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Sample records for carboxylation

  1. Free carboxylate stretching modes

    NARCIS (Netherlands)

    Oomens, J.; Steill, J. D.

    2008-01-01

    We report the first IR spectroscopic observation of carboxylate stretching modes in free space, i.e., in the complete absence of solvent or counterions. Gas-phase spectra of a series of benzoate anions have been recorded and compared to condensed-phase spectra, revealing the profound influence of th

  2. 1-Azaniumylcyclobutane-1-carboxylate monohydrate

    Directory of Open Access Journals (Sweden)

    Ray J. Butcher

    2014-02-01

    Full Text Available In the title compound, C5H9NO2·H2O, the amino acid is in the usual zwitterionic form involving the α-carboxylate group. The cyclobutane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7 and 0.118 (7. In the crystal, N—H...O and O—H...O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3+ and donor (through a single carboxylate O from two different aminocyclobutane carboxylate moities], resulting in a two-dimensional layered structure lying parallel to (100.

  3. Carboxyl group reactivity in actin

    International Nuclear Information System (INIS)

    While earlier work showed that the carboxyl groups of proteins could be quantitatively coupled to amino groups at pH 4.75 in the presence of EDC and a denaturing agent, the work presented here indicates that under milder conditions the modification of sidechain carboxyls is limited and somewhat specific. Most of the incorporated glycine ethyl ester (GEE) is apparently bound to five carboxyls. The total GEE incorporated was 3 to 4 moles/mole of protein as measured by an increase in Gly upon acid hydrolysis and amino acid analysis, as well as total radioactivity. 3.55 residues were found in peptides, 2.75 bound to residues 1 to 4, and 0.8 bound to Gly-100. 9 refs., 2 figs., 2 tabs

  4. Complicated Composting: Persistent Pyridine Carboxylic Acid Herbicides

    OpenAIRE

    Reimer, Julie

    2013-01-01

    This paper reviews pyridine carboxylic acid herbicide impacts on compost. Pyridine carboxylic acid herbicides are not completely broken down during grass growth, harvest and drying of hay, in the digestive tract of livestock, or during composting. These herbicides are a popular choice for broadleaf weed control because of this persistence: they remain effective for months or years. Pyridine carboxylic acids are also more effective than the common herbicide 2, 4-dichlorophenoxyacetic acid and ...

  5. Carboxylic acids as substrates in homogeneous catalysis.

    Science.gov (United States)

    Goossen, Lukas J; Rodríguez, Nuria; Goossen, Käthe

    2008-01-01

    In organic molecules carboxylic acid groups are among the most common functionalities. Activated derivatives of carboxylic acids have long served as versatile connection points in derivatizations and in the construction of carbon frameworks. In more recent years numerous catalytic transformations have been discovered which have made it possible for carboxylic acids to be used as building blocks without the need for additional activation steps. A large number of different product classes have become accessible from this single functionality along multifaceted reaction pathways. The frontispiece illustrates an important reason for this: In the catalytic cycles carbon monoxide gas can be released from acyl metal complexes, and gaseous carbon dioxide from carboxylate complexes, with different organometallic species being formed in each case. Thus, carboxylic acids can be used as synthetic equivalents of acyl, aryl, or alkyl halides, as well as organometallic reagents. This review provides an overview of interesting catalytic transformations of carboxylic acids and a number of derivatives accessible from them in situ. It serves to provide an invitation to complement, refine, and use these new methods in organic synthesis.

  6. Understanding biocatalyst inhibition by carboxylic acids

    Directory of Open Access Journals (Sweden)

    Laura R Jarboe

    2013-09-01

    Full Text Available Carboxylic acids are an attractive biorenewable chemical in terms of their flexibility and usage as precursors for a variety of industrial chemicals. It has been demonstrated that such carboxylic acids can be fermentatively produced using engineered microbes, such as Escherichia coli and Saccharomyces cerevisiae. However, like many other attractive biorenewable fuels and chemicals, carboxylic acids become inhibitory to these microbes at concentrations below the desired yield and titer. In fact, their potency as microbial inhibitors is highlighted by the fact that many of these carboxylic acids are routinely used as food preservatives. This review highlights the current knowledge regarding the impact that saturated, straight-chain carboxylic acids, such as hexanoic, octanoic, decanoic and lauric acids can have on E. coli and S. cerevisiae, with the goal of identifying metabolic engineering strategies to increase robustness. Key effects of these carboxylic acids include damage to the cell membrane and a decrease of the microbial internal pH. Certain changes in cell membrane properties, such as composition, fluidity, integrity and hydrophobicity, and intracellular pH are often associated with increased tolerance. The availability of appropriate exporters, such as Pdr12, can also increase tolerance. The effect on metabolic processes, such as maintaining appropriate respiratory function, regulation of Lrp activity and inhibition of production of key metabolites such as methionine, are also considered. Understanding the mechanisms of biocatalyst inhibition by these desirable products can aid in the engineering of robust strains with improved industrial performance.

  7. EPOXY RESINS TOUGHENED WITH CARBOXYL TERMINATED POLYETHERS

    Institute of Scientific and Technical Information of China (English)

    YU Yunchao; LI Yiming

    1983-01-01

    Carboxyl terminated polyethers, the adducts of hydroxyl terminated polytetrahydrofuran and maleic anhydride, were used as toughener for epoxy resins. The morphology of the toughened resins was investigated by means of turbidity measurement, dynamic mechanical testing and scanning electron microscope observation. It turned out that the molecular weight and the carboxyl content of the polyether and the cure conditions are important factors, which affect the particle size of the polyether-rich domains and, in turn, the mechanical properties of the cured resin. Carboxyl terminated polytetrahydrofurans have a low glass transition temperature, and in appropriate amount they do not affect the thermal resistance of the resin. These advantages make them preferable as toughener for epoxy resins.

  8. Novel Polymers with Carboxylic Acid Loading

    DEFF Research Database (Denmark)

    Thomsen, Anders Daugaard; Malmström, Eva; Hvilsted, Søren

    2006-01-01

    Click chemistry has been used to prepare a range of novel polymers with pendant carboxylic acid side groups. Four azido carboxylic acids, either mono- or difunctional and aliphatic or aromatic, have been prepared and thoroughly characterized. Extensive model reactions with 1-ethyl-4-hydroxybenzene......, the simplest model for poly(4-hydroxystyrene), and the four azido carboxylic acids have been conducted to establish the proper reaction conditions and provide an analytical frame for the corresponding polymers. Poly(4-hydroxystyrene) moieties in three different polymers—poly(4-hydroxystyrene), poly(4...... the polymers in general exhibit [when poly(4-hydroxystyrene) is a substantial part] significant changes in the glass-transition temperature from the polar poly(4-hydroxystyrene) (120–130 °C) to the much less polar alkyne polymers (46–60 °C). A direct correlation between the nature of the pendant groups...

  9. Hygroscopic Characteristics of Alkylaminium Carboxylate Aerosols.

    Science.gov (United States)

    Gomez-Hernandez, Mario; McKeown, Megan; Secrest, Jeremiah; Marrero-Ortiz, Wilmarie; Lavi, Avi; Rudich, Yinon; Collins, Don R; Zhang, Renyi

    2016-03-01

    The hygroscopic growth factor (HGF) and cloud condensation nuclei (CCN) activity for a series of alkylaminium carboxylate aerosols have been measured using a hygroscopicity tandem differential mobility analyzer coupled to a condensation particle counter and a CCN counter. The particles, consisting of the mixtures of mono- (acetic, propanoic, p-toluic, and cis-pinonic acid) and dicarboxylic (oxalic, succinic, malic, adipic, and azelaic acid) acid with alkylamine (mono-, di-, and trimethylamines), represent those commonly found under diverse environmental conditions. The hygroscopicity parameter (κ) of the alkylaminium carboxylate aerosols was derived from the HGF and CCN results and theoretically calculated. The HGF at 90% RH is in the range of 1.3 to 1.8 for alkylaminium monocarboxylates and 1.1 to 2.2 for alkylaminium dicarboxylates, dependent on the molecular functionality (i.e., the carboxylic or OH functional group in organic acids and methyl substitution in alkylamines). The κ value for all alkylaminium carboxylates is in the range of 0.06-1.37 derived from the HGF measurements at 90% RH, 0.05-0.49 derived from the CCN measurements, and 0.22-0.66 theoretically calculated. The measured hygroscopicity of the alkylaminium carboxylates increases with decreasing acid to base ratio. The deliquescence point is apparent for several of the alkylaminium dicarboxylates but not for the alkylaminium monocarboxylates. Our results reveal that alkylaminium carboxylate aerosols exhibit distinct hygroscopic and deliquescent characteristics that are dependent on their molecular functionality, hence regulating their impacts on human health, air quality, and direct and indirect radiative forcing on climate. PMID:26794419

  10. Mass spectrometric behaviour of carboxylated polyethylene glycols and carboxylated octylphenol ethoxylates.

    Science.gov (United States)

    Frańska, Magdalena; Zgoła, Agnieszka; Rychłowska, Joanna; Szymański, Andrzej; Łukaszewski, Zenon; Frański, Rafał

    2003-01-01

    Mass spectrometric behaviour of mono- and di-carboxylated polyethylene glycols (PEGCs and CPEGCs) and carboxylated octylphenol ethoxylates (OPECs) are discussed. The tendency for ionisation (deprotonation, protonation and cationisation by alkali metal cations) of carboxylated PEGs was compared with that of non-carboxylated correspondents by using both secondary ion mass spectrometry (SIMS) and electrospray ionisation (ESI). The fragmentation of the PEGCs and CPEGCs is discussed and also compared with their neutral correspondents, PEGs. The B/E mass spectra were recorded, using secondary ion mass spectrometry as a method for generation, for deprotonated and protonated molecules and molecules cationised by alkali metal cations. The fragmentation behaviour of PEGs is found to be different from that of CPEGCs, The presence of carboxylic groups may be confirmed not only by the determination of molecular weights of the ethoxylates studied, but also on the basis of the fragment ions formed. The metastable decomposition of the [OPEC-H](-) ions proceed through the cleavage of the bond between the octylphenol moiety and the ethoxylene chain leading to the octylphenoxy anions. It permits determination of the mass of the hydrophobic moiety of the studied carboxylated alkylphenol ethoxylate. ESI mass spectra recorded in the negative ion mode were found to be more suitable for the determination of the average molecular weight of carboxylated ethoxylates than SI mass spectra. PMID:12939494

  11. Nitric Acid Dehydration Using Perfluoro Carboxylate and Mixed Sulfonate/Carboxylate Membranes

    Energy Technology Data Exchange (ETDEWEB)

    R.L. Ames

    2004-09-01

    Perfluoro ionomer membranes are tetrafluoro ethylene-based materials with microheterogeneous structures consisting of a hydrophobic polymer backbone and a hydrophilic side-chain cluster region. Due to the ionomer cluster morphology, these films exhibit unique transport properties. Recent investigations with perfluoro sulfonate and perfluoro sulfonate/carboxylate composite polymers have demonstrated their value in the dehydration of nitric acid and they show potential as an alternative to conventional, energy intensive unit operations in the concentration of acid feeds. As a result, investigations were conducted to determine the feasibility of using pure perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films for the dehydration of nitric acid because of the speculation of improved water selectivity of the carboxylate pendant chain. During the first phase of these investigations the effort was focused on generating a thin, solution cast perfluoro carboxylate ionomer film, to evaluate the general, chemical and physical characteristics of the polymer, and to assess the material's aqueous transport performance (flux and nitrate separation efficiencies) in pervaporation and high-pressure environments. Results demonstrated that generating robust solution-cast films was difficult yet a number of membranes survived high trans-membrane pressures up to 700 psig. General characterization of the solution cast product showed reduced ion exchange capacities when compared with thicker, ''as received'' perfluoro carboxylate and similar sulfonate films. Small angle x-ray scattering analysis results suggested that the solution cast carboxylate films contained a small fraction of sulfonate terminated side-chains. Aqueous transport experimentation showed that permeate fluxes for both pure water and nitric acid were approximately two orders of magnitude smaller for the carboxylate solution cast membranes when compared to their sulfonate

  12. Methyl 3-(Quinolin-2-ylindolizine-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Roumaissa Belguedj

    2015-12-01

    Full Text Available A novel compound, methyl 3-(quinolin-2-ylindolizine-1-carboxylate (2 has been synthesized by cycloaddition reaction of 1-(quinolin-2-ylmethylpyridinium ylide (1 with methyl propiolate in presence of sodium hydride in THF. The structure of this compound was established by IR, 1H-NMR, 13C-NMR and MS data

  13. Cationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids

    Science.gov (United States)

    Naruto, Masayuki; Saito, Susumu

    2015-01-01

    Carboxylic acids are ubiquitous in bio-renewable and petrochemical sources of carbon. Hydrogenation of carboxylic acids to yield alcohols produces water as the only byproduct, and thus represents a possible next generation, sustainable method for the production of these alternative energy carriers/platform chemicals on a large scale. Reported herein are molecular insights into cationic mononuclear ruthenium carboxylates ([Ru(OCOR)]+) as prototypical catalysts for the hydrogenation of carboxylic acids. The substrate-derived coordinated carboxylate was found to function initially as a proton acceptor for the heterolytic cleavage of dihydrogen, and subsequently also as an acceptor for the hydride from [Ru–H]+, which was generated in the first step (self-induced catalysis). The hydrogenation proceeded selectively and at high levels of functional group tolerance, a feature that is challenging to achieve with existing heterogeneous/homogeneous catalyst systems. These fundamental insights are expected to significantly benefit the future development of metal carboxylate-catalysed hydrogenation processes of bio-renewable resources. PMID:26314266

  14. Carboxylated Polyurethanes Containing Hyperbranched Polyester Soft Segments

    Directory of Open Access Journals (Sweden)

    Žigon, M.

    2006-09-01

    Full Text Available hyperbranched polyester soft segments (HB PU with functional carboxylic groups in order to enable the preparation of stable HB PU dispersions. Carboxylated hyperbranched polyurethanes were synthesized using a hyperbranched polyester based on 2,2-bis(methylolpropionic acid of the fourth pseudo-generation (Boltorn H40 and hexamethylene (HDI or isophorone diisocyanate (IPDI. The reactivity of hyperbranched polyester with HDI was lower than expected, possibly due to the presence of less reactive hydroxyl groups in the linear repeat units. A gel was formed at mole ratios rNCO/OH = 1:2 or 1:4. The synthesis of HB PU was performed with partly esterified hyperbranched polyester with lowered hydroxyl functionality. The carboxyl groups were incorporated in the HB PU backbone by reaction of residual hydroxyl groups with cis-1,2-cyclohexanedicarboxylic anhydride. HB PU aqueous dispersions were stable at least for two months, although their films were brittle. The tensile strength and Young's modulus of blends of linear and HB PU decreased with increasing content of HB PU whereas elongation at break remained nearly constant, which was explained in terms of looser chain packing due to more open tree-like hyperbranched structures.

  15. Methyl (Sp-2-(diphenylphosphinoferrocene-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Petr Štěpnička

    2009-10-01

    Full Text Available The title compound, [Fe(C5H5(C19H16O2P], obtained serendipitously during recrystallization of 1-hydroxybenzotriazolyl (Sp-2-(diphenylphosphinoferrocene-1-carboxylate from methanol, crystallizes in the chiral space group P212121. Its crystal structure not only confirms the anticipated absolute configuration but also establishes a rather regular geometry for the ferrocene unit, devoid of any significant deformation due to the attached substituents. In the crystal, symmetry-related molecules are linked via weak C—H...O interactions.

  16. Metal extraction by amides of carboxylic acids

    International Nuclear Information System (INIS)

    Extraction ability of various amides was studied. Data on extraction of rare earths, vanadium, molybdenum, rhenium, uranium, niobium, tantalum by N,N-dibutyl-amides of acetic, nonanic acids and fatly synthetic acids of C7-C9 fractions are presented. Effect of salting-out agents, inorganic acid concentrations on extraction process was studied. Potential ability of using amides of carboxylic acids for extractional concentration of rare earths as well as for recovery and separation of iron, rhenium, vanadium, molybdenum, uranium, niobium, and tantalum was shown

  17. Carboxylation and Decarboxylation of Aluminum Oxide Nanoparticles Using Bifunctional Carboxylic Acids and Octylamine

    Directory of Open Access Journals (Sweden)

    Shirin Alexander

    2016-01-01

    Full Text Available The carboxylation of alumina nanoparticles (NPs, with bifunctional carboxylic acids, provides molecular anchors that are used for building more complexed structures via either physisorption or chemisorption. Colloidal suspensions of the NPs may be prepared by covalently bonding a series of carboxylic acids with secondary functional groups (HO2C-R-X to the surface of the NPs: lysine (X = NH2, p-hydroxybenzoic acid (X = OH, fumaric acid (X = CO2H, and 4-formylbenzoic acid (X = C(OH. Subsequent reaction with octylamine at either 25°C or 70°C was investigated. Fourier transform IR-attenuated reflectance spectroscopy (FTIR-ATR, thermogravimetric analysis (TGA, and scanning electron microscopy (SEM along with energy dispersive X-ray (EDX analysis were used to characterize the bifunctionalized monolayers and/or multilayer corona surrounding the alumina NPs and investigate the reaction mechanism of octylamine with the functional groups (X of the NPs. Except for the fumaric functionalized NPs, addition of octylamine to the functionalized NPs leads to removal of excess carboxylic acid corona from the surface via an amide formation. The extent of the multilayer is dependent on the strength of the acid⋯acid interaction.

