energy gain. The solubilizing ability, which is represented by the maximum surfactant-lipid ratio in the bilayer, Reb also decreases in accord with the K parameter. It is because the change in temperature influences the surfactant incorporation into the bilayer more than the formation of micelles.

The translesion polymerase Rev3L in the tolerance of alkylating anticancer drugs.

PubMed

Roos, Wynand Paul; Tsaalbi-Shtylik, Anastasia; Tsaryk, Roman; Güvercin, Fatma; de Wind, Niels; Kaina, Bernd

2009-10-01

Temozolomide and fotemustine, representing methylating and chloroethylating agents, respectively, are used in the treatment of glioma and malignant melanoma. Because chemoresistance of these tumors is a common phenomenon, identification of the underlying mechanisms is needed. Here we show that Rev3L, the catalytic subunit of the translesion DNA polymerase zeta, mediates resistance to both temozolomide and fotemustine. Rev3L knockout cells are hypersensitive to both agents. It is remarkable that cells heterozygous for Rev3L showed an intermediate sensitivity. Rev3L is not involved in the tolerance of the toxic O6-methylguanine lesion. However, a possible role of Rev3L in the tolerance of O6-chloroethylguanine or the subsequently formed N1-guanine-N3-cytosine interstrand cross-link is shown. Rev3L had no influence on base excision repair (BER) of the N-alkylation lesions but is very likely to be involved in the tolerance of N-alkylations or apurinic/apyrimidinic sites originating from them. We also show that Rev3L exerts its protective effect in replicating cells and that loss of Rev3L leads to a significant increase in DNA double-strand breaks after temozolomide and fotemustine treatment. These data show that Rev3L contributes to temozolomide and fotemustine resistance, thus acting in concert with O6-methylguanine-DNA methyltransferase, BER, mismatch repair, and double-strand break repair in defense against simple alkylating anticancer drugs.

Radiation-induced changes affecting polyester based polyurethane binder

NASA Astrophysics Data System (ADS)

Pierpoint, Sujita Basi

The application of thermoplastic polyurethane elastomers as binders in the high energy explosives particularly when used in weapons presents a significantly complex and challenging problem due to the impact of the aging of this polymer on the useful service life of the explosive. In this work, the effects of radiation on the aging of the polyester based polyurethane were investigated using both electron beam and gamma irradiation at various dose rates in the presence and absence of oxygen. It was found by means of GPC that, in the presence and absence of oxygen, the poly (ester urethane) primarily undergoes cross-linking, by means of a carbon-centered secondary alkyl radical. It was also concluded that the polymer partially undergoes scission of the backbone of the main chain at C-O, N-C, and C-C bonds. Substantial changes in the conditions of irradiation and in dose levels did not affect the cross-linking and scission yields. Experiments were also performed with EPR spectroscopy for the purpose of identifying the initial carbon-centered free radicals and for studying the decay mechanisms of these radicals. It was found that the carbon-centered radical which is produced via C-C scission (primary alkyl radical) is rapidly converted to a long-lived allylic species at higher temperatures; more than 80% radicals are converted to allyl species in 2.5 hours. In the presence of oxygen, the allyl radical undergoes a fast reaction to produce a peroxyl radical; this radical decays with a 1.7 hour half-life by pseudo first-order kinetics to negligible levels in 13 hours. FTIR measurements were conducted to identify the radiation-induced changes to the functional groups in the polyester polyurethane. These measurements show an increase in carbonyl, amine and carboxylic groups as a result of reaction of H atoms with R-C-O·, ·NH-R and R-COO·. The FTIR results also demonstrate the production of the unsaturation resulting from hydrogen atom transfer during intrachain conversion of the primary alkyl radical to the allyl species, prompt trans-vinylene production in tetramethylene units, and hydrogen atom abstraction by alkyl radicals on neighboring chains. The production of unsaturation is substantiated by the EPR studies. Finally, a free radical mechanism is proposed for the production of cross-linking in polyester polyurethane.

RECOVERY OF LACTIC ACID FROM AMERICAN CRYSTAL SUGAR COMPANY WASTEWATER

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

Daniel J. Stepan; Edwin S. Olson; Richard E. Shockey

2001-04-30

This project has shown that the recovery of several valuable lactic acid products is both technically feasible and economically viable. One of the original objectives of this project was to recover lactic acid. However, the presence of a variety of indigenous bacteria in the wastewater stream and technical issues related to recovery and purification have resulted in the production of lactic acid esters. These esters could by hydrolyzed to lactic acid, but only with unacceptable product losses that would be economically prohibitive. The developed process is projected to produce approximately 200,000 lb per day of lactate esters from wastewater atmore » a single factory at costs that compete with conventional solvents. The lactate esters are good solvents for polymers and resins and could replace acetone, methyl ethyl ketone, MIBK, and other polar solvents used in the polymer industry. Because of their low volatility and viscosity-lowering properties, they will be especially useful for inks for jet printers, alkyl resins, and high-solid paints. Owing to their efficiency in dissolving salts and flux as well as oils and sealants, lactate esters can be used in cleaning circuit boards and machine and engine parts. Unlike conventional solvents, lactate esters exhibit low toxicity, are biodegradable, and are not hazardous air pollutants. Another application for lactate esters is in the production of plasticizers. Severe health problems have been attributed to widely used phthalate ester plasticizers. The U.S. Department of Agriculture showed that replacement of these with inexpensive lactate esters is feasible, owing to their superior polymer compatibility properties. A very large market is projected for polymers prepared from lactic acid. These are called polylactides and are a type of polyester. Thermoplastics of this type have a variety of uses, including moldings, fibers, films, and packaging of both manufactured goods and food products. Polylactides form tough, orientable, self-supporting thin films and have, therefore, been used for adhesives, safety glass, and finishes. If the bacterial culture produces the L-lactic acid enanatiomer form exclusively, the L-lactide prepared from this form can be used for making polymers with good fiber-forming properties. We have not currently achieved the exclusive production of L-lactate in our efforts. However, markets in films and structural shapes are available for polymers and copolymers prepared from the mixed D,L-lactide forms that result from processing the D,L-lactic acid obtained from fermentation such as that occurring naturally in sugar beet wastewater. These materials are slowly biodegraded to harmless compounds in the environment, and they burn with a clean blue flame when incinerated. These materials represent excellent opportunities for utilization of the D,L-lactic mixture produced from natural fermentation of the ACS flume water. Esters can be converted into a lactide, and the alcohol released from the ester can be recycled with no net consumption of the alcohol. Lactide intermediates could be produced locally and shipped to polymer producers elsewhere. The polymer and copolymer markets are extremely large, and the role of lactides in these markets is continuously expanding. The overall process can be readily integrated into existing factory wastewater operations. There are several environmental benefits that would be realized at the factories with incorporation of the lactate recovery process. The process reduces the organic loading to the existing wastewater treatment system that should result in enhanced operability with respect to both solids handling and treated-water quality. A higher-quality treated water will also help reduce odor levels from holding ponds. Several water reuse opportunities are probable, depending on the quality of treated water from the FT process.« less

A simple sample preparation for simultaneous determination of chloramphenicol and its succinate esters in food products using high-performance liquid chromatography/high-resolution mass spectrometry.

PubMed

Amelin, Vasiliy; Korotkov, Anton

2017-02-01

A simple method is described for the determination of chloramphenicol and its succinate esters in food products. Examination of food products using high-performance liquid chromatography/high-resolution mass spectrometry showed the presence not only of chloramphenicol but also of its succinate forms. A scheme is proposed for determining chloramphenicol and its succinate esters (calculated as chloramphenicol) in meat (beef, pork, poultry), milk, liver, kidney, eggs, fish and honey. Analytes are extracted from a 1.0 g sample with 5 ml acetonitrile. It was found that using the method of standard addition and diluting the extract with water leads to the elimination of matrix effects and also eliminates errors associated with peak splitting due to the separate elution of the differing forms of the analyte. Validation results were satisfactory, with recoveries from 85% to 111% (meat, milk, liver, kidney, eggs, fish and honey) and a relative standard deviation (RSD) lower than 13% for spiked levels of 0.3, 1.0 and 5 µg kg - 1 . The limits of detection and quantification (calculated as chloramphenicol for all forms) were 0.1 and 0.3 µg kg - 1 , respectively. The RSD of the results of the analysis was < 10%. The duration of the analysis was less than 1 h.

Preparation of novel alumina nanowire solid-phase microextraction fiber coating for ultra-selective determination of volatile esters and alcohols from complicated food samples.