  18. Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties

    OpenAIRE

    H. F. Xie; Wang, Y. T.; Wang, C. S.; H. Y. Yin; Wang, L.L.; R. S. Cheng

    2012-01-01

    Carboxyl-modified multi-walled carbon nanotubes (MWCNT–COOHs) as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA) toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN). The carboxyl functional carbon nanotubes were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. Furthermore, cure kinetics, glass transition temperature (Tg), mechanical properties, thermal stability and morphology of DGEBA/CTBN/MWCNT–COOH...

  19. Carboxylates and the uptake of ammonium by excised maize roots

    NARCIS (Netherlands)

    Breteler, H.

    1975-01-01

    The effect of carboxylates (organic acid anions) on NH 4 uptake was studied by changing the carboxylate level of roots prior to uptake experi ments. Succinate was the most effective stimulator of ammonium uptake. The oxocarboxylates (α-oxoglutarate, oxaloacetate and

  20. Noncovalent catch and release of carboxylates in water.

    Science.gov (United States)

    Beck, Christie L; Winter, Arthur H

    2014-04-01

    Association constants of a bis-(acetylguanidinium)ferrocene dication to various (di)carboxylates were determined through UV-vis titrations. Association constant values greater than 10(4) M(-1) were determined for both phthalate and maleate carboxylates to the bis-(acetylguanidinium)ferrocene salt in pure water. Density functional theory computations of the binding enthalpy of the rigid carboxylates for these complexes agree well with the experimentally determined association constants. Catch and release competitive binding experiments were done by NMR for the cation-carboxylate ion-pair complexes with cucurbit[7]uril, and they show dissociation of the ion-pair complex upon addition of cucurbit[7]uril and release of the free (di)carboxylate.

  1. Critical Design Features of Phenyl Carboxylate-Containing Polymer Microbicides

    OpenAIRE

    Rando, Robert F.; Obara, Sakae; Osterling, Mark C.; Mankowski, Marie; Miller, Shendra R.; Ferguson, Mary L.; Krebs, Fred C.; Wigdahl, Brian; Labib, Mohamed; Kokubo, Hiroyasu

    2006-01-01

    Recent studies of cellulose-based polymers substituted with carboxylic acids like cellulose acetate phthalate (CAP) have demonstrated the utility of using carboxylic acid groups instead of the more common sulfate or sulfonate moieties. However, the pKa of the free carboxylic acid group is very important and needs careful selection. In a polymer like CAP the pKa is approximately 5.28. This means that under the low pH conditions found in the vaginal lumen, CAP would be only minimally soluble an...

  2. Applications of Carboxylic Acid Reductases in Oleaginous Microbes

    Energy Technology Data Exchange (ETDEWEB)

    Resch, Michael G.; Linger, Jeffrey; McGeehan, John; Tyo, Keith; Beckham, Gregg

    2016-04-24

    Carboxylic acid reductases (CARs) are recently emerging reductive enzymes for the direct production of aldehydes from biologically-produced carboxylic acids. Recent work has demonstrated that these powerful enzymes are able to reduce a very broad range of volatile- to long-chain fatty acids as well as aromatic acids. Here, we express four CAR enzymes from different fungal origins to test their activity against fatty acids commonly produced in oleaginous microbes. These in vitro results will inform metabolic engineering strategies to conduct mild biological reduction of carboxylic acids in situ, which is conventionally done via hydrotreating catalysis at high temperatures and hydrogen pressures.

  3. Ethyl coumarin-3-carboxylate: synthesis and chemical properties

    Directory of Open Access Journals (Sweden)

    Bakr F. Abdel-Wahab

    2014-03-01

    Full Text Available Ethyl coumarin-3-carboxylate occupies an important position in the organic synthesis and is used in production of biologically active compounds. Thus, the data published over the last few years on the methods of synthesis and chemical properties of ethyl coumarin-3-carboxylate are reviewed here for the first time. The reactions were classified as coumarin ring reactions and ester group reactions, and some of these reactions have been applied successfully to the synthesis of biologically and industrially important compounds.

  4. The essential activated carboxyl group of inorganic pyrophosphatase.

    Science.gov (United States)

    Avaeva, S M; Bakuleva, N P; Baratova, L A; Nazarova, T I; Fink, N Y

    1977-05-12

    1. A carboxyl group of high reactivity has been found in inorganic pyrophosphatase (pyrophosphate phosphohydrolase, EC 3.6.1.1) from yeast. This group interacts with agents which react neither with carboxyl groups of low molecular weight compounds nor with other carboxyl groups of the protein. 2. The reaction of this activated carboxyl group with inorganic phosphate, hydroxylamine, N-methyl- and O-methylhydroxylamines, and glycine methyl ester has been studied. 3. Homoserine and homoserine lactone were found in the hydrolyzate of phosphorylated and NaBH4-reduced pyrophosphatase, indicating that an aspartyl residue is phosphorylated. 4. Hydroxylamine and other nucleophilic agents cause inactivation of pyrophosphatase as a result of interaction with a carboxyl group. Both diaminobutyric and diaminopropionic acids were seen in the acid hydrolyzate of the protein treated with hydroxylamine and subjected to rearrangement in the presence of carbodiimide. 5. The ways in which the activation of a carboxyl group in the enzyme is achieved and the presumed mechanism of action of inorganic pyrophosphatase are discussed. PMID:16652

  5. Selective esterification of non-conjugated carboxylic acids in the presence of conjugated or aromatic carboxylic acids over active carbon supported methanesulfonic acid

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Non-conjugated carboxylic acids are selectively esterified in good yields in the presence of conjugated or aromatic carboxylic acids by stirring over active carbon supported methanesulfonic acid in di-chloromethane at room temperature.

  6. Kinetic and Thermodynamic Parameters for Uncatalyzed Esterification of Carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Kehinde S. Bankole

    2014-06-01

    Full Text Available A fundamental study on uncatalyzed esterification of various biomass-derived aliphatic carboxylic acids with stoichiometric amount of ethanol has been investigated in an isothermal batch reactor, with the objective to convert carboxylic acids to corresponding ethyl esters and to determine both the kinetic and thermodynamic parameters. The effects of temperature on the conversion of carboxylic acid, kinetic and thermodynamic parameters have been investigated. Temperature was found to have significant effect on the rate of reaction and conversion of carboxylic acid. A simple second order reversible kinetic model was developed to determine the kinetic and thermodynamic parameters. The thermodynamic and kinetic parameters varied for uncatalyzed esterification reaction of both short-chain and long-chain carboxylic acids considered. The predicted data from the kinetic model were correlated with experimental data and the two sets of data agreed reasonably well for the uncatalyzed esterification systems. It was observed that the Van’t Hoff plot for uncatalyzed esterification of linoleic acid was non-linear curve, whereas for the Arrhenius and Eyring plots, they were linear. Additional experiments to assess the catalytic and corrosion effects of several metallic substances revealed Inconel 625 alloy, nickel wire and stainless steel materials were susceptible to corrosion problem with uncatalyzed esterification reaction at elevated reaction temperatures. However, tantalum and grade-5 titanium materials were corrosion resistance metals, suitable for similar reaction conditions and this can encourage the design of a flow reactor system. Although, uncatalyzed esterification of carboxylic acids at elevated reaction temperature is still at laboratory scale. It is our hope that the estimated kinetic and thermodynamic parameters would be the guiding tools for reactor scale-up, thus providing a new perspective into the conversion of biomass-derived carboxylic

  7. Pyrazine Carboxylic Acid Derivatives of Dichlorobis(Cyclopentadienyltitanium(IV

    Directory of Open Access Journals (Sweden)

    Satish Chandra Dixit

    2012-07-01

    Full Text Available Reactions of dichlorobis(cyclopentadienyltitanium(IV with pyrazine carboxylic acids viz. 2-pyrazine carboxylic acid (2-PzCH, 5-methyl-2-pyrazine carboxylic acid (MPzCH and 2,3-pyrazine dicarboxylic acid (2,3-PzDCH2 were carried out in different stoichiometric ratios. Complexes of the type Cp2Ti(2-PzCCl , Cp2Ti(2-PzC2 ,Cp2Ti(MPzCCl,Cp2Ti(MPzC2, Cp2Ti(2,3-PzDCHCl and Cp2Ti(2,3-PzDCH2 were obtained. These newly synthesized complexes were characterized on the basis of elemental analyses, electrical conductance, magnetic moment and spectral data.

  8. Pyrazine Carboxylic Acid Derivatives of Dichlorobis(Cyclopentadienyl)titanium(IV)

    OpenAIRE

    Satish Chandra Dixit; Rohit Kumar Singh

    2012-01-01

    Reactions of dichlorobis(cyclopentadienyl)titanium(IV) with pyrazine carboxylic acids viz. 2-pyrazine carboxylic acid (2-PzCH), 5-methyl-2-pyrazine carboxylic acid (MPzCH) and 2,3-pyrazine dicarboxylic acid (2,3-PzDCH2) were carried out in different stoichiometric ratios. Complexes of the type Cp2Ti(2-PzC)Cl , Cp2Ti(2-PzC)2 ,Cp2Ti(MPzC)Cl,Cp2Ti(MPzC)2, Cp2Ti(2,3-PzDCH)Cl and Cp2Ti(2,3-PzDCH)2 were obtained. These newly synthesized complexes were characterized on the basis of elemental analyse...

  9. Biotin Carboxyl Carrier Protein in Barley Chloroplast Membranes

    DEFF Research Database (Denmark)

    Kannangara, C. G.; Jense, C J

    1975-01-01

    Biotin localized in barley chloroplast lamellae is covalently bound to a single protein with an approximate molecular weight of 21000. It contains one mole of biotin per mole of protein and functions as a carboxyl carrier in the acetyl-CoA carboxylase reaction. The protein was obtained by solubil......Biotin localized in barley chloroplast lamellae is covalently bound to a single protein with an approximate molecular weight of 21000. It contains one mole of biotin per mole of protein and functions as a carboxyl carrier in the acetyl-CoA carboxylase reaction. The protein was obtained...

  10. Palladium-Catalyzed Carboxylation of Activated Vinylcyclopropanes with CO2.

    Science.gov (United States)

    Mita, Tsuyoshi; Tanaka, Hiroyuki; Higuchi, Yuki; Sato, Yoshihiro

    2016-06-01

    By using a palladium catalyst with ZnEt2, activated vinylcyclopropanes were successfully converted into the corresponding β,γ-unsaturated carboxylic acids in high yields under a CO2 atmosphere (1 atm). The intermediate in this reaction is thought to be a nucleophilic η(1)-allylethylpalladium species, which would be produced from π-allylpalladium and ZnEt2 (umpolung reactivity).

  11. Cyclodextrin derivatives with cyanohydrin and carboxylate groups as artificial glycosidases

    DEFF Research Database (Denmark)

    Bols, Mikael; Ortega-Caballero, Fernando

    2006-01-01

    Two cyclodextrin derivatives (1 and 2) were prepared in an attempt to create glycosidase mimics with a general acid catalyst and a nucleophilic carboxylate group. The catalysts 1 and 2 were found to catalyse the hydrolysis of 4-nitrophenyl beta-D-glucopyranoside at pH 8.0, but rapidly underwent...

  12. Conformation of some carboxylic acids and their derivatives

    NARCIS (Netherlands)

    Kanters, J.A.; Kroon, Jan; Peerdeman, A.F.; Schoone, J.C.

    1967-01-01

    The conformation in the crystalline state of some aliphatic carboxylic acids and their derivatives has been analysed. This analysis, based upon the results of structure determinations by means of X-ray diffraction, seems to support the concept that the conformation of a molecule is governed chiefly

  13. Synthon preferences in cocrystals of cis-carboxamides:carboxylic acids

    NARCIS (Netherlands)

    A.M. Moragues-Bartolome; W. Jones; A.J. Cruz-Cabeza

    2012-01-01

    We study synthon preferences in cocrystals of cis-carboxamides with carboxylic acids using a combination of database analyses, cocrystallisation experiments and theoretical calculations. We classify the cis-carboxamides into three families: primary amides, cyclic amides (lactams) and cyclic imides.

  14. Carboxylic ester hydrolases in mitochondria from rat skeletal muscle

    DEFF Research Database (Denmark)

    Kirkeby, S; Moe, D; Zelander, T

    1990-01-01

    A mitochondrial pellet, prepared from rat skeletal muscle, contained a number of carboxylic ester hydrolase isoenzymes. The esterases which split alpha-naphthyl acetate were organophosphate sensitive, whereas two out of three indoxyl acetate hydrolysing enzymes were resistant to both organophosph...

  15. Light dependence of carboxylation capacity for C3 photosynthesis models

    Science.gov (United States)

    Photosynthesis at high light is often modelled by assuming limitation by the maximum capacity of Rubisco carboxylation at low carbon dioxide concentrations, by electron transport capacity at higher concentrations, and sometimes by triose-phosphate utilization rate at the highest concentrations. Pho...

  16. Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

    Science.gov (United States)

    Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

    2011-02-01

    Clouds are multiphasic atmospheric systems in which the dissolved organic compounds, dominated by carboxylic acids, are subject to multiple chemical transformations in the aqueous phase. Among them, solar radiation, by generating hydroxyl radicals (•OH), is considered as the main catalyzer of the reactivity of organic species in clouds. We investigated to which extent the active biomass existing in cloud water represents an alternative route to the chemical reactivity of carboxylic acids. Pure cultures of seventeen bacterial strains (Arthrobacter, Bacillus, Clavibacter, Frigoribacterium, Pseudomonas, Sphingomonas and Rhodococcus), previously isolated from cloud water and representative of the viable community of clouds were first individually incubated in two artificial bulk cloud water solutions at 17 °C and 5 °C. These solutions mimicked the chemical composition of cloud water from "marine" and "continental" air masses, and contained the major carboxylic acids existing in the cloud water (i.e. acetate, formate, succinate and oxalate). The concentrations of these carboxylic compounds were monitored over time and biodegradation rates were determined. In average, they ranged from 2 ×10-19 for succinate to 1 × 10-18 mol cell-1 s-1 for formate at 17 °C and from 4 × 10-20 for succinate to 6 × 10-19 mol cell-1 s-1 for formate at 5 °C, with no significant difference between "marine" and "continental" media. In parallel, irradiation experiments were also conducted in these two artificial media to compare biodegradation and photodegradation of carboxylic compounds. To complete this comparison, the photodegradation rates of carboxylic acids by •OH radicals were calculated from literature data. Inferred estimations suggested a significant participation of microbes to the transformation of carboxylic acids in cloud water, particularly for acetate and succinate (up to 90%). Furthermore, a natural cloud water sample was incubated (including its indigenous microflora

  17. Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

    Directory of Open Access Journals (Sweden)

    M. Vaïtilingom

    2011-02-01

    Full Text Available Clouds are multiphasic atmospheric systems in which the dissolved organic compounds, dominated by carboxylic acids, are subject to multiple chemical transformations in the aqueous phase. Among them, solar radiation, by generating hydroxyl radicals (OH, is considered as the main catalyzer of the reactivity of organic species in clouds. We investigated to which extent the active biomass existing in cloud water represents an alternative route to the chemical reactivity of carboxylic acids. Pure cultures of seventeen bacterial strains (Arthrobacter, Bacillus, Clavibacter, Frigoribacterium, Pseudomonas, Sphingomonas and Rhodococcus, previously isolated from cloud water and representative of the viable community of clouds were first individually incubated in two artificial bulk cloud water solutions at 17 °C and 5 °C. These solutions mimicked the chemical composition of cloud water from "marine" and "continental" air masses, and contained the major carboxylic acids existing in the cloud water (i.e. acetate, formate, succinate and oxalate. The concentrations of these carboxylic compounds were monitored over time and biodegradation rates were determined. In average, they ranged from 2 ×10−19 for succinate to 1 × 10−18 mol cell−1 s−1 for formate at 17 °C and from 4 × 10−20 for succinate to 6 × 10−19 mol cell−1 s−1 for formate at 5 °C, with no significant difference between "marine" and "continental" media. In parallel, irradiation experiments were also conducted in these two artificial media to compare biodegradation and photodegradation of carboxylic compounds. To complete this comparison, the photodegradation rates of carboxylic acids by OH radicals were calculated from literature data. Inferred estimations suggested a significant participation of microbes to the transformation of carboxylic acids in cloud water

  18. Highly Regioselective Palladium-Catalyzed Carboxylation of Allylic Alcohols with CO2.

    Science.gov (United States)

    Mita, Tsuyoshi; Higuchi, Yuki; Sato, Yoshihiro

    2015-11-01

    Various allylic alcohols were carboxylated in the presence of a catalytic amount of PdCl2 and PPh3 using ZnEt2 as a stoichiometric transmetalation agent under a CO2 atmosphere (1 atm). This carboxylation proceeded in a highly regioselective manner to afford branched carboxylic acids predominantly. The β,γ-unsaturated carboxylic acid thus obtained was successfully converted into an optically active γ-butyrolactone, a known intermediate of (R)-baclofen.

  19. CARBOXYLIC ACIDS OF HERB OF THYMUS CRETACEUS KLOK. ET SCHOST

    Directory of Open Access Journals (Sweden)

    V. N. Bubenchikova

    2014-01-01

    Full Text Available We have studied carboxylic acids of the herb of Thymus cretaceus Klok. et Schost which is widespread on a territory of some regions (Belgorod, Voronezh. The study was carried out using gas-liquid chromatography at Agilent Technologies 6890 chromatographer with massspectrometric detector 5973 N. Acids concentration was calculated by means of inner standard.We have established that carboxylic acids of Thymus cretaceus are represented by 34 compounds. Palmitic (1779.02 mg/kg, behenic (1084.15 mg/kg, levulinic (986.24 mg/kg and linoleic acids (678.82 mg/kg predominate among fatty acids; citric (9835.14 mg/kg, malonic (447.91 mg/kg and oxalic acids (388.32 mg/kg predominate among organic acids; andferulic acid predominate amongphenolcarbonic acids.

  20. Functionalization of carbon nanotube by carboxyl group under radial deformation

    Science.gov (United States)

    Lara, Ivi Valentini; Zanella, Ivana; Fagan, Solange Binotto

    2014-01-01

    The dependence of the structural and the electronic properties of functionalized (5, 5) single-walled carbon nanotubes (SWNT) were investigated through ab initio density functional simulations when the carboxyl group is bonded on the flatter or curved regions. Radial deformations result in diameter decrease of up to 20 per cent of the original size, which was the limit reduction that maintains the SWNT functionalized structure. Changes on the electronic structure were observed due to the symmetry break of the SWNT caused by both the carboxyl group and the C-C bond distortions resulted by the radial deformation. It is observed that the functionalization process is specially favored by the sp3 hybridization induced on the more curved region of the deformed SWNT.

  1. Enhance decarboxylation reaction of carboxylic acids in clay minerals

    International Nuclear Information System (INIS)

    Clay minerals are important constituents of the Earth's crust. These minerals catalyze reactions in several ways: by energy transfer processes, redox reactions, stabilization of intermediates and by Broensted or Lewis acidity behavior. Important set of organic reactions can be improved in the precedence of clay minerals. Besides the properties of clays to catalyze chemical reactions, it is possible to enhance some of its reactions by using ionizing radiation. The phenomenon of radiation-induced catalysis may be connected with ionizing process in the solid and with the trapped non-equilibrium charge carriers. In this paper we are reporting the decarboxylation reaction of carboxylic acids catalyzed by clay and by irradiation of the system acid-clay. We studied the behaviour of several carboxylic acids and analyzed them by gas chromatography, X-ray and infrared spectroscopy. The results showed that decarboxylation of the target compound is the dominating pathway. The reaction is enhanced by gamma radiation in several orders of magnitude. (author)

  2. Influences of Carboxyl Methyl Cellulose on Performances of Mortar

    Institute of Scientific and Technical Information of China (English)

    WANG Yuli; ZHOU Mingkai; SHAN Junhong; XU Fang; YANG Yuhui

    2007-01-01

    Carboxyl methyl cellulose (CMC) was mixed into mortar to improve the waterretention performance of mortar, the quality of floated coat of aerated concrete became better. The consistency and compression strength of mortar with CMC were studied. The water absorption was studied with the method of filter paper. The micro mechanism was researched with X-ray diffraction and scanning electron microscopy(SEM). The experimental results show the water-holding performance of mortar with CMC is largely improved and it is better when the mixed amount is about 1.5%; the compression strength had a descending trend with the increase of CMC; CMC reacted with calcium hydroxide(CH) into the deposition of calcium carboxyl methyl cellulose.

  3. Enhancing magnetoresistance in tetrathiafulvalene carboxylate modified iron oxide nanoparticle assemblies

    Science.gov (United States)

    Lv, Zhong-Peng; Luan, Zhong-Zhi; Cai, Pei-Yu; Wang, Tao; Li, Cheng-Hui; Wu, Di; Zuo, Jing-Lin; Sun, Shouheng

    2016-06-01

    We report a facile approach to stabilize Fe3O4 nanoparticles (NPs) by using tetrathiafulvalene carboxylate (TTF-COO-) and to control electron transport with an enhanced magnetoresistance (MR) effect in TTF-COO-Fe3O4 NP assemblies. This TTF-COO-coating is advantageous over other conventional organic coatings, making it possible to develop stable Fe3O4 NP arrays for sensitive spintronics applications.We report a facile approach to stabilize Fe3O4 nanoparticles (NPs) by using tetrathiafulvalene carboxylate (TTF-COO-) and to control electron transport with an enhanced magnetoresistance (MR) effect in TTF-COO-Fe3O4 NP assemblies. This TTF-COO-coating is advantageous over other conventional organic coatings, making it possible to develop stable Fe3O4 NP arrays for sensitive spintronics applications. Electronic supplementary information (ESI) available: Experimental details; supplementary figures and tables. See DOI: 10.1039/c6nr03311c

  4. Substrate specificity within a family of outer membrane carboxylate channels.

    Directory of Open Access Journals (Sweden)

    Elif Eren

    2012-01-01

    Full Text Available Many Gram-negative bacteria, including human pathogens such as Pseudomonas aeruginosa, do not have large-channel porins. This results in an outer membrane (OM that is highly impermeable to small polar molecules, making the bacteria intrinsically resistant towards many antibiotics. In such microorganisms, the majority of small molecules are taken up by members of the OprD outer membrane protein family. Here we show that OprD channels require a carboxyl group in the substrate for efficient transport, and based on this we have renamed the family Occ, for outer membrane carboxylate channels. We further show that Occ channels can be divided into two subfamilies, based on their very different substrate specificities. Our results rationalize how certain bacteria can efficiently take up a variety of substrates under nutrient-poor conditions without compromising membrane permeability. In addition, they explain how channel inactivation in response to antibiotics can cause resistance but does not lead to decreased fitness.

  5. Fluorescently tuned nitrogen-doped carbon dots from carbon source with different content of carboxyl groups

    International Nuclear Information System (INIS)

    In this study, fluorescent nitrogen-doped carbon dots (NCDs) were tuned via varying the sources with different number of carboxyl groups. Owing to the interaction between amino and carboxyl, more amino groups conjugate the surface of the NCDs by the source with more carboxyl groups. Fluorescent NCDs were tuned via varying the sources with different content of carboxyl groups. Correspondingly, the nitrogen content, fluorescence quantum yields and lifetime of NCDs increases with the content of carboxyl groups from the source. Furthermore, cytotoxicity assay and cell imaging test indicate that the resultant NCDs possess low cytotoxicity and excellent biocompatibility

  6. Fluorescently tuned nitrogen-doped carbon dots from carbon source with different content of carboxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hao; Wang, Yun; Dai, Xiao; Zou, Guifu, E-mail: kqzhang@suda.edu.cn, E-mail: zouguifu@suda.edu.cn [College of Physics, Optoelectronics and Energy and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China); Gao, Peng; Zhang, Ke-Qin, E-mail: kqzhang@suda.edu.cn, E-mail: zouguifu@suda.edu.cn; Du, Dezhuang [National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou 215123 (China); Guo, Jun [Testing and Analysis Center, Soochow University, Suzhou 215123 (China)

    2015-08-01

    In this study, fluorescent nitrogen-doped carbon dots (NCDs) were tuned via varying the sources with different number of carboxyl groups. Owing to the interaction between amino and carboxyl, more amino groups conjugate the surface of the NCDs by the source with more carboxyl groups. Fluorescent NCDs were tuned via varying the sources with different content of carboxyl groups. Correspondingly, the nitrogen content, fluorescence quantum yields and lifetime of NCDs increases with the content of carboxyl groups from the source. Furthermore, cytotoxicity assay and cell imaging test indicate that the resultant NCDs possess low cytotoxicity and excellent biocompatibility.

  7. Complex formation of Np(V) with various carboxylates

    International Nuclear Information System (INIS)

    The stability constants of Np(V) complexes with a series of aliphatic and aromatic carboxylates, including hydroxycarboxylates, hydroxydicarboxylates, dicarboxylates and pyridinecarboxylates have been obtained in 1.0 M NaClO4 by a solvent extraction method using thenoyltrifluoroacetone and 1,10- phenanthroline in isoamyl alcohol. Stabilities of these complexes are discussed in terms of their structures and ligand basicities. (orig.)

  8. Circulating Nonphosphorylated Carboxylated Matrix Gla Protein Predicts Survival in ESRD

    OpenAIRE

    Schlieper, Georg; Westenfeld, Ralf; Krüger, Thilo; Cranenburg, Ellen C.; Magdeleyns, Elke J.; Brandenburg, Vincent M.; Djuric, Zivka; Damjanovic, Tatjana; Ketteler, Markus; Vermeer, Cees; Dimkovic, Nada; Floege, Jürgen; Schurgers, Leon J.

    2011-01-01

    The mechanisms for vascular calcification and its associated cardiovascular mortality in patients with ESRD are not completely understood. Dialysis patients exhibit profound vitamin K deficiency, which may impair carboxylation of the calcification inhibitor matrix gla protein (MGP). Here, we tested whether distinct circulating inactive vitamin K–dependent proteins associate with all-cause or cardiovascular mortality. We observed higher levels of both desphospho-uncarboxylated MGP (dp-ucMGP) a...

  9. ELECTROANALYTICAL APPLICATIONS OF CARBOXYL-MODIFIED CARBON NANOTUBE FILM ELECTRODES

    Institute of Scientific and Technical Information of China (English)

    C.G. Hu; W.L. Wang; K.J. Liao; W. Zhu

    2003-01-01

    The electrochemical behavior of a carboxyl-modified carbon nanotube films was investigated to explore its possibility in electroanalytical applicaton. Cyclic voltammetry of quinone was conducted in 1mol/L Na2SO4, which showed a stable, quasi-reversible voltammetric response for quinone / hydroquinone, and the anodic and the cathodic peak potentials were 0.657V and -0.029V (vs. SCE) at a scan rate of 0.1V.s-1, respectively. Both anodic and cathodic peak currents depended linearly on the square root of the scan rate over the range of 0.01-0. 5 V.s-1, which suggested that the process of the electrode reactions was diffusion-controlled. Carboxyl-modified carbon nanotube electrodes made it possible to determine low level of dopamine selectively in the presence of a large excess of ascorbic acid in acidic media using derivative voltammetry.The results obtained were discussed in details. This work demonstrates the potential of carboxyl-modified carbon nanotube electrodes for electroanalytical applications.

  10. Carboxylic acid-functionalized SBA-15 nanorods for gemcitabine delivery

    International Nuclear Information System (INIS)

    The present study deals with the functionalization of mesoporous silica nanoparticles as drug delivery systems. Mono, di, and tri amino-functionalized SBA-15 nanorods were synthesized by post-grafting method using (3-aminopropyl) triethoxysilane, N-(2-aminoethyl-)3- aminopropyltrimethoxysilane, and 3-[2-(2-aminoethylamino) ethylamino] propyl trimethoxysilane, respectively. The carboxylic acid derivatives of the amino-functionalized samples were obtained using succinic anhydride. Tminopropyltrimethoxysilanehe obtained modified materials were investigated as matrixes for the anticancer drug (gemcitabine) delivery. The prepared samples were characterized by SAXS, N2 adsorption/desorption, SEM, transmission electron microscopy, thermogravimetric analysis, and FTIR and UV spectroscopies. The adsorption and release properties of all samples were studied. It was revealed that the adsorption capacity and release behavior of gemcitabine were highly dependent on the type of the introduced functional groups. The carboxylic acid-modified samples have higher loading content, due to the strong interaction with gemcitabine. The maximum content of deposited drug in the modified SBA-15 nanorods is close to 40 wt%. It was found that the surface functionalization leads toward significant decrease of the drug release rate. The carboxylic acid-functionalized samples have slower release rate in contrast with the amino-functionalized samples

  11. Biarylalkyl Carboxylic Acid Derivatives as Novel Antischistosomal Agents.

    Science.gov (United States)

    Mäder, Patrick; Blohm, Ariane S; Quack, Thomas; Lange-Grünweller, Kerstin; Grünweller, Arnold; Hartmann, Roland K; Grevelding, Christoph G; Schlitzer, Martin

    2016-07-01

    Parasitic platyhelminths are responsible for serious infectious diseases, such as schistosomiasis, which affect humans as well as animals across vast regions of the world. The drug arsenal available for the treatment of these diseases is limited; for example, praziquantel is the only drug currently used to treat ≥240 million people each year infected with Schistosoma spp., and there is justified concern about the emergence of drug resistance. In this study, we screened biarylalkyl carboxylic acid derivatives for their antischistosomal activity against S. mansoni. These compounds showed significant influence on egg production, pairing stability, and vitality. Tegumental lesions or gut dilatation was also observed. Substitution of the terminal phenyl residue in the biaryl scaffold with a 3-hydroxy moiety and derivatization of the terminal carboxylic acid scaffold with carboxamides yielded compounds that displayed significant antischistosomal activity at concentrations as low as 10 μm with satisfying cytotoxicity values. The present study provides detailed insight into the structure-activity relationships of biarylalkyl carboxylic acid derivatives and thereby paves the way for a new drug-hit moiety for fighting schistosomiasis. PMID:27159334

  12. Cellular uptake and anticancer activity of carboxylated gallium corroles.

    Science.gov (United States)

    Pribisko, Melanie; Palmer, Joshua; Grubbs, Robert H; Gray, Harry B; Termini, John; Lim, Punnajit

    2016-04-19

    We report derivatives of gallium(III) tris(pentafluorophenyl)corrole, 1 [Ga(tpfc)], with either sulfonic (2) or carboxylic acids (3, 4) as macrocyclic ring substituents: the aminocaproate derivative, 3 [Ga(ACtpfc)], demonstrated high cytotoxic activity against all NCI60 cell lines derived from nine tumor types and confirmed very high toxicity against melanoma cells, specifically the LOX IMVI and SK-MEL-28 cell lines. The toxicities of 1, 2, 3, and 4 [Ga(3-ctpfc)] toward prostate (DU-145), melanoma (SK-MEL-28), breast (MDA-MB-231), and ovarian (OVCAR-3) cancer cells revealed a dependence on the ring substituent: IC50values ranged from 4.8 to >200 µM; and they correlated with the rates of uptake, extent of intracellular accumulation, and lipophilicity. Carboxylated corroles 3 and 4, which exhibited about 10-fold lower IC50values ( 3 > 2 > 1 (intracellular accumulation of gallium corroles was fastest in melanoma cells). We conclude that carboxylated gallium corroles are promising chemotherapeutics with the advantage that they also can be used for tumor imaging. PMID:27044076

  13. Carboxylic acid-functionalized SBA-15 nanorods for gemcitabine delivery

    Energy Technology Data Exchange (ETDEWEB)

    Bahrami, Zohreh; Badiei, Alireza, E-mail: abadiei@khayam.ut.ac.ir [University of Tehran, School of Chemistry, College of Science (Iran, Islamic Republic of); Ziarani, Ghodsi Mohammadi [Alzahra University, Research Laboratory of Pharmaceutical (Iran, Islamic Republic of)

    2015-03-15

    The present study deals with the functionalization of mesoporous silica nanoparticles as drug delivery systems. Mono, di, and tri amino-functionalized SBA-15 nanorods were synthesized by post-grafting method using (3-aminopropyl) triethoxysilane, N-(2-aminoethyl-)3- aminopropyltrimethoxysilane, and 3-[2-(2-aminoethylamino) ethylamino] propyl trimethoxysilane, respectively. The carboxylic acid derivatives of the amino-functionalized samples were obtained using succinic anhydride. Tminopropyltrimethoxysilanehe obtained modified materials were investigated as matrixes for the anticancer drug (gemcitabine) delivery. The prepared samples were characterized by SAXS, N{sub 2} adsorption/desorption, SEM, transmission electron microscopy, thermogravimetric analysis, and FTIR and UV spectroscopies. The adsorption and release properties of all samples were studied. It was revealed that the adsorption capacity and release behavior of gemcitabine were highly dependent on the type of the introduced functional groups. The carboxylic acid-modified samples have higher loading content, due to the strong interaction with gemcitabine. The maximum content of deposited drug in the modified SBA-15 nanorods is close to 40 wt%. It was found that the surface functionalization leads toward significant decrease of the drug release rate. The carboxylic acid-functionalized samples have slower release rate in contrast with the amino-functionalized samples.

  14. Oxidation of Alpha-Ketoglutarate Is Required for Reductive Carboxylation in Cancer Cells with Mitochondrial Defects

    Directory of Open Access Journals (Sweden)

    Andrew R. Mullen

    2014-06-01

    Full Text Available Mammalian cells generate citrate by decarboxylating pyruvate in the mitochondria to supply the tricarboxylic acid (TCA cycle. In contrast, hypoxia and other impairments of mitochondrial function induce an alternative pathway that produces citrate by reductively carboxylating α-ketoglutarate (AKG via NADPH-dependent isocitrate dehydrogenase (IDH. It is unknown how cells generate reducing equivalents necessary to supply reductive carboxylation in the setting of mitochondrial impairment. Here, we identified shared metabolic features in cells using reductive carboxylation. Paradoxically, reductive carboxylation was accompanied by concomitant AKG oxidation in the TCA cycle. Inhibiting AKG oxidation decreased reducing equivalent availability and suppressed reductive carboxylation. Interrupting transfer of reducing equivalents from NADH to NADPH by nicotinamide nucleotide transhydrogenase increased NADH abundance and decreased NADPH abundance while suppressing reductive carboxylation. The data demonstrate that reductive carboxylation requires bidirectional AKG metabolism along oxidative and reductive pathways, with the oxidative pathway producing reducing equivalents used to operate IDH in reverse.

  15. Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties

    Directory of Open Access Journals (Sweden)

    H. F. Xie

    2012-09-01

    Full Text Available Carboxyl-modified multi-walled carbon nanotubes (MWCNT–COOHs as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN. The carboxyl functional carbon nanotubes were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. Furthermore, cure kinetics, glass transition temperature (Tg, mechanical properties, thermal stability and morphology of DGEBA/CTBN/MWCNT–COOHs nanocomposites were investigated by differential scanning calorimetry (DSC, dynamic mechanical analysis (DMA, universal test machine, thermogravimetric analysis and scanning electron microscopy (SEM. DSC kinetic studies showed that the addition of MWCNT–COOHs accelerated the curing reaction of the rubber-toughened epoxy resin. DMA results revealed that Tg of rubber-toughened epoxy nanocomposites lowered with MWCNT–COOH contents. The tensile strength, elongation at break, flexural strength and flexural modulus of DGEBA/CTBN/MWCNT-COOHs nanocomposites were increased at lower MWCNT-COOH concentration. A homogenous dispersion of nanocomposites at lower MWCNT–COOH concentration was observed by SEM.

  16. Sodium borohydride reduction of aromatic carboxylic acids via methyl esters

    Indian Academy of Sciences (India)

    Aamer Saeed; Zaman Ashraf

    2006-09-01

    A number of important aromatic carboxylic acids precursors, or intermediates in the syntheses of natural products, are converted into methyl esters and reduced to the corresponding primary alcohols using a sodium borohydride-THF-methanol system. The alcohols are obtained in 70-92% yields in 2-5 hours, in a pure state. This two-step procedure not only provides a better alternative to aluminum hydride reduction of acids but also allows the selective reduction of esters in presence of acids, amides, nitriles or nitro functions which are not affected under these conditions.

  17. Dimeric supramolecular motifs of two carboxylate-guanidinium compounds.

    Science.gov (United States)

    Ashiq, Muhammad Irfan; Hussain, Ishtiaq; Dixon, Sally; Light, Mark E; Kilburn, Jeremy D

    2010-09-01

    The structures of N-benzyl-N'-{6-[(4-carboxylatobenzyl)aminocarbonyl]-2-pyridylmethyl}guanidinium, C(23)H(23)N(5)O(3), (I), and N-[2-(benzylaminocarbonyl)ethyl]-N'-{6-[(4-carboxylatobenzyl)aminocarbonyl]-2-pyridylmethyl}guanidinium monohydrate, C(26)H(28)N(6)O(4).H(2)O, (II), both form three-dimensional supramolecular hydrogen-bonded networks based on a dimeric primary synthon involving carboxylate-guanidinium linkages. The differences in the geometries and hydrogen-bonding connectivities are driven by the additional methylpropionamide group and water of crystallization of (II). PMID:20814105

  18. (2S,4R-4-Fluoropyrrolidinium-2-carboxylate

    Directory of Open Access Journals (Sweden)

    David B. Hobart Jr

    2012-08-01

    Full Text Available The crystal structure of the title compound, C5H8FNO2, at 100 K, displays intermolecular N—H...O hydrogen bonding between the ammonium and carboxylate groups as a result of its zwitterionic nature in the solid state. The five-membered ring adopts an envelope conformation with the C atom at the 3-position as the flap. The compound is of interest with respect to the synthesis and structural properties of synthetic collagens. The absolute structure was determined by comparison with the commercially available material.

  19. Study on Copolymerization of Rare Earth-Carboxylic Acid Complex

    Institute of Scientific and Technical Information of China (English)

    Qiu Guanmin(邱关明); Zhang Ming(张明); Yan Chang hao(严长浩); Zhou Lanxiang(周兰香); Dai Shaojun(戴少俊); Okamo to Hiroshi

    2003-01-01

    Complex of rare earth with carboxylic acid was prepared by precipita tion and direct method. It was copolymerized with such monomers as acrylic acid and other ones to synthesize ionomer of rare earth and organic polymer with different rare earth contents. Its glass-transition temperature and heat stability were analyzed by TG and DTA. Infra-red detector was used to show its structure. The effect of rare earth complex prepared by different methods on copolymerization and properties of copolymers was also discussed.

  20. Separation and determination of some carboxylic acids by capillary electrophoresis

    Energy Technology Data Exchange (ETDEWEB)

    Sladkov, V.; Fourest, B

    2006-07-01

    Separation and determination of some organic acids, mono-carboxylic (formic and acetic), dicarboxylic (oxalic and tartaric), tricarboxylic (citric) acids and aromatic acids (phtalic, benzoic, mellitic and trimellitic), by capillary electrophoresis are reviewed. The method development parameters, such as separation and injection mode, are discussed. Special attention is paid to the comparison of different detection types (spectroscopic and electrochemical). The optimisation of the carrier electrolyte composition (choice of carrier electrolyte, effect of pH, ionic strength, electro-osmotic flow modifier) is treated. Different additives (alkali-earth and transition metal ions, cyclodextrins and alcohol), which are often used for improving organic acid separation, are also considered. (authors)

  1. Azetidine-2-carboxylic acid in garden beets (Beta vulgaris).

    Science.gov (United States)

    Rubenstein, Edward; Zhou, Haihong; Krasinska, Karolina M; Chien, Allis; Becker, Christopher H

    2006-05-01

    Azetidine-2-carboxylic acid (L-Aze) is a toxic and teratogenic non-protein amino acid. In many species, including man, L-Aze is misincorporated into protein in place of proline, altering collagen, keratin, hemoglobin, and protein folding. In animal models of teratogenesis, it causes a wide range of malformations. The role of L-Aze in human disease has been unexplored, probably because the compound has not been associated with foods consumed by humans. Herein we report the presence of L-Aze in the garden or table beet (Beta vulgaris).

  2. Modeling Donnan Dialysis Separation for Carboxylic Anion Recovery

    DEFF Research Database (Denmark)

    Prado Rubio, Oscar Andres; Møllerhøj, Martin; Jørgensen, Sten Bay;

    2010-01-01

    dynamic model for transport of multiple ions through an anion exchange membrane is derived based on an irreversible thermodynamics approach. This model accounts for the convective transport of the dissociated and undissociated species in the channels with diffusion and migration across the boundary...... boundary layers and membranes. The model consists of a system of partial differential equations that are solved numerically. The aim of this paper is to corroborate this general model for several monoprotic carboxylic acids reported in the literature. The model reproduces satisfactorily experimental fluxes...

  3. Two Dimensional Polyamides Prepared From Unsaturated Carboxylic Acids And Amines.

    Energy Technology Data Exchange (ETDEWEB)

    McDonald, William F. (Utica, OH); Huang, Zhi Heng (East Lansing, MI); Wright, Stacy C. (Lansing, MI); Danzig, Morris (Northbrook, IL); Taylor, Andrew C. (Ann Arbor, MI)

    2002-07-17

    A polyamide and a process for preparing the polyamide are disclosed. The process comprises reacting in a reaction mixture a monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and mixtures thereof, and a first amine to form an intermediate reaction product in the reaction mixture, wherein the first amine is selected from RR.sub.1 NH, RNH.sub.2, RR.sub.1 NH.sub.2.sup.+, RNH.sub.3.sup.+ and mixtures thereof, wherein R and R.sub.1 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, and reacting the intermediate reaction product and a second amine to form a polyamide, wherein the second amine is selected from R.sub.2 R.sub.3 NH, R.sub.2 NH.sub.2, R.sub.2 R.sub.3 NH.sub.2.sup.+, R.sub.2 NH.sub.3.sup.+ and mixtures thereof wherein R.sub.2 and R.sub.3 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, wherein multiple of the R, R.sub.1, R.sub.2, and R.sub.3 are in vertically aligned spaced relationship along a backbone formed by the polyamide. In one version of the invention, the monomer is selected from maleic anhydride, maleic acid esters, and mixtures thereof. In another version of the invention, the first amine is an alkylamine, such as tetradecylamine, and the second amine is a polyalkylene polyamine, such as pentaethylenehexamine. In yet another version of the invention, the first amine and the second amine are olefinic or acetylenic amines, such as the reaction products of an alkyldiamine and an acetylenic carboxylic acid. The first amine and the second amine may be the same or different depending on the desired polyamide polymer structure.

  4. Separation and determination of some carboxylic acids by capillary electrophoresis

    International Nuclear Information System (INIS)

    Separation and determination of some organic acids, mono-carboxylic (formic and acetic), dicarboxylic (oxalic and tartaric), tricarboxylic (citric) acids and aromatic acids (phtalic, benzoic, mellitic and trimellitic), by capillary electrophoresis are reviewed. The method development parameters, such as separation and injection mode, are discussed. Special attention is paid to the comparison of different detection types (spectroscopic and electrochemical). The optimisation of the carrier electrolyte composition (choice of carrier electrolyte, effect of pH, ionic strength, electro-osmotic flow modifier) is treated. Different additives (alkali-earth and transition metal ions, cyclodextrins and alcohol), which are often used for improving organic acid separation, are also considered. (authors)

  5. A synthetic approach to carbon-14 labeled anti-bacterial naphthyridine and quinolone carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Ekhato, I.V.; Huang, C.C. (Parke, Davis and Co., Ann Arbor, MI (United States))

    1993-09-01

    Labeled versions of (S)-clinafloxacin (1) and two napththyridine carboxylic acid anti-bacterial compounds 2 and 3 which are currently in development were synthesized. Preparations started from hitherto unknown bromo compounds 22 and 10, from which the corresponding [sup 14]C-labeled aromatic carboxylic acids 23 and 12 were generated by metal-halogen exchange followed by carboxylation reaction. Details of these preparations are given. (author).

  6. Exploring the reductive capacity of Pyrococcus furiosus. The reduction of carboxylic acids and pyridine nucleotides

    OpenAIRE

    Ban, van den, A.W.

    2001-01-01

    This Ph.D. project started in 1997 and its main goal was to obtain insight in the reductive capacity of the hyperthermophilic archaeon Pyrococcus furiosus . The research was focused on the biocatalytic reduction of carboxylic acids.Reductions of carboxylic acids are interesting reactions, since the generated products, aldehydes and alcohols, are potentially applicable in the fine-chemical industry. However, the reduction of carboxylic acids to the corresponding aldehydes is a thermodynamicall...

  7. Electrochemical deposition of a copper carboxylate layer on copper as potential corrosion inhibitor

    OpenAIRE

    Elia, Alice; De Wael, Karolien; Dowsett, Mark; Adriaens, Annemie

    2012-01-01

    Carboxylic acids and sodium carboxylates are used to protect metals against aqueous and atmospheric corrosion. In this paper we describe the application of a layer of copper carboxylate on the surface of a copper electrode by means of cyclic voltammetry technique, and tests which measure the corresponding resistance to aqueous corrosion. Unlike the soaking process, which also forms a film on the surface, the use of cyclic voltammetry allows one to follow the deposition process of the copper c...

  8. Substituent effects on hydrogen bonding of aromatic amide-carboxylate.

    Science.gov (United States)

    Sen, Ibrahim; Kara, Hulya; Azizoglu, Akın

    2016-10-01

    N-(p-benzoyl)-anthranilic acid (BAA) derivatives have been synthesized with different substituents (X: Br, Cl, OCH3, CH3), and their crystal structures have been analyzed in order to understand the variations in their molecular geometries with respect to the substituents by using (1)H NMR, (13)C NMR, IR and X-ray single-crystal diffraction. The carboxylic acid group forms classic OH⋯O hydrogen bonded dimers in a centrosymmetric R2(2)(8) ring motifs for BAA-Br and BAA-Cl. However, no carboxylic acid group forms classic OH⋯O hydrogen bonded dimers in BAA-OCH3 and BAA-CH3. The asymmetric unit consists of two crystallographically independent molecules in BAA-OCH3. DFT computations show that the interaction energies between monomer and dimer are in the range of 0.5-3.8kcal/mol with the B3LYP/6-31+G*, B3LYP/6-31++G*, B3LYP/6-31++G**, and B3LYP/AUG-cc-pVDZ levels of theory. The presence of different hydrogen bond patterns is also governed by the substrate. For monomeric compounds studied herein, theoretical calculations lead to two low-energy conformers; trans (a) and cis (b). Former one is more stable than latter by about 4kcal/mol. PMID:27239947

  9. Integrated process for preparing a carboxylic acid from an alkane

    Energy Technology Data Exchange (ETDEWEB)

    Benderly, Abraham (Elkins Park, PA); Chadda, Nitin (Radnor, PA); Sevon, Douglass (Fairless Hills, PA)

    2011-12-20

    The present invention relates to an integrated process for producing unsaturated carboxylic acids from the corresponding C.sub.2-C.sub.4 alkane. The process begins with performance of thermally integrated dehydrogenation reactions which convert a C.sub.2-C.sub.4 alkane to its corresponding C.sub.2-C.sub.4 alkene, and which involve exothermically converting a portion of an alkane to its corresponding alkene by oxidative dehydrogenation in an exothermic reaction zone, in the presence of oxygen and a suitable catalyst, and then feeding the products of the exothermic reaction zone to an endothermic reaction zone wherein at least a portion of the remaining unconverted alkane is endothermically dehydrogenated to form an additional quantity of the same corresponding alkene, in the presence of carbon dioxide and an other suitable catalyst. The alkene products of the thermally integrated dehydrogenation reactions are then provided to a catalytic vapor phase partial oxidation process for conversion of the alkene to the corresponding unsaturated carboxylic acid or nitrile. Unreacted alkene and carbon dioxide are recovered from the oxidation product stream and recycled back to the thermally integrated dehydrogenation reactions.

  10. Substituent effects on hydrogen bonding of aromatic amide-carboxylate

    Science.gov (United States)

    Sen, Ibrahim; Kara, Hulya; Azizoglu, Akın

    2016-10-01

    N-(p-benzoyl)-anthranilic acid (BAA) derivatives have been synthesized with different substituents (X: Br, Cl, OCH3, CH3), and their crystal structures have been analyzed in order to understand the variations in their molecular geometries with respect to the substituents by using 1H NMR, 13C NMR, IR and X-ray single-crystal diffraction. The carboxylic acid group forms classic Osbnd H ⋯ O hydrogen bonded dimers in a centrosymmetric R22(8) ring motifs for BAA-Br and BAA-Cl. However, no carboxylic acid group forms classic Osbnd H ⋯ O hydrogen bonded dimers in BAA-OCH3 and BAA-CH3. The asymmetric unit consists of two crystallographically independent molecules in BAA-OCH3. DFT computations show that the interaction energies between monomer and dimer are in the range of 0.5-3.8 kcal/mol with the B3LYP/6-31 + G*, B3LYP/6-31 ++G*, B3LYP/6-31 ++G**, and B3LYP/AUG-cc-pVDZ levels of theory. The presence of different hydrogen bond patterns is also governed by the substrate. For monomeric compounds studied herein, theoretical calculations lead to two low-energy conformers; trans (a) and cis (b). Former one is more stable than latter by about 4 kcal/mol.

  11. Biocompatibility studies of polyacrylonitrile membranes modified with carboxylated polyetherimide

    Energy Technology Data Exchange (ETDEWEB)

    Senthilkumar, S.; Rajesh, S.; Jayalakshmi, A.; Mohan, D., E-mail: mohantarun@gmail.com

    2013-10-15

    Poly (ether-imide) (PEI) was carboxylated and used as the hydrophilic modification agent for the preparation of polyacrylonitrile (PAN) membranes. Membranes were prepared with different blend compositions of PAN and CPEI by diffusion induced precipitation. The modified membranes were characterized by thermo gravimetric analysis (TGA), mechanical analysis, scanning electron microscopy (SEM) and contact angle measurement to understand the influence of CPEI on the properties of the membranes. The biocompatibility studies exhibited reduced plasma protein adsorption, platelet adhesion and thrombus formation on the modified membrane surface. The complete blood count (CBC) results of CPEI incorporated membranes showed stable CBC values and significant decrease in the complement activation were also observed. In addition to good cytocompatibility, monocytes cultured on these modified membranes exhibited improved functional profiles in 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide (MTT) assay. Thus it could be concluded that PAN/CPEI membranes with excellent biocompatibility can be useful for hemodialysis. Highlights: • Carboxylated PEI was prepared and utilized as hydrophilic modification agent. • CPEI incorporated into PAN to improved biocompatibility and cyto compatibility • Biocompatibility of membranes was correlated with morphology and hydrophilicity. • Antifouling studies of the PAN/CPEI membranes was studied by BSA as model foulant.

  12. Dispersion of Co-poly Carboxylate Superplasticizer Containing Polyether Side Chain

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Free radical co-polymerization was employed to synthesize co-poly carboxylate (PC) superplasticizers with different amount of carboxyl and methyl polyethylene glycol (MPEG) side chain.Dispersion ability and retention of PC were compared with one another. The results show that increase of side chain is advantageous to dispersion, but it decreases when amount of MPEG is beyond a certain value which is different with the proportion of carboxyl. If the amount of carboxyl increases, the influence of side chain in copolymer on dispersion diminishes. Polyether side chain is advantageous to retention. And the author explained the mechanism of PC using the theory of steric repulsive force.

  13. Microarray of DNA probes on carboxylate functional beads surface

    Institute of Scientific and Technical Information of China (English)

    黄承志; 李原芳; 黄新华; 范美坤

    2000-01-01

    The microarray of DNA probes with 5’ -NH2 and 5’ -Tex/3’ -NH2 modified terminus on 10 um carboxylate functional beads surface in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) is characterized in the preseni paper. it was found that the microarray capacity of DNA probes on the beads surface depends on the pH of the aqueous solution, the concentra-tion of DNA probe and the total surface area of the beads. On optimal conditions, the minimum distance of 20 mer single-stranded DNA probe microarrayed on beads surface is about 14 nm, while that of 20 mer double-stranded DNA probes is about 27 nm. If the probe length increases from 20 mer to 35 mer, its microarray density decreases correspondingly. Mechanism study shows that the binding mode of DNA probes on the beads surface is nearly parallel to the beads surface.

  14. Biocompatibility studies of polyacrylonitrile membranes modified with carboxylated polyetherimide.

    Science.gov (United States)

    Senthilkumar, S; Rajesh, S; Jayalakshmi, A; Mohan, D

    2013-10-01

    Poly (ether-imide) (PEI) was carboxylated and used as the hydrophilic modification agent for the preparation of polyacrylonitrile (PAN) membranes. Membranes were prepared with different blend compositions of PAN and CPEI by diffusion induced precipitation. The modified membranes were characterized by thermo gravimetric analysis (TGA), mechanical analysis, scanning electron microscopy (SEM) and contact angle measurement to understand the influence of CPEI on the properties of the membranes. The biocompatibility studies exhibited reduced plasma protein adsorption, platelet adhesion and thrombus formation on the modified membrane surface. The complete blood count (CBC) results of CPEI incorporated membranes showed stable CBC values and significant decrease in the complement activation were also observed. In addition to good cytocompatibility, monocytes cultured on these modified membranes exhibited improved functional profiles in 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide (MTT) assay. Thus it could be concluded that PAN/CPEI membranes with excellent biocompatibility can be useful for hemodialysis. PMID:23910257

  15. Spectrofluorimetric determination of gallium with calon-carboxylic acid

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A simple and sensitive spectrofluorimetric procedure for the analysis of microquantities of gallium in alloy wasdescribed. The method is based on the formation of Ga(Ⅲ)-CCA (calon-carboxylic acid) complex. The emission of thefluorescent complex was measured at λ = 620 nm with excitation at λ = 584 nm. A good linearity was found in the galliumrange of 0.7-280 ng/mL. The precision of the method is good and the relative standard deviation is 1.9% for a gallium stan-dard solution of 70 ng/mL. The procedure was proved to be suitable in terms of accuracy and selectivity for the mi-croamount of gallium in alloy.

  16. Biohydrogen and carboxylic acids production from wheat straw hydrolysate.

    Science.gov (United States)

    Chandolias, Konstantinos; Pardaev, Sindor; Taherzadeh, Mohammad J

    2016-09-01

    Hydrolyzed wheat straw was converted into carboxylic acids and biohydrogen using digesting bacteria. The fermentations were carried out using both free and membrane-encased thermophilic bacteria (55°C) at various OLRs (4.42-17.95g COD/L.d), in semi-continuous conditions using one or two bioreactors in a series. The highest production of biohydrogen and acetic acid was achieved at an OLR of 4.42g COD/L.d, whilst the highest lactic acid production occurred at an OLR of 9.33g COD/L.d. Furthermore, the bioreactor with both free and membrane-encased cells produced 60% more lactic acid compared to the conventional, free-cell bioreactor. In addition, an increase of 121% and 100% in the production of acetic and isobutyric acid, respectively, was achieved in the 2nd-stage bioreactor compared to the 1st-stage bioreactor.

  17. 14CO2 ratios method for detecting pyruvate carboxylation

    International Nuclear Information System (INIS)

    The pattern of oxidative metabolism of pyruvate may be assessed by comparing the steady-state 14CO2 production from four isotopes in identical samples. The assay requires measuring the ratios of steady-state 14CO2 production from two isotope pairs, [2-14C]pyruvate:[3-14C]pyruvate and [1-14C]acetate:[2-14C]acetate. These ratios are defined as the ''pyruvate 14CO2 ratio'' and the ''acetate 14CO2 ratio,'' respectively. If pyruvate is metabolized exclusively via pyruvate dehydrogenase (PDH), the two ratios will be identical. Alternatively, if any pyruvate enters the tricarboxylic acid (TCA) cycle via pyruvate carboxylation (PC), the pyruvate 14CO2 ratio will be less than the acetate 14CO2 ratio. If pyruvate enters the TCA cycle only through PC (with oxaloacetate and fumarate in equilibrium) the pyruvate 14CO2 ratio will approach a value of 1.0. An equation is presented for the quantitative evaluation of pyruvate oxidation by these two pathways. We have used this method to detect relative changes in the pattern of pyruvate metabolism in rat liver mitochondria produced by exposure to 1 mM octanoyl carnitine, a compound known to alter the PC:PDH activity ratio. The major advantages of the method are (i) that it provides a sensitive method for detecting pyruvate carboxylation at physiological pyruvate concentrations and (ii) that it provides a method for distinguishing between effects on pyruvate transport and effects on pyruvate oxidation

  18. Exploring the reductive capacity of Pyrococcus furiosus. The reduction of carboxylic acids and pyridine nucleotides

    NARCIS (Netherlands)

    Ban, van den E.C.D.

    2001-01-01

    This Ph.D. project started in 1997 and its main goal was to obtain insight in the reductive capacity of the hyperthermophilic archaeon Pyrococcus furiosus . The research was focused on the biocatalytic reduction of carboxylic acids.Reductions of carboxylic acids are interes

  19. Preparations and applications in UV curing coatings of epoxy acrylates containing carboxyl

    International Nuclear Information System (INIS)

    This paper introduces preparations of epoxy acrylates containing carboxyl through the reactions of epoxy acrylates with butanedioic anhydride, pentanedioic anhydride, cis-butenedioic anhydride, phthalic anhydride, tetrabromophthalic anhydride and -tetrahydrophthalic anhydride. These epoxy acrylates containing carboxyl have been applied to UV-curing coatings and their effects on properties of UV-curing coatings have been studied

  20. Carboxyl-modified single-walled carbon nanotubes negatively affect bacterial growth and denitrification activity

    Science.gov (United States)

    Zheng, Xiong; Su, Yinglong; Chen, Yinguang; Wan, Rui; Li, Mu; Wei, Yuanyuan; Huang, Haining

    2014-07-01

    Single-walled carbon nanotubes (SWNTs) have been used in a wide range of fields, and the surface modification via carboxyl functionalization can further improve their physicochemical properties. However, whether carboxyl-modified SWNT poses potential risks to microbial denitrification after its release into the environment remains unknown. Here we present the possible effects of carboxyl-modified SWNT on the growth and denitrification activity of Paracoccus denitrificans (a model denitrifying bacterium). It was found that carboxyl-modified SWNT were present both outside and inside the bacteria, and thus induced bacterial growth inhibition at the concentrations of 10 and 50 mg/L. After 24 h of exposure, the final nitrate concentration in the presence of 50 mg/L carboxyl-modified SWNT was 21-fold higher than that in its absence, indicating that nitrate reduction was substantially suppressed by carboxyl-modified SWNT. The transcriptional profiling revealed that carboxyl-modified SWNT led to the transcriptional activation of the genes encoding ribonucleotide reductase in response to DNA damage and also decreased the gene expressions involved in glucose metabolism and energy production, which was an important reason for bacterial growth inhibition. Moreover, carboxyl-modified SWNT caused the significant down-regulation and lower activity of nitrate reductase, which was consistent with the decreased efficiency of nitrate reduction.

  1. 40 CFR 721.2088 - Carboxylic acids, (C6-C9) branched and linear.

    Science.gov (United States)

    2010-07-01

    ... linear. 721.2088 Section 721.2088 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.2088 Carboxylic acids, (C6-C9) branched and linear. (a) Chemical... as carboxylic acids, (C6-C9) branched and linear (PMNs P-93-313, 314, 315, and 316) are subject...

  2. Plastic scintillators with high loading of one or more metal carboxylates

    Energy Technology Data Exchange (ETDEWEB)

    Cherepy, Nerine; Sanner, Robert Dean

    2016-09-20

    According to one embodiment, a method includes incorporating a metal carboxylate complex into a polymeric matrix to form an optically transparent material. According to another embodiment, a material includes at least one metal carboxylate complex incorporated into a polymeric matrix, where the material is optically transparent.

  3. 40 CFR 721.10142 - Oxabicycloalkane carboxylic acid alkanediyl ester (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Oxabicycloalkane carboxylic acid alkanediyl ester (generic). 721.10142 Section 721.10142 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10142 Oxabicycloalkane carboxylic acid...

  4. 3-Methyl-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Rajendiran Nagappan

    2010-01-01

    Full Text Available 3-Methyl-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxylic acid was synthesized chemoselectively from 3-formyl-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxylic acid, using Et3SiH/I2 as a reducing agent. The title compound was characterized by IR, 1H NMR, 13C NMR and LCMS.

  5. Efficient Fixation of Carbon Dioxide by Electrolysis - Facile Synthesis of Useful Carboxylic Acids -

    Institute of Scientific and Technical Information of China (English)

    Masao Tokuda

    2006-01-01

    Electrochemical fixation of atmospheric pressure of carbon dioxide to organic compounds is a useful and attractive method for synthesizing of various carboxylic acids. Electrochemical fixation of carbon dioxide, electrochemical carboxylation, organic halides, organic triflates, alkenes, aromatic compounds, and carbonyl compounds can readily occur in the presence of an atmospheric pressure of carbon dioxide to form the corresponding carboxylic acids with high yields, when a sacrificial anode such as magnesium or aluminum is used in the electrolysis. The electrochemical carboxylation of vinyl bromides was successfully applied for the synthesis of the precursor of nonsteroidal anti-inflammatory agents such as ibuprofen and naproxen. On the other hand, supercritical carbon dioxide (scCO2) has significant potential as an environmentally benign solvent in organic synthesis and it could be used both as a solvent and as a reagent in these electrochemical carboxylations by using a small amount of cosolvent.

  6. 40 CFR 721.984 - Amino-hydroxy sulfonaphthylazo-disubstituted phenyl azo benzene carboxylate salt (generic).

    Science.gov (United States)

    2010-07-01

    ...-disubstituted phenyl azo benzene carboxylate salt (generic). 721.984 Section 721.984 Protection of Environment...-disubstituted phenyl azo benzene carboxylate salt (generic). (a) Chemical substance and significant new uses...-disubstituted phenyl azo benzene carboxylate salt (PMN P-00-0351) is subject to reporting under this section...

  7. Thermal stability of carboxylic acid functionality in coal; Sekitanchu ni sonzaisuru karubokishiruki no netsubunkai kyodo

    Energy Technology Data Exchange (ETDEWEB)

    Tsutsumi, Y.; Aida, T. [Kinki University, Osaka (Japan). Faculty of Engineering

    1996-10-28

    Carboxyl in coal was focused in discussing its pyrolytic behavior while tracking change of its absolute amount relative to the heating temperatures. A total of four kinds of coals, consisting of two kinds brown coals, sub-bituminous coal and bituminous coal were used. Change in the absolute amount of carboxyl due to heating varies with coalification degree. Decomposition starts in the bituminous coal from around 300{degree}C, and is rapidly accelerated when 400{degree}C is exceeded. Carboxyls in brown coals exist two to three times as much as those in bituminous and sub-bituminous coals, of which 40% is decomposed at a temperature as low as about 300{degree}C. Their pyrolytic behavior at temperatures higher than 400{degree}C resembles that of the bituminous coal. Carboxyls consist of those easy to decompose and difficult to decompose. Aromatic and aliphatic carboxylic acids with simple structure are stable at temperatures lower than 300{degree}C, and decompose abruptly from about 400{degree}C, hence their behavior resembles that of carboxyls in bituminous and sub-bituminous coals. Structure of low-temperature decomposing carboxyls in brown coals is not known, but it is assumed that humic acid originated from natural materials remains in the structure. 4 refs., 3 figs., 1 tab.

  8. Transition from Bioinert to Bioactive Material by Tailoring the Biological Cell Response to Carboxylated Nanocellulose.

    Science.gov (United States)

    Hua, Kai; Rocha, Igor; Zhang, Peng; Gustafsson, Simon; Ning, Yi; Strømme, Maria; Mihranyan, Albert; Ferraz, Natalia

    2016-03-14

    This work presents an insight into the relationship between cell response and physicochemical properties of Cladophora cellulose (CC) by investigating the effect of CC functional group density on the response of model cell lines. CC was carboxylated by electrochemical TEMPO-mediated oxidation. By varying the amount of charge passed through the electrolysis setup, CC materials with different degrees of oxidation were obtained. The effect of carboxyl group density on the material's physicochemical properties was investigated together with the response of human dermal fibroblasts (hDF) and human osteoblastic cells (Saos-2) to the carboxylated CC films. The introduction of carboxyl groups resulted in CC films with decreased specific surface area and smaller total pore volume compared with the unmodified CC (u-CC). While u-CC films presented a porous network of randomly oriented fibers, a compact and aligned fiber pattern was depicted for the carboxylated-CC films. The decrease in surface area and total pore volume, and the orientation and aggregation of the fibers tended to augment parallel to the increase in the carboxyl group density. hDF and Saos-2 cells presented poor cell adhesion and spreading on u-CC, which gradually increased for the carboxylated CC as the degree of oxidation increased. It was found that a threshold value in carboxyl group density needs be reached to obtain a carboxylated-CC film with cytocompatibility comparable to commercial tissue culture material. Hence, this study demonstrates that a normally bioinert nanomaterial can be rendered bioactive by carefully tuning the density of charged groups on the material surface, a finding that not only may contribute to the fundamental understanding of biointerface phenomena, but also to the development of bioinert/bioactive materials. PMID:26886265

  9. Nano-sized carboxylates as anode materials for rechargeable lithium-ion batteries

    Institute of Scientific and Technical Information of China (English)

    Xiaoyan Wu; Jie Ma; Yong-Sheng Hu; Hong Li; Liquan Chen

    2014-01-01

    Nano-sized carboxylates Na2C7H3NO4 and Na2C6H2N2O4 were prepared and investigated as anode materials for lithium-ion batteries. Both carboxylates exhibit high reversible capacities around 190 mAh/g above a cut-off voltage of 0.8 V vs. Li+/Li, potentially improving the safety of the batteries. In addition, good rate performance and long cycle life of these carboxylates make them promising candidates as anode materials for lithium-ion batteries.

  10. Palladium(II)-Catalyzed Tandem Synthesis of Acenes Using Carboxylic Acids as Traceless Directing Groups.

    Science.gov (United States)

    Kim, Kiho; Vasu, Dhananjayan; Im, Honggu; Hong, Sungwoo

    2016-07-18

    A straightforward synthetic strategy for generating useful anthracene derivatives was developed involving palladium(II)-catalyzed tandem transformation with carboxylic acids as traceless directing groups. Carboxyl-directed C-H alkenylation, carboxyl-directed secondary C-H activation and rollover, intramolecular C-C bond formation, and decarboxylative aromatization are proposed as the key steps in the tandem reaction pathway. This novel synthetic route utilizes a broad range of substrates and provides a convenient synthetic tool that allows access to acenes. PMID:27244536

  11. The investigation of the reactions of some pyrazole-3-carboxylic acids with various diamines and diols

    OpenAIRE

    Rahmi Kasımoğulları; Makbule Maden; Samet Mert

    2012-01-01

    In this study, some new derivatives were synthesized of 4-benzoyl-1-(3-nitrophenyl)-5-phenyl-1H-pyrazole-3-carboxylic acid (1) and 4-(ethoxycarbonyl)-1-(3-nitrophenyl)-5-phenyl-1H-pyrazole-3-carboxylic acid (2) that they were pyrazole carboxylic acid derivatives. Firstly, 1 and 2 reacted with SOCl2 to transform them into acyl chlorides (3, 4). Then various bis-carboxamide derivatives (58) were obtained from the reaction of 3 and 4 with various diamines and also a ;#946;-hydroxy ester (9) deri...

  12. The investigation of the reactions of some pyrazole-3-carboxylic acids with various diamines and diols

    OpenAIRE

    Kasımoğulları, Rahmi; Maden, Makbule; Mert, Samet

    2012-01-01

    In this study, some new derivatives were synthesized of 4-benzoyl-1-(3-nitrophenyl)-5-phenyl-1H-pyrazole-3-carboxylic acid (1) and 4-(ethoxycarbonyl)-1-(3-nitrophenyl)-5-phenyl-1H-pyrazole-3-carboxylic acid (2) that they were pyrazole carboxylic acid derivatives. Firstly, 1 and 2 reacted with SOCl2 to transform them into acyl chlorides (3, 4). Then various bis-carboxamide derivatives (5–8) were obtained from the reaction of 3 and 4 with various diamines and also a β-hydroxy ester (9)...

  13. A novel synthesis of carbon-labelled quinolone-3-carboxylic acid antibacterials

    Energy Technology Data Exchange (ETDEWEB)

    Carr, R.M.; Sutherland, D.R. (Glaxo Research and Development Ltd., Greenford (United Kingdom). Isotope Chemistry Group)

    1994-10-01

    3-Iodoquinolones were prepared from the corresponding quinolone-3-carboxylic acids by Hunsdiecker-type iododecarboxylation reactions with lead tetraacetate and iodine. Cyanation of the iodo compounds with mixtures of potassium [[sup 13]C]cyanide and copper (1) iodide, gave [3-[sup 13]C]cyanoquinolones which on acidic hydrolysis afforded quinolone-[3-[sup 13]C]carboxylic acids. In this way, nalidixic acid, an immediate precursor of norfloxacin, and quinolone WIN57273 were labelled with carbon-13 in the metabolically stable carboxylic acid fragment. (author).

  14. Influence of cyclic dimer formation on the phase behavior of carboxylic acids.

    Science.gov (United States)

    Janecek, Jiri; Paricaud, Patrice

    2012-07-12

    A new thermodynamic approach based on the Sear and Jackson association theory for doubly bonded dimers [Mol. Phys.1994, 82, 1033] is proposed to describe the thermodynamic properties of carboxylic acids. The new model is able to simultaneously represent the vapor pressures, saturated densities, and vaporization enthalpies of the shortest acids and is in a much better agreement with experimental data than other approaches that do no consider the formation of cyclic dimers. The new model is applied to mixtures of carboxylic acids with nonassociating compounds, and a very good description of the vapor-liquid equilibria in mixtures of alkanes + carboxylic acids is obtained.

  15. Z-effect reversal in carboxylic acid associates.

    Science.gov (United States)

    Medvedev, Michael G; Bushmarinov, Ivan S; Lyssenko, Konstantin A

    2016-05-01

    The carboxylic group is a common fragment in synthetic compounds and biomolecules. Its conformation is assumed to be dominantly cis due to so-called Z-effect. However, in this study, we show that the nature of the H-bond acceptor in RCOOHX directly affects the conformational preference of the resulting supermolecule. This result is evident from the statistical analysis of available crystallographic data and was quantified using accurate quantum chemical calculations. We propose the term "supramolecular stereoelectronic effect" for the observed conformational preference. The likely reason for this is the interaction of the O-HX hydrogen bond with the C[double bond, length as m-dash]O double bond in the trans conformation, which in case of anionic X is strong enough to reverse the Z-effect. Explicit consideration of trans COOHX stabilization can help crystal structure predictions and biomolecular simulations. In particular, this effect plays a key role in the transition between the T6 and R6 forms of human insulin. PMID:27109148

  16. Keto-Enol Tautomerizations Catalyzed by Water and Carboxylic Acids

    Science.gov (United States)

    da Silva, G.

    2009-12-01

    The ability of weakly-bound complexes to influence the kinetics of gas phase reactions, particularly in atmospheric chemistry, has long been speculated. This study uses quantum chemistry and statistical reaction rate theory to identify that bound water molecules can significantly reduce barriers to intramolecular hydrogen shift reactions, via a double-hydrogen-shift mechanism. The bound water molecule directly participates in the hydrogen shift reaction, exchanging a H atom with its counterpart. For the vinyl alcohol to acetaldehyde keto-enol tautomerization this mechanism cuts the reaction barrier approximately in half, reducing it by over 30 kcal mol-1. In contrast, while a non-participatory ‘bystander’ water molecule also reduces the hydrogen shift barrier, it is only by around 3 kcal/mol. When a carboxylic acid replaces water in the double-hydrogen-shift mechanism the barrier to keto-enol tautomerization is decimated, reduced to less than 6 kcal/mol (around 15 kcal/mol in the reverse direction). This results from reduced strain in the hydrogen shift transition state, and achieves enol lifetimes in the troposphere that become short on relevant timescales. Rapid enol to ketone isomerizations are currently required to explain the oxidation products of isoprene. The wider significance of rapid hydrogen shift reactions in atmospherically relevant molecules and radicals is also explored.

  17. Electrosynthesis and comparative studies on carboxyl-functionalized polythiophene derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Toth, Peter S.; Janaky, Csaba; Hiezl, Zoltan [Department of Physical Chemistry and Materials Science, University of Szeged, Aradi V. Sq. 1., Szeged H-6720 (Hungary); Visy, Csaba, E-mail: visy@chem.u-szeged.h [Department of Physical Chemistry and Materials Science, University of Szeged, Aradi V. Sq. 1., Szeged H-6720 (Hungary)

    2011-04-01

    Electrochemical synthesis of a novel carboxylic acid functionalized polythiophene - poly(3-thiophene-butyric-acid), PTBA - has been realized. Its morphology, electrochemical, spectral and conducting properties have been compared to those of poly(3-thiophene-acetic-acid), PTAA, which is widely used to immobilise both bioactive molecules and inorganic nanoparticles. According to scanning electron microscopic (SEM) images, the difference in the real and geometric surface area of the modified electrodes is much more expressed in the case of PTBA. Both the symmetry of the cyclic voltammograms and the concurrent, sustained optical changes proved that this polymer possesses an improved and more stable redox activity. According to simultaneously performed in situ ac. impedance and UV-Vis measurements, both films could be uniformly transformed between the insulating and conducting forms, but PTAA exhibited some degradation. The development of the conducting state during the redox switching of both thiophene derivative polymers proved to be primarily connected to the formation of di-cationic species. The electrochemical quartz crystal microbalance (EQCM) results evidenced also differences between the two polymers, which difference can be interpreted by assuming the more expressed effect of the deprotonation-connected (self-) doping process in PTAA. The results confirm that the new conducting polymer, PTBA is much more convenient for being considered as the polymer matrix of practically applicable composites.

  18. Structural and thermal properties of carboxylic acid functionalized polythiophenes

    Directory of Open Access Journals (Sweden)

    Ariane de França Mescoloto

    2014-01-01

    Full Text Available Polythiophenes functionalized with polar groups at the end of side-chain have emerged as an alternative method to obtain good compatibility between this class of conjugated polymers and electron acceptor compounds. The aim is to prevent phase segregation and to improve the efficiency of the polythiophene technological devices. However, homopolymers synthesized from thiophene rings with high polar groups at the end of the side-chain, such as hydroxyl and carboxylic acid groups, are poorly soluble in common volatile organic solvents. We report on a systematic preparation of copolymers of 3-hexylthiophene (HT and thiophene-3-acetic acid (TAA, using different feed ratios. The chemical structures of the copolymers were confirmed by FTIR and ¹H-NMR. The TAA content in these copolymers were 33, 38 and 54 mol %. HPSEC results did not show any remarkable correlation with TAA contents in the copolymers. In contrast, the thermal analyses showed a decrease in the thermal stability and an increase in rigidity of their backbones, for the copolymers with high amounts of TAA. The solubility and optical property of copolymers were also related to the TAA contents. Thus, the properties of these copolymers can be modulated by a simple control of feed ratio of TAA in the copolymerization.

  19. Biogeochemistry of the stable carbon isotopes in carboxylic acids

    International Nuclear Information System (INIS)

    The carbon isotopic compositions of the carboxyl carbons of fatty acids were determined by measuring the isotopic composition of the carbon dioxide quantitatively released from the acid. A modified version of the Schmidt decarboxylation developed and tested in this work was employed. A study of the evolution of CO2 at 5 +- 20C from the Schmidt decarboxylation of octanoic acid during the developmental program revealed two kinetic phases, each characterized by different rate constants and carbon isotope effects. The first, slower reaction phase displayed overall first-order kinetics, its rate being independent of HN3 concentration. Both pre-equilibration of the HN3-CHCl3 decarboxylation reagent with H2SO4 and saturation of the catalytic H2SO4 phase with KHSO4 drastically altered the rate of evolution and isotopic composition of the product CO2. The mechanistic implications of these results were discussed. A review of the metabolism of saturated fatty acids was made in which the impact of potential isotope fractionations in the various chemical reactions comprising the biosynthetic pathways on the intramolecular carbon isotope distribution within fatty acids was discussed

  20. High-level production of C-11-carboxyl-labeled amino acids

    International Nuclear Information System (INIS)

    Carbon-11-labeled amino acids have significant potential as agents for positron tomographic functional imaging. We have developed a rapid, high-temperature, high-pressure modification of the Buecherer--Strecker amino acid synthesis and found it to be quite general for the production of C-11-carboxyl-labeled neutral amino acids. Production of C-11-carboxyl-labeled DL-tryptophan requires certain modifications in the procedure. Twelve different amino acids have been produced to date by this technique. Synthesis and chromatographic purification require approximately 40 min, and C-11-carboxyl-labeled amino acids have been produced in yields of up to 425 mCi. Two C-11-carboxyl-labeled amino acids are being investigated clinically for tumor scanning and two others for pancreatic imaging. Over 120 batches of the various agents have been produced for clinical use over a three-year period

  1. EFFECT OF CARBOXYLIC IONOPHOROUS ANTIBACTERIALS ON THE GROWTH OF SELECTED MICROALGAE

    Science.gov (United States)

    Carboxylic ionophorous antibiotics are routinely used in cattle, chicken and turkey concentrated feedlot operations as anticoccidial and growth promotant feed additives and may, through runoff and effluents, enter adjacent waterways. The effects of these compounds on the growth o...

  2. Efficient Debromination of Vicinal (, (-Dibromo Carboxylic Acid Derivatives with the Sm/HOAc System

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The α, β vicinal dibromo carboxylic acid and its derivatives were debrominated with Sm/HOAc system to afford the corresponding cinnamic acid and its derivatives in good yields under mild conditions.

  3. Plastic scintillators with high loading of one or more metal carboxylates

    Science.gov (United States)

    Cherepy, Nerine; Sanner, Robert Dean

    2016-01-12

    In one embodiment, a material includes at least one metal compound incorporated into a polymeric matrix, where the metal compound includes a metal and one or more carboxylate ligands, where at least one of the one or more carboxylate ligands includes a tertiary butyl group, and where the material is optically transparent. In another embodiment, a method includes: processing pulse traces corresponding to light pulses from a scintillator material; and outputting a result of the processing, where the scintillator material comprises at least one metal compound incorporated into a polymeric matrix, the at least one metal compound including a metal and one or more carboxylate ligands, where at least one of the one or more carboxylate ligands has a tertiary butyl group, and where the scintillator material is optically transparent and has an energy resolution at 662 keV of less than about 20%.

  4. Measuring the concentration of carboxylic acid groups in torrefied spruce wood.

    Science.gov (United States)

    Khazraie Shoulaifar, Tooran; Demartini, Nikolai; Ivaska, Ari; Fardim, Pedro; Hupa, Mikko

    2012-11-01

    Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction.

  5. Amino Acids, Aromatic Compounds, and Carboxylic Acids: How Did They Get Their Common Names?

    Science.gov (United States)

    Leung, Sam H.

    2000-01-01

    Surveys the roots of the common names of organic compounds most likely to be encountered by undergraduate organic chemistry students. Includes information for 19 amino acids, 17 aromatic compounds, and 21 carboxylic acids. (WRM)

  6. Theoretical study of structure and stability of small gadolinium carboxylate complexes in liquid scintillator solvents.

    Science.gov (United States)

    Huang, Pin-Wen

    2014-09-01

    The structural properties of three small gadolinium carboxylate complexes in three liquid scintillator solvents (pseudocumene, linear alkylbenzene, and phenyl xylylethane) were theoretically investigated using density functional theory (B3LYP/LC-RECP) and polarizable continuum model (PCM). The average interaction energy between gadolinium atom and carboxylate ligand (E(int)) and the energy difference of the highest singly occupied molecular orbital and lowest unoccupied molecular orbital (Δ(SL)) were calculated to evaluate and compare the relative stability of these complexes in solvents. The calculation results show that the larger (with a longer alkyl chain) gadolinium carboxylate complex has greater stability than the smaller one, while these gadolinium carboxylates in linear alkylbenzene were found to have greater stability than those in the other two solvents.

  7. Synthesis and Anti-influenza Virus Activity of Ethyl 6-Bromo-5-hydroxyindole-3-carboxylate Derivatives

    Institute of Scientific and Technical Information of China (English)

    Yan Fang ZHAO; Jin Hua DONG; Ping GONG

    2004-01-01

    A series of ethyl 6-bromo-5-hydroxyindole-3-carboxylate derivatives were synthesized and their in vitro anti-influenza virus activity was evaluated. All the compounds were characterized by 1H NMR and MS.

  8. Palladium-Catalyzed C–C Bond Formations via Activation of Carboxylic Acids and Their Derivatives

    OpenAIRE

    Song, Bingrui

    2013-01-01

    Applications of carboxylic acids and their derivatives in transition metal-catalyzed cross-coupling reactions regio-selectively forming Csp3-Csp2, and Csp2-Csp2 bonds were explored in this thesis. Several important organic building blocks such as aryl acetates, diaryl acetates, imines, ketones, biaryls, styrenes and polysubstituted alkenes were successfully accessed from carboxylic acids and their derivatives by the means of C–H activation and decarboxylative cross-couplings. An efficient ...

  9. Expedited Synthesis of Benzofuran-2-Carboxylic Acids via Microwave-Assisted Perkin Rearrangement Reaction

    OpenAIRE

    Marriott, Karla-Sue C.; Bartee, Rena; Morrison, Andrew Z.; Stewart, Leonard; Wesby, Julian

    2012-01-01

    3-Halocoumarins are readily converted into benzofuran-2-carboxylic acids via a Perkin (coumarin-benzofuran ring contraction) rearrangement reaction. This rearrangement entails initial base catalyzed ring fission. The resulting phenoxide anion then attacks a vinyl halide to produce the final benzofuran moiety. We explored this reaction under microwave reaction conditions and were able to significantly reduce reaction times as well as obtain very high yields of a series of benzofuran-2-carboxyl...

  10. Gamma-aminoadamantane carboxylic acids : orientating building blocks in peptide chemistry

    OpenAIRE

    Wanka, Lukas

    2007-01-01

    The present thesis deals with gamma-aminoadamantane carboxylic acids. Allthough the simplest of these structural analogues of GABA were known for decades, no significant peptide chemistry has been disclosed. Therefore, improved syntheses of these compounds were worked out that allowed for facilitated syntheses of already known as well as new members of gamma-aminoadamantane carboxylic acids. Fmoc-/tert. butyl protective group chemistry was utilized to synthesize peptides incorporating the gam...

  11. Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines

    Directory of Open Access Journals (Sweden)

    Brett N. Hemric

    2016-01-01

    Full Text Available This paper reports a novel approach for the direct and facile synthesis of 1,2-oxyamino moieties via an intermolecular copper-catalyzed oxyamination of olefins. This strategy utilizes O-benzoylhydroxylamines as an electrophilic amine source and carboxylic acids as a nucleophilic oxygen source to achieve a modular difunctionalization of olefins. The reaction proceeded in a regioselective manner with moderate to good yields, exhibiting a broad scope of carboxylic acid, amine, and olefin substrates.

  12. A Simple Method for the Determination of Enantiomeric Excess and Identity of Chiral Carboxylic Acids

    OpenAIRE

    Joyce, Leo A.; Maynor, Marc S.; Dragna, Justin M.; da Cruz, Gabriella M.; Lynch, Vincent M.; Canary, James W.; Eric V. Anslyn

    2011-01-01

    The association between an achiral copper(II) host (1) and chiral carboxylate guests was studied using exciton-coupled circular dichroism (ECCD). Enantiomeric complexes were created upon binding of the enantiomers of the carboxylate guests to the host, and the sign of the resultant CD signal allowed for determination of the configuration of the studied guest. The difference in magnitudes and shapes of the CD signals, in conjunction with linear discriminant analysis (LDA), allowed for the iden...

  13. How many carboxyl groups does an average molecule of humic-like substances contain?

    Directory of Open Access Journals (Sweden)

    I. Salma

    2008-05-01

    Full Text Available The carboxyl groups of atmospheric humic-like substances (HULIS are of special interest because they influence the solubility in water, affect the water activity and surface tension of droplets in the air, and allow formation of chelates with biologically active elements. Experimentally determined abundances of the carboxyl group within HULIS by functional group analysis are consistent with our knowledge on the average molecular mass of HULIS if the number of dissociable carboxyl groups is assumed to be rather small. The best agreement between the average molecular mass derived from the existing abundance data and the average molecular mass published earlier occurs for assuming approximately one dissociable carboxyl group only. This implies that HULIS can not be regarded as polycarboxilic acid. The average molecular mass of HULIS derived from our electrochemical measurements with the assumption of one dissociable carboxyl group per molecule ranges from 248 to 305 Da. It was concluded that HULIS are a moderately strong/weak acid with a dissociation constant of about pK=3.4, which fits well into the interval represented by fulvic and humic acids. The mean number of dissociable carboxyl groups in HULIS molecules was refined to be between 1.1 and 1.4.

  14. How many carboxyl groups does an average molecule of humic-like substances contain?

    Directory of Open Access Journals (Sweden)

    I. Salma

    2008-10-01

    Full Text Available The carboxyl groups of atmospheric humic-like substances (HULIS are of special interest because they influence the solubility in water, affect the water activity and surface tension of droplets in the air, and allow formation of chelates with biologically active elements. Experimentally determined abundances of the carboxyl group within HULIS by functional group analysis are consistent with our knowledge on the average molecular mass of HULIS if the number of dissociable carboxyl groups is assumed to be rather small. The best agreement between the average molecular mass derived from the existing abundance data and the average molecular mass published earlier occurs for assuming approximately one dissociable carboxyl group only. This implies that HULIS can not be regarded as polycarboxilic acid in diluted solutions. The average molecular mass of HULIS derived from our electrochemical measurements with the assumption of one dissociable carboxyl group or equivalently, one dissociable sulphate ester per molecule ranges from 250 to 310 Da. It was concluded that HULIS are a moderately strong/weak acid with a dissociation constant of about pK=3.4, which fits well into the interval represented by fulvic and humic acids. The mean number of dissociable hydrogen (i.e. of carboxyl groups and sulphate esters jointly in HULIS molecules was refined to be between 1.1 and 1.4 in acidic solutions.

  15. Spectrophotometric tool for the determination of the total carboxylate content in proteins; molar extinction coefficient of the enol ester from Woodward's reagent K reacted with protein carboxylates

    NARCIS (Netherlands)

    Kosters, H.A.; Jongh, H.H.J.de

    2003-01-01

    A number of relevant properties of Woodward's reagent K have been determined, such as the stability of the reactant and the optimal reaction conditions of the reactant with protein carboxylates. A Woodward's reagent K stock solution was stable at 4°C for prolonged time, whereas upon storage at 22°C,

  16. Effect of substituent position on electrodeposition, morphology, and capacitance performance of polyindole bearing a carboxylic group

    International Nuclear Information System (INIS)

    Graphical abstract: The effect of carboxylic substituent position on the electrodeposition, morphology, and capacitance performance of substituted polyindole derivative nanowires were investigated for the first time. The results indicated that the position of the carboxylic substitution had remarkable impact on the diameter size and capacitance performance of these polymer nanowires. Furthermore, these polymers with high specific capacitance and excellent stability would be strong candidates as electrode material for supercapacitor. - Highlights: • Three carboxylic group substituted polyindole nanowires were synthesized. • Effect of substituent position on their morphology was firstly reported. • Effect of substituent position on their capacitance performance was reported. • The three polyindole nanowires showed excellent capacitance performance. - Abstract: In this paper, the effects of carboxylic substituent position on their electrodeposition, morphology and capacitance properties were investigated for the first time. The results indicated that three carboxylic group substituted polyindole derivatives nanowires, namely poly(indole-5-carboxylic acid) (5-PICA), poly(indole-6-carboxylic acid) (6-PICA), and poly(indole-7-carboxylic acid) (7-PICA), were successfully electrochemically synthesized in acetonitrile containing 0.1 M LiClO4, whereas poly(indole-4-carboxylic acid) (4-PICA) was difficult to be obtained. For 5-PICA, 6-PICA and 7-PICA nanowires, the diameters of nanowires demonstrated by the scanning electron microscopy were about 100 nm, 50 nm, and 30 nm, respectively. Their specific capacitances and energy densities in 1.0 M H2SO4 solution were measured to be 355 F g−1, 383 F g−1, 430 F g−1 at 2.5 A g−1 and 40.0, 43.1, 48.3 Wh kg−1 at a power density of 1125 W kg−1, respectively, and their specific capacitance retentions after 1000 charge/discharge processes reached 94.5%, 95.1%, and 96%, respectively. These results indicated that the

  17. Synthesis, spectroscopic characterization, biological screenings, DNA binding study and POM analyses of transition metal carboxylates

    Science.gov (United States)

    Uddin, Noor; Sirajuddin, Muhammad; Uddin, Nizam; Tariq, Muhammad; Ullah, Hameed; Ali, Saqib; Tirmizi, Syed Ahmed; Khan, Abdur Rehman

    2015-04-01

    This article contains the synthesis of a novel carboxylic acid derivative, its transition metal complexes and evaluation of biological applications. Six carboxylate complexes of transition metals, Zn(II) and Hg(II), have been successfully synthesized and characterized by FT-IR and NMR (1H, 13C). The ligand, HL, (4-[(2,6-Diethylphenyl)amino]-4-oxobutanoic acid) was also characterized by single crystal X-ray analysis. The complexation occurs via oxygen atoms of the carboxylate moiety. FT-IR date show the bidentate nature of the carboxylate moiety of the ligand as the Δν value in all complexes is less than that of the free ligand. The ligand and its complexes were screened for antifungal and antileishmanial activities. The results showed that the ligand and its complexes are active with few exceptions. UV-visible spectroscopy and viscometry results reveal that the ligand and its complexes interact with the DNA via intercalative mode of interaction. A new and efficient strategy to identify the pharmacophores and anti-pharmacophores sites in carboxylate derivatives for the antibacterial/antifungal activity using Petra, Osiris and Molinspiration (POM) analyses was also carried out.

  18. Phosphorescent emissions of phosphine copper(I) complexes bearing 8-hydroxyquinoline carboxylic acid analogue ligands

    International Nuclear Information System (INIS)

    The pseudotetrahedral complexes of [Cu(PPh3)2(L)], where L=8-hydroxy-2-methylquinoline-7-carboxylic acid (1), 8-hydroxy-2,5-dimethylquinoline-7-carboxylic acid (2) or 5-chloro-8-hydroxy-2-methylquinoline-7-carboxylic acid (3) have been synthesized and structurally characterized by X-ray crystallography. Their properties have been examined through combinations of IR, NMR, electronic absorption spectroscopy and cyclic voltammetry. The complexes exhibit extraordinary photophysical properties. Complex (1) in solid state exhibits an emission quantum yield of 4.67% and an excited life time of 1.88 ms (frozen DCM solution up to 6.7 ms). When dissolved in a coordinating solvent (acetonitrile) the charge transfer emission was quenched on a microsecond scale. - Highlights: • Synthesis of copper(I) complexes with 8-hydroxyquinoline carboxylic acid ligands. • Very long lived phosphorescent copper(I) complexes. • [Cu(PPh3)2(L)] where L=8-hydroxy-2-methylquinoline-7-carboxylic acid luminesce in the solid state exhibits extremely long lifetime on millisecond scale (1.9 ms). • In frozen MeOH:EtOH solution lifetime increases to 7 ms. • Quantum efficiency equal to 4.7%

  19. Improved antifouling properties of polyamide nanofiltration membranes by reducing the density of surface carboxyl groups.

    Science.gov (United States)

    Mo, Yinghui; Tiraferri, Alberto; Yip, Ngai Yin; Adout, Atar; Huang, Xia; Elimelech, Menachem

    2012-12-18

    Carboxyls are inherent functional groups of thin-film composite polyamide nanofiltration (NF) membranes, which may play a role in membrane performance and fouling. Their surface presence is attributed to incomplete reaction of acyl chloride monomers during the membrane active layer synthesis by interfacial polymerization. In order to unravel the effect of carboxyl group density on organic fouling, NF membranes were fabricated by reacting piperazine (PIP) with either isophthaloyl chloride (IPC) or the more commonly used trimesoyl chloride (TMC). Fouling experiments were conducted with alginate as a model hydrophilic organic foulant in a solution, simulating the composition of municipal secondary effluent. Improved antifouling properties were observed for the IPC membrane, which exhibited lower flux decline (40%) and significantly greater fouling reversibility or cleaning efficiency (74%) than the TMC membrane (51% flux decline and 40% cleaning efficiency). Surface characterization revealed that there was a substantial difference in the density of surface carboxyl groups between the IPC and TMC membranes, while other surface properties were comparable. The role of carboxyl groups was elucidated by measurements of foulant-surface intermolecular forces by atomic force microscopy, which showed lower adhesion forces and rupture distances for the IPC membrane compared to TMC membranes in the presence of calcium ions in solution. Our results demonstrated that a decrease in surface carboxyl group density of polyamide membranes fabricated with IPC monomers can prevent calcium bridging with alginate and, thus, improve membrane antifouling properties. PMID:23205860

  20. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part I. Regeneration of Amine-Carboxylic Acid Extracts

    Energy Technology Data Exchange (ETDEWEB)

    Poole, L.J.; King, C.J.

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The concentration

  1. Absence of Vitamin K-Dependent γ-Carboxylation in Human Periostin Extracted from Fibrotic Lung or Secreted from a Cell Line Engineered to Optimize γ-Carboxylation.

    Directory of Open Access Journals (Sweden)

    Douglas S Annis

    Full Text Available Periostin (PN, gene name POSTN is an extracellular matrix protein that is up-regulated in bronchial epithelial cells and lung fibroblasts by TH-2 cytokines. Its paralog, TGF-β-induced protein (βig-h3, gene name TGFBI, is also expressed in the lung and up-regulated in bronchial myofibroblasts by TGF-β. PN and βig-h3 contain fasciclin 1 modules that harbor putative recognition sequences for γ-glutamyl carboxylase and are annotated in UniProt as undergoing vitamin K-dependent γ-carboxylation of multiple glutamic acid residues. γ-carboxylation profoundly alters activities of other proteins subject to the modification, e.g., blood coagulation factors, and would be expected to alter the structure and function of PN and βig-h3. To analyze for the presence of γ-carboxylation, proteins extracted from fibrotic lung were reacted with monoclonal antibodies specific for PN, βig-h3, or modification with γ-carboxyglutamic acid (Gla. In Western blots of 1-dimensional gels, bands stained with anti-PN or -βig-h3 did not match those stained with anti-Gla. In 2-dimensional gels, anti-PN-positive spots had pIs of 7.0 to >8, as expected for the unmodified protein, and there was no overlap between anti-PN-positive and anti-Gla-positive spots. Recombinant PN and blood coagulation factor VII were produced in HEK293 cells that had been transfected with vitamin K 2, 3-epoxide reductase C1 to optimize γ-carboxylation. Recombinant PN secreted from these cells did not react with anti-Gla antibody and had pIs similar to that found in extracts of fibrotic lung whereas secreted factor VII reacted strongly with anti-Gla antibody. Over 67% coverage of recombinant PN was achieved by mass spectrometry, including peptides with 19 of the 24 glutamates considered targets of γ-carboxylation, but analysis revealed no modification. Over 86% sequence coverage and three modified glutamic acid residues were identified in recombinant fVII. These data indicate that PN and

  2. Water-enhanced solubility of carboxylic acids in organic solvents and its applications to extraction processes

    Energy Technology Data Exchange (ETDEWEB)

    Starr, J.N.; King, C.J.

    1991-11-01

    The solubilities of carboxylic acids in certain organic solvents increase remarkably with an increasing amount of water in the organic phase. This phenomenon leads to a novel extract regeneration process in which the co-extracted water is selectively removed from an extract, and the carboxylic acid precipitates. This approach is potentially advantageous compared to other regeneration processes because it removes a minor component of the extract in order to achieve a large recovery of acid from the extract. Carboxylic acids of interest include adipic acid, fumaric acid, and succinic acid because of their low to moderate solubilities in organic solvents. Solvents were screened for an increase in acid solubility with increased water concentration in the organic phase. Most Lewis-base solvents were found to exhibit this increased solubility phenomena. Solvents that have a carbonyl functional group showed a very large increase in acid solubility. 71 refs., 52 figs., 38 tabs.

  3. Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2.

    Science.gov (United States)

    Juliá-Hernández, Francisco; Gaydou, Morgane; Serrano, Eloisa; van Gemmeren, Manuel; Martin, Ruben

    2016-08-01

    The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO2) as a C1 building block has recently attracted considerable attention. Among the different alternatives in CO2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via waste-producing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO2 by using cheap and available Ni or Fe catalytic species. PMID:27573397

  4. Beyond ketonization: selective conversion of carboxylic acids to olefins over balanced Lewis acid–base pairs

    Energy Technology Data Exchange (ETDEWEB)

    Baylon, Rebecca A. L.; Sun, Junming; Martin, Kevin J.; Venkitasubramanian, Padmesh; Wang, Yong

    2016-01-01

    Dwindling petroleum reserves combined with increased energy demand and political factors encouraging an increase in energy independence have led to a large amount of research on sustainable alternatives. To this end, biomass conversion has been recognized as themost readily viable technology to produce biofuel concerning our reliance on liquid fuels for transportation and has the advantage of being easily integrated into our heavy use of combustion engines. The interest in biomass conversion has also resulted in reduced costs and a greater abundance of bio-oil, a mixture of hundreds of oxygenates including alcohols, aldehydes, carboxylic acids, and ketones. However, the presence of carboxylic acids in bio-oil derived from lignocellulose pyrolysis leads to low pH, instability, and corrosiveness. In addition, carboxylic acids (i.e. acetic acid) can also be produced via fermentation of sugars. This can be accomplished by a variety of homoacetogenic microorganisms that can produce acetic acid with 100% carbon yield.

  5. The investigation of the reactions of some pyrazole-3-carboxylic acids with various diamines and diols

    Directory of Open Access Journals (Sweden)

    Rahmi Kasımoğulları

    2012-06-01

    Full Text Available In this study, some new derivatives were synthesized of 4-benzoyl-1-(3-nitrophenyl-5-phenyl-1H-pyrazole-3-carboxylic acid (1 and 4-(ethoxycarbonyl-1-(3-nitrophenyl-5-phenyl-1H-pyrazole-3-carboxylic acid (2 that they were pyrazole carboxylic acid derivatives. Firstly, 1 and 2 reacted with SOCl2 to transform them into acyl chlorides (3, 4. Then various bis-carboxamide derivatives (5–8 were obtained from the reaction of 3 and 4 with various diamines and also a ;#946;-hydroxy ester (9 derivative was obtained from the reaction of 3 with ethylene glycol. The structures of synthesized compounds were elucidated with using FT-IR, 1H NMR, 13C NMR and elemental analysis methods.

  6. Crystal Structure and Properties of the Carboxylic Acid Derivatives of Schizonpeta mulifida (L.) Briq.

    Institute of Scientific and Technical Information of China (English)

    LIU,Ju-Tao; YU,Ji-Cheng; JIANG,Hui-Ming; ZHANG,Li-Ying; ZHAO,Xiao-Jing; FAN,Sheng-Di

    2008-01-01

    The chemical constituents of the carboxylic acid derivatives from the ear of Schizonepeta were investigated,1H and 13C NMR chemical shifts of the carboxylic acid derivatives were accurately assigned.Two carboxylic acid derivative constituents were separated by a silica gel column.The structures were elucidated by the physical and chemical properties,IR,1H NMR,13C NMR,MALDI-TDF-MS and X-ray single crystal diffractometry.They were identified as 3-imino-N-(a-imidoethylamino)butyrolactam and neononane tetracid,respectively.The antitumoral activity on liver tumor ceils SMMC-7721 was determined in vitro.The experimental results showed that the former was better than the latter,and with increasing the concentration of the former the inhibitory activity was increased.

  7. Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2.

    Science.gov (United States)

    Juliá-Hernández, Francisco; Gaydou, Morgane; Serrano, Eloisa; van Gemmeren, Manuel; Martin, Ruben

    2016-08-01

    The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO2) as a C1 building block has recently attracted considerable attention. Among the different alternatives in CO2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via waste-producing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO2 by using cheap and available Ni or Fe catalytic species.

  8. Chiral trans-1,2-diaminocyclohexane derivatives as chiral solvating agents for carboxylic acids

    Indian Academy of Sciences (India)

    Mariappan Periasamy; Manasi Dalai; Meduri Padmaja

    2010-07-01

    Efficient use of the readily accessible chiral 2-symmetric acyclic diamines (1-2) as well as macrocyclic amines (3-5) containing trans-1,2-diaminocyclohexyl moiety as chiral solvating agents (CSA) for the determination of enantiomeric excess of representative carboxylic acids (6-7) and an amino acid derivative (8) is illustrated. The enantiomeric composition of different carboxylic acids estimated here by the 1H NMR method, based on the integration of the corresponding methine proton signals are in good correlation with that determined using HPLC method. The data are in accordance with the formation of multimolecular diastereomeric complexes in solution, which render good splitting of NMR signals for the enantiomers of representative carboxylic acids as well as for -Ts-phenylglycine (up to = 0.295 ppm, 118 Hz).

  9. Preparation, Photo and Electroluminescence Properties of Novel Rare Earth Aromatic Carboxylates

    Institute of Scientific and Technical Information of China (English)

    林秦; 符连社; 梁玉军; 郑佑轩; 林君; 张洪杰

    2002-01-01

    Novel soluble rare earth aromatic carboxylates were prepared. The triplet energy level of organic ligand was measured. The photoluminescence properties of the Tb3+ and Eu3+ aromatic carboxylates and lifetimes were investigated, which indicated that these rare earth complexes have high quantum efficiency. Because of their excellent solubility, polymer-doping rare earth carboxylates were fabricated as thin films by spin-coating method and their luminescence properties were studied. Some rare earth organic light-emitting diodes were successfully fabricated which performed high pure color. The maximum luminance of the device of ITO/PVK/PVK∶Tb(AS)3Phen∶PBD/PBD/Al is 32 cd*m-2 at 28 V.

  10. Communication: Physical origins of ionization potential shifts in mixed carboxylic acids and water complexes

    Science.gov (United States)

    Gu, Quanli; Tang, Zhen; Su, Peifeng; Wu, Wei; Yang, Zhijun; Trindle, Carl O.; Knee, Joseph L.

    2016-08-01

    The ionization potential (IP) of the aromatic alpha hydroxy carboxylic acid, 9-hydroxy-9-fluorene carboxylic acid (9HFCA), is shifted by complexation with hydrogen bonding ligands such as water and formic acid. Generalized Kohn-Sham energy decomposition analysis decomposes the intermolecular binding energies into a frozen energy term, polarization, correlation, and/or dispersion energy terms, as well as terms of geometric relaxation and zero point energy. We observe that in each dimer the attractive polarization always increases upon ionization, enhancing binding in the cation and shifting the IP toward the red. For 9HFCA—H2O, a substantial decrease of the repulsive frozen energy in cation further shifts the IP toward red. For 9HFCA—HCOOH, the increase of the frozen energy actually occurs in the cation and shifts the IP toward blue. Consistent with the experimental measurements, our analysis provides new, non-intuitive perspectives on multiple hydrogen bonds interactions in carboxylic acids and water complexes.

  11. Carboxylated dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, electronic properties, and complexation with zinc ions

    Directory of Open Access Journals (Sweden)

    Yunfei Wang

    2015-06-01

    Full Text Available A class of carboxyl and carboxylate ester-substituted dithiafulvene (DTF derivatives and tetrathiafulvalene vinylogues (TTFVs has been synthesized and their electronic and electrochemical redox properties were characterized by UV–vis spectroscopic and cyclic voltammetric analyses. The carboxyl-TTFV was applied as a redox-active ligand to complex with Zn(II ions, forming a stable Zn-TTFV coordination polymer. The structural, electrochemical, and thermal properties of the coordination polymer were investigated by infrared spectroscopy, cyclic voltammetry, powder X-ray diffraction, and differential scanning calorimetric analyses. Furthermore, the microscopic porosity and surface area of the Zn-TTFV coordination polymer were measured by nitrogen gas adsorption analysis, showing a BET surface of 148.2 m2 g−1 and an average pore diameter of 10.2 nm.

  12. Quantitative structure-property relationship of aromatic sulfur-containing carboxylates

    Institute of Scientific and Technical Information of China (English)

    LIU Xin-hui; YANG Zhi-feng; WANG Lian-sheng

    2003-01-01

    Based on quantum chemical calculations, TLSER model (theoretical linear solvation energy relationships) and atomic charge approach were applied to model the partition properties(water solubility and octanol/water partition coefficient) of 96 aromatic sulfur-containing carboxylates, including phenylthio, phenylsulfinyl and phenylsulfonyl carboxylates. In comparison with TLSER models, the atomic charge models are more accurate and reliable to predict the partition properties of the kind of compounds. For the atomic charge models, the molecular descriptors are molecular surface area( S ), molecular shape( O ), weight( Mw ), net charges on carboxyl group( QOC ), net charges of nitrogen atoms(Q N), and the most negative atomic charge( q- ) of the solute molecule. For water solubility (log Sw ) and octanol/water partition coefficient(log Kow), the correction coefficients r2adj(adjusted for degrees of freedom) are 0.936 and 0.938, and the standard deviations are 0.364 and 0.223, respectively.

  13. Carboxylic acid derivatives via catalytic carboxylation of unsaturated hydrocarbons: whether the nature of a reductant may determine the mechanism of CO2 incorporation?

    OpenAIRE

    Kirillov, E.; Carpentier, J.-F.; Bunel, E

    2015-01-01

    International audience Application of CO2 as a renewable feedstock and C1 building block for prodn. of commodity and fine chems. is a highly challenging but obvious industry-relevant task. Of particular interest is the catalytic coupling of CO2 with inexpensive unsatd. hydrocarbons (olefins, dienes, styrenes, alkynes), providing direct access to carboxylic acids and their derivs. Although not brand new for the scientific community, it is still a complete challenge, as no truly effective ca...

  14. Photosensitization of Nanocrystalline TiO2 Electrode Modifiedwith C60 Carboxylic Acid Derivatives

    Institute of Scientific and Technical Information of China (English)

    张文; 史亚茹; 甘良兵; 黄春辉; 王艳琴; 虎民

    2001-01-01

    C60 carboxylic acid derivatives can be readily adsorbed on the surface of nanocrystalline TiO2 films act as charge-transfer sensitizer. The electron transport from TiO2 to the C60 derivatives results in the generation of the cathodic photocurrent. The short-circuit photocurrent of a C60 tetracarboxylic acid is 0.45 μA/cm2 under 464 um light illumination. The photoelectric behaviour of ITO electrodes modified by the same C60 carboxylic acids is different from that of the modified TiO2 electrodes, and shows anodic photocurrent.

  15. 2-sec-Butyl-1-(2-hydroxyethyl-1H-benzimidazole-5-carboxylic acid

    Directory of Open Access Journals (Sweden)

    Nurasyikin Hamzah

    2012-07-01

    Full Text Available In the title compound, C14H18N2O3, the carboxylic group is tilted by 12.00 (4° with respect to the mean plane throught the benzimidazole ring system. The alcohol and carboxyl hydroxy groups are involved in intermolecular O—H...O and O—H...N hydrogen bonds, forming a two-dimensional network extending parallel the ab plane. The network is further stabilized by weak C—H...O interactions. The sec-butyl group is disordered over two sets of sites with refined occupancies of 0.484 (4 and 0.516 (4.

  16. Toward interfacing organic semiconductors with ferromagnetic transition metal substrates: enhanced stability via carboxylate anchoring.

    Science.gov (United States)

    Han, R; Blobner, F; Bauer, J; Duncan, D A; Barth, J V; Feulner, P; Allegretti, F

    2016-07-28

    We demonstrate that chemically well-defined aromatic self-assembled monolayers (SAMs) bonded via a carboxylate head group to surfaces of ferromagnetic (FM = Co, Ni, Fe) transition metals can be prepared at ambient temperature in ultra-high vacuum and are thermally stable up to 350-400 K (depending on the metal). The much superior stability over thiolate-bonded SAMs, which readily decompose above 200 K, and the excellent electronic communication guaranteed by the carboxylate bonding render benzoate/FM-metal interfaces promising candidates for application in spintronics. PMID:27417687

  17. Facile synthesis of α-hydroxy carboxylic acids from the corresponding α-amino acids

    DEFF Research Database (Denmark)

    Stuhr-Hansen, Nicolai; Padrah, Shahrokh; Strømgaard, Kristian

    2014-01-01

    An effective and improved procedure is developed for the synthesis of α-hydroxy carboxylic acids by treatment of the corresponding protonated α-amino acid with tert-butyl nitrite in 1,4-dioxane-water. The amino moiety must be protonated and located α to a carboxylic acid function in order...... to undergo initial diazotization and successive hydroxylation, since neither β-amino acids nor acid derivatives such as esters and amides undergo hydroxylations. The method is successfully applied for the synthesis of 18 proteinogenic amino acids. © 2014 Elsevier Ltd. All rights reserved....

  18. (±)-trans-3-Benzoyl-bicyclo-[2.2.2]octane-2-carboxylic acid.

    Science.gov (United States)

    Lalancette, Roger A; Thompson, Hugh W; Brunskill, Andrew P J

    2008-01-01

    The title keto acid, C(16)H(18)O(3), displays significant twisting of all three ethyl-ene bridges in its bicyclo-[2.2.2]octane structure owing to steric inter-actions; the bridgehead-to-bridgehead torsion angles are 13.14 (12), 13.14 (13) and 9.37 (13)°. The compound crystallizes as centrosymmetric carboxyl dimers [O⋯O = 2.6513 (12) Å and O-H⋯O = 178°], which have two orientations within the cell and contain no significant carboxyl disorder. PMID:21201657

  19. (±-trans-3-Benzoylbicyclo[2.2.2]octane-2-carboxylic acid

    Directory of Open Access Journals (Sweden)

    Andrew P. J. Brunskill

    2008-09-01

    Full Text Available The title keto acid, C16H18O3, displays significant twisting of all three ethylene bridges in its bicyclo[2.2.2]octane structure owing to steric interactions; the bridgehead-to-bridgehead torsion angles are 13.14 (12, 13.14 (13 and 9.37 (13°. The compound crystallizes as centrosymmetric carboxyl dimers [O...O = 2.6513 (12 Å and O—H...O = 178°], which have two orientations within the cell and contain no significant carboxyl disorder.

  20. 5,6-dihydroxyindole-2-carboxylic acid (DHICA): a First Principles Density-Functional Study

    CERN Document Server

    Powell, B J

    2016-01-01

    We report first principles density functional calculations for 5,6-dihydroxyindole-2-carboxylic acid (DHICA) and several reduced forms. DHICA and 5,6-dihydroxyindole (DHI) are believed to be the basic building blocks of the eumelanins. Our results show that carboxylation has a significant effect on the physical properties of the molecules. In particular, the relative stabilities and the HOMO-LUMO gaps (calculated with the $\\Delta$SCF method) of the various redox forms are strongly affected. We predict that, in contrast to DHI, the density of unpaired electrons, and hence the ESR signal, in DHICA is negligibly small.

  1. IDENTIFICATION AND QUANTIFICATION OF AEROSOL POLAR OXYGENATED COMPOUNDS BEARING CARBOXYLIC AND/OR HYDROXYL GROUPS. 1. METHOD DEVELOPMENT

    Science.gov (United States)

    In this study, a new analytical technique was developed for the identification and quantification of multi-functional compounds containing simultaneously at least one hydroxyl or one carboxylic group, or both. This technique is based on derivatizing first the carboxylic group(s) ...

  2. Solvent-Free Esterification of Carboxylic Acids Using Supported Iron Oxide Nanoparticles as an Efficient and Recoverable Catalyst

    Directory of Open Access Journals (Sweden)

    Fatemeh Rajabi

    2016-07-01

    Full Text Available Supported iron oxide nanoparticles on mesoporous materials (FeNP@SBA-15 have been successfully utilized in the esterification of a variety carboxylic acids including aromatic, aliphatic, and long-chain carboxylic acids under convenient reaction conditions. The supported catalyst could be easily recovered after reaction completion and reused several times without any loss in activity after up to 10 runs.

  3. Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

    KAUST Repository

    Zhang, Tao

    2014-01-01

    Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

  4. Formation of biologically relevant carboxylic acids during the gamma irradiation of acetic acid

    Science.gov (United States)

    Negron-Mendoza, A.; Ponnamperuma, C.

    1976-01-01

    Irradiation of aqueous solutions of acetic acid with gamma rays produced several carboxylic acids in small yield. Their identification was based on the technique of gas chromatography combined with mass spectrometry. Some of these acids are Krebs Cycle intermediates. Their simultaneous formation in experiments simulating the primitive conditions on the earth suggests that metabolic pathways may have had their origin in prebiotic chemical processes.

  5. Optimal activation of carboxyl-superparamagnetic iron oxide nanoparticles bioconjugated with antibody using orthogonal array design.

    Science.gov (United States)

    Liu, Lin; Zhang, Xiaoqang; Zhang, Yu; Pu, Yuepu; Yin, Lihong; Tang, Meng; Liu, Hui

    2013-12-01

    This study aims to bioconjugate anti-EMMPRIN monoclonal antibody on the surface of carboxyl-SPIO nanoparticles and to optimize the activated conditions of bioconjugation. Anti-EMMPRIN monoclonal antibody bioconjugated carboxyl-SPIO nanoparticles were performed through a coupling strategy of EDC and sulfo-NHS. The procedure was comprised of two steps by activation of carboxyl-SPIO nanoparticles and conjugation with monoclonal antibody. The optimal activated parameters of bioconjugation were evaluated by single factor design and orthogonal array design. SDS-PAGE analysis and Bradford assay was used for testing and verifying the efficiency of activated conditions obtained from orthogonal array. The results show that pH value, temperature and reaction time were important factors that influence bioconjugated efficiency. The activated parameters with pH value 6.2, temperature 25 degrees C and reaction time 30 min were obviously optimal for activation of carboxyl-SPIO nanoparticles and conjugation with monoclonal EMMPEIN antibody. This coupling strategy for anti-EMMPRIN mAb bioconjugated on SPIO nanoparticles was efficient, and may be further applied in the fields of medical or biological practices. PMID:24266206

  6. Carboxylic Group Embedded Carbon Balls as a New Supported Catalyst for Hydrogen Economic Reactions.

    Science.gov (United States)

    Bordoloi, Ankur

    2016-03-01

    Carboxylic group functionalized carbon balls have been successfully synthesized by using a facile synthesis method and well characterized with different characterization techniques such as XPS, MAS NMR, SEM, ICP and N2 physi-sorption analysis. The synthesized material has been effectively utilized as novel support to immobilized ruthenium catalyst for hydrogen economic reactions. PMID:27455763

  7. Carboxyl terminal of rhodopsin kinase is required for the phosphorylation of photo—activated rhodopsin

    Institute of Scientific and Technical Information of China (English)

    YUQINGMING; LANMA; 等

    1998-01-01

    Human rhodopsin kinase (RK) and a carboxyl terminus-truncated mutant RK lacking the last 59 amino acids (RKC) were expressed in human embryonic kidney 293 cells to investigate the role of the carboxyl terminus of RK in recognition and phosphorylation of rhodopsin.RKC,like the wild-type RK,was detected in both plasma membranes and cytosolic fractions.The Cterminal truncated rhodopsin kinase was unable to phosphorylate photo-activated rhodopsin,but possesses kinase activity similar to the wild-type RK in phosphorylation of small peptide substrate.It suggests that the truncation did not disturb the gross structures of RK catalytic domain.Our results also show that RKC failed to translocate to photo-activated rod out segments.Taken together,our study demonstrate the carboxyl terminus of RK is required for phosphorylation of photo-activated rhodopsin and strongly indicate that carboxyl-terminus of RK may be involved in interaction with photo-activated rhodopsin.

  8. Catalysis of the Carbonylation of Alcohols to Carboxylic Acids Including Acetic Acid Synthesis from Methanol.

    Science.gov (United States)

    Forster, Denis; DeKleva, Thomas W.

    1986-01-01

    Monsanto's highly successful synthesis of acetic acid from methanol and carbon monoxide illustrates use of new starting materials to replace pretroleum-derived ethylene. Outlines the fundamental aspects of the acetic acid process and suggests ways of extending the synthesis to higher carboxylic acids. (JN)

  9. Templating route for mesostructured calcium phosphates with carboxylic acid- and amine-type surfactants.

    Science.gov (United States)

    Ikawa, Nobuaki; Hori, Hideki; Kimura, Tatsuo; Oumi, Yasunori; Sano, Tsuneji

    2008-11-18

    Mesostructured calcium phosphates constructed by ionic frameworks were synthesized using carboxylic acid- and amine-type surfactants in mixed solvent systems of ethanol and water. A lamellar mesostructured calcium phosphate was prepared using palmitic acid as an anionic surfactant, as in the case using n-alkylamines. A wormhole-like mesostructured calcium phosphate can be obtained using dicarboxyl N-lauroyl- l-glutamic acid, whose headgroup is larger than that of palmitic acid. Similar mesostructured product was obtained using 4-dodecyldiethylenetriamine with a large headgroup containing two primary amine groups. Interactions of carboxyl and primary amino groups in the surfactant molecules with inorganic species are quite important for the formation of mesostructured calcium phosphates. The Ca/P molar ratio of mesostructured calcium phosphates was strongly affected by the molecular structure of surfactants containing carboxyl and primary amino groups. Ca-rich materials can be obtained using carboxylic acid-type surfactants (Ca/P approximately 1.7) rather than amine-type surfactants (Ca/P approximately 1.0). PMID:18947246

  10. Carboxylic acid functional group analysis using constant neutral loss scanning-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Dron, Julien [Laboratoire de Chimie et Environnement, Marseille Universites (case 29), 3 place Victor Hugo, 13331 Marseille Cedex 3 (France)], E-mail: julien.dron@up.univ-mrs.fr; Eyglunent, Gregory; Temime-Roussel, Brice; Marchand, Nicolas; Wortham, Henri [Laboratoire de Chimie et Environnement, Marseille Universites (case 29), 3 place Victor Hugo, 13331 Marseille Cedex 3 (France)

    2007-12-12

    The present study describes the development of a new analytical technique for the functional group determination of the carboxylic moiety using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS/MS) operated in the constant neutral loss scanning (CNLS) mode. Carboxylic groups were first derivatized into their corresponding methyl esters by reacting with BF{sub 3}/methanol mix and the reaction mixture was then directly injected into the APCI chamber. The loss of methanol (m/z = 32 amu) resulting from the fragmentation of the protonated methyl esters was then monitored. Applying this method together with a statistical approach to reference mixtures containing 31 different carboxylic acids at randomly calculated concentrations demonstrated its suitability for quantitative functional group measurements with relative standard deviations below 15% and a detection limit of 0.005 mmol L{sup -1}. Its applicability to environmental matrices was also shown through the determination of carboxylic acid concentrations inside atmospheric aerosol samples. To the best of our knowledge, it is the first time that the tandem mass spectrometry was successfully applied to functional group analysis, offering great perspectives in the characterization of complex mixtures which are prevailing in the field of environmental analysis as well as in the understanding of the chemical processes occurring in these matrices.

  11. Carboxylate-bridged dinuclear manganese systems - From catalases to oxidation catalysis

    NARCIS (Netherlands)

    de Boer, Johannes W.; Browne, Wesley R.; Feringa, Ben L.; Hage, Ronald

    2007-01-01

    Dinuclear manganese based enzymes engage in processes as diverse as amino acid hydrolysis and hydrogen peroxide disproportionation. Despite the mechanistic diversity displayed by this class of enzymes, a common feature is the presence of carboxylate residues, which serve to bridge the manganese cent

  12. Application of IBX Method for the Synthesis of Ketones from Carboxylic Acids

    OpenAIRE

    KARABULUT, H. R. Ferhat; KAÇAN, Mesut

    2003-01-01

    Methoxy phenyl propionic acid and some derivatives are converted to ketones using a new method. All classical methods to obtain ketones from carboxylic acids via acid halide consistently gave very low yields and regularly generated intermolecular cyclisation products or polymeric materials. However, high ketones yields are obtained by using the new IBX method.

  13. Ionic liquids as solvent for efficient esterification of carboxylic acids with alkyl halides

    OpenAIRE

    carboxylic, Ionic liquids as solvent for efficient e

    2010-01-01

    The selective esterification of carboxylic acid derivatives with a variety of alkyl halides was carried out using ionic liquid as solvent in the presence of triethylamine. The reaction was found to proceed under relatively mild conditions with excellent conversions (up to 99%) and selectivities. The ionic liquid was recycled and reused.

  14. Acyl Radicals from Aromatic Carboxylic Acids by Means of Visible-Light Photoredox Catalysis

    OpenAIRE

    Bergonzini, Giulia; Cassani, Carlo; Wallentin, Carl-Johan

    2015-01-01

    Simple and abundant carboxylic acids have been used as acyl radical precursor by means of visible-light photoredox catalysis. By the transient generation of a reactive anhydride intermediate, this redox-neutral approach offers a mild and rapid entry to high-value heterocyclic compounds without the need of UV irradiation, high temperature, high CO pressure, tin reagents, or peroxides.

  15. The cannabinoid type-1 receptor carboxyl-terminus, more than just a tail.

    Science.gov (United States)

    Stadel, Rebecca; Ahn, Kwang H; Kendall, Debra A

    2011-04-01

    The cannabinoid type-1 (CB(1)) receptor is a G protein-coupled receptor that binds the main active ingredient of marijuana, Δ(9)-tetrahydrocannabinol, and has been implicated in several disease states, including drug addiction, anxiety, depression, obesity, and chronic pain. In the two decades since the discovery of CB(1), studies at the molecular level have centered on the transmembrane core. This interest has now expanded as we discover that other regions of CB(1), including the CB(1) carboxyl-terminus, have critical structures that are important for CB(1) activity and regulation. Following the recent description of the three dimensional structure of the full-length CB(1) carboxyl-terminal tail [Biopolymers (2009) vol. 91, pp. 565-573], several residues and structural motifs including two α-helices (termed H8 and H9) have been postulated to interact with common G protein-coupled receptor accessory proteins, such as G-proteins and β-arrestins. This discourse will focus on the CB(1) carboxyl-terminus; our current understanding of the structural features of this region, evidence for its interaction with proteins, and the impact of structure on the binding and regulatory function of CB(1) accessory proteins. The involvement of the carboxyl-terminus in the receptor life cycle including activation, desensitization, and internalization will be highlighted.

  16. Carboxylate-assisted C(sp³)-H activation in olefin metathesis-relevant ruthenium complexes.

    Science.gov