PubMed

Zhang, Zhuomin; Ma, Yunjian; Wang, Qingtang; Chen, An; Pan, Zhuoyan; Li, Gongke

2013-05-17

A novel alumina nanowire (ANW) solid-phase microextraction (SPME) fiber coating was prepared by a simple and rapid anodization-chemical etching method for ultra-selective determination of volatile esters and alcohols from complicated food samples. Preparation conditions for ANW SPME fiber coating including corrosion solution concentration and corrosion time were optimized in detail for better surface morphology and higher surface area based on scanning electron microscope (SEM). Under the optimum conditions, homogeneous alumina nanowire structure of ANW SPME fiber coating was achieved with the average thickness of 20 μm around. Compared with most of commercial SPME fiber coatings, ANW SPME fiber coatings achieved the higher extraction capacity and special selectivity for volatile esters and alcohols. Finally, an efficient gas sampling technique based on ANW SPME fiber coating as the core was established and successfully applied for the ultra-selective determination of trace volatile esters and alcohols from complicated banana and fermented glutinous rice samples coupled with gas chromatography/mass spectrometry (GC/MS) detection. It was interesting that 25 esters and 2 alcohols among 30 banana volatile organic compounds (VOCs) identified and 4 esters and 7 alcohols among 13 identified VOCs of fermented glutinous rice were selectively sampled by ANW SPME fiber coatings. Furthermore, new analytical methods for the determination of some typical volatile esters and alcohols from banana and fermented glutinous rice samples at specific storage or brewing phases were developed and validated. Good recoveries for banana and fermented glutinous rice samples were achieved in range of 108-115% with relative standard deviations (RSDs) of 2.6-6.7% and 80.0-91.8% with RSDs of 0.3-1.3% (n=3), respectively. This work proposed a novel and efficient gas sampling technique of ANW SPME which was quite suitable for ultra-selectively sampling trace volatile esters and alcohols from complicated food samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Peroxyoxalate chemiluminescence enhanced by oligophenylenevinylene fluorophores in the presence of various surfactants.

PubMed

Motoyoshiya, Jiro; Takigawa, Setsuko

2014-11-01

The effect of several surfactants on peroxyoxalate chemiluminescence (PO-CL) using oligophenylenevinylene fluorophores was investigated. Among several oligophenylenevinylenes consisting of stilbene units, linearly conjugated ones, such as distyrylbenzene and distyrylstilbene, effectively enhanced PO-CL efficiency. Various effects of anionic, cationic, amphoteric and non-ionic surfactants on the CL efficiency of PO-CL were determined using three oxalates and the distyrylbenzene fluorophore. Anionic and non-ionic surfactants effectively enhanced CL efficiency, in contrast to the negative effect of cationic and amphoteric surfactants. Non-ionic surfactants were also effective in CL reactions of oxalates bearing dodecyl ester groups by the hydrophobic interaction between their alkyl chains. Considering these results, the surfactants not only increase the concentrations of water-insoluble interacting species in the hydrophobic micelle cores, but also control rapid degradation of the oxalates by alkaline hydrolysis. Copyright © 2014 John Wiley & Sons, Ltd.

Fast, Low-Cost and Non-Destructive Physico-Chemical Analysis of Virgin Olive Oils Using Near-Infrared Reflectance Spectroscopy

PubMed Central

Garrido-Varo, Ana; Sánchez, María-Teresa; De la Haba, María-José; Torres, Irina; Pérez-Marín, Dolores

2017-01-01

Near-Infrared (NIR) Spectroscopy was used for the non-destructive assessment of physico-chemical quality parameters in olive oil. At the same time, the influence of the sample presentation mode (spinning versus static cup) was evaluated using two spectrophotometers with similar optical characteristics. A total of 478 olive oil samples were used to develop calibration models, testing various spectral signal pre-treatments. The models obtained by applying MPLS regression to spectroscopic data yielded promising results for olive oil quality measurements, particularly for acidity, the peroxide index and alkyl and ethyl ester content. The results obtained indicate that this non-invasive technology can be used successfully by the olive oil sector to categorize olive oils, to detect potential fraud and to provide consumers with more reliable information. Although both sample presentation modes yielded comparable results, equations constructed with samples scanned using the spinning mode provided greater predictive capacity. PMID:29144417

High-Efficiency Polymer Solar Cells by Using Co-solvents 1-Chloronaphthalene and 1,8-Octanedithiol as Processing Additives

NASA Astrophysics Data System (ADS)

Gao, Bowen; Meng, Jing

2018-07-01

The copolymer poly-BDT-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (PC20BDTDPP) with the bulkier alkoxy on BDT and alkyl on DPP is widely used in organic photovoltaic cells as a potential donor material. Power conversion efficiency (PCE) of polymer solar cells fabricated withPC20BDTDPP as the electron donor blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the electron acceptor was improved from 4.90% to 9.10% by adding 1-5% of the co-solvents (1-chloronaphthalene and 1,8-octanedithiol) as processing additives. The enhanced PCE was attributed to optimized surface morphology and packed polymer chains leading to better phase separation morphology by the solvent additive. Furthermore, owing to its very narrow band gap, the synthesized polymer demonstrates a great potential for tandem or parallel-like solar cells.

Synthesis of geopolymer from rice husk ash for biodiesel production of Calophyllum inophyllum seed oil

NASA Astrophysics Data System (ADS)

Saputra, E.; Nugraha, M. W.; Helwani, Z.; Olivia, M.; Wang, S.

2018-04-01

In this work, geopolymer was prepared from rice husk ash (RHA) made into sodium silicate then synthesized by reacting metakaolin, NaOH, and water. The catalyst was characterized using Scanning Electron Microscopy (SEM), Energy-dispersive X-Ray analysis (EDX), Brunaeur Emmet Teller (BET), and basic strength. Then, the catalyst used for transesterification of Calophyllum inophyllum seed oil in order to produce biodiesel. The variation of process variables conducted to assess the effect on the yield of biodiesel. The highest yield obtained 87.68% biodiesel with alkyl ester content 99.29%, density 866 kg/m3, viscosity 4.13 mm2/s, the acid number of 0.42 mg-KOH/g biodiesel and the flash point 140 °C. Generally, variations of %w/w catalyst provides a dominant influence on the yield response of biodiesel. The physicochemical properties of the produced biodiesel comply with ASTM standard specifications.

Emissive sensors and devices incorporating these sensors

DOEpatents

Swager, Timothy M; Zhang, Shi-Wei

2013-02-05

The present invention generally relates to luminescent and/or optically absorbing compositions and/or precursors to those compositions, including solid films incorporating these compositions/precursors, exhibiting increased luminescent lifetimes, quantum yields, enhanced stabilities and/or amplified emissions. The present invention also relates to sensors and methods for sensing analytes through luminescent and/or optically absorbing properties of these compositions and/or precursors. Examples of analytes detectable by the invention include electrophiles, alkylating agents, thionyl halides, and phosphate ester groups including phosphoryl halides, cyanides and thioates such as those found in certain chemical warfare agents. The present invention additionally relates to devices and methods for amplifying emissions, such as those produced using the above-described compositions and/or precursors, by incorporating the composition and/or precursor within a polymer having an energy migration pathway. In some cases, the compositions and/or precursors thereof include a compound capable of undergoing a cyclization reaction.

High-Efficiency Polymer Solar Cells by Using Co-solvents 1-Chloronaphthalene and 1,8-Octanedithiol as Processing Additives

NASA Astrophysics Data System (ADS)

Gao, Bowen; Meng, Jing

2018-04-01

The copolymer poly-BDT-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (PC20BDTDPP) with the bulkier alkoxy on BDT and alkyl on DPP is widely used in organic photovoltaic cells as a potential donor material. Power conversion efficiency (PCE) of polymer solar cells fabricated withPC20BDTDPP as the electron donor blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the electron acceptor was improved from 4.90% to 9.10% by adding 1-5% of the co-solvents (1-chloronaphthalene and 1,8-octanedithiol) as processing additives. The enhanced PCE was attributed to optimized surface morphology and packed polymer chains leading to better phase separation morphology by the solvent additive. Furthermore, owing to its very narrow band gap, the synthesized polymer demonstrates a great potential for tandem or parallel-like solar cells.

Integration of CuAAC Polymerization and Controlled Radical Polymerization into Electron Transfer Mediated "Click-Radical" Concurrent Polymerization.

PubMed

Xue, Wentao; Wang, Jie; Wen, Ming; Chen, Gaojian; Zhang, Weidong

2017-03-01

The successful chain-growth copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization employing Cu(0)/pentamethyldiethylenetriamine (PMDETA) and alkyl halide as catalyst is first investigated by a combination of nuclear magnetic resonance, gel-permeation chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In addition, the electron transfer mediated "click-radical" concurrent polymerization utilizing Cu(0)/PMDETA as catalyst is successfully employed to generate well-defined copolymers, where controlled CuAAC polymerization of clickable ester monomer is progressed in the main chain acting as the polymer backbone, the controlled radical polymerization (CRP) of acrylic monomer is carried out in the side chain. Furthermore, it is found that there is strong collaborative effect and compatibility between CRP and CuAAC polymerization to improve the controllability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biodiesel production with immobilized lipase: A review.

PubMed

Tan, Tianwei; Lu, Jike; Nie, Kaili; Deng, Li; Wang, Fang

2010-01-01

Fatty acid alkyl esters, also called biodiesel, are environmentally friendly and show great potential as an alternative liquid fuel. Biodiesel is produced by transesterification of oils or fats with chemical catalysts or lipase. Immobilized lipase as the biocatalyst draws high attention because that process is "greener". This article reviews the current status of biodiesel production with immobilized lipase, including various lipases, immobilization methods, various feedstocks, lipase inactivation caused by short chain alcohols and large scale industrialization. Adsorption is still the most widely employed method for lipase immobilization. There are two kinds of lipase used most frequently especially for large scale industrialization. One is Candida antartica lipase immobilized on acrylic resin, and the other is Candida sp. 99-125 lipase immobilized on inexpensive textile membranes. However, to further reduce the cost of biodiesel production, new immobilization techniques with higher activity and stability still need to be explored. Copyright 2010 Elsevier Inc. All rights reserved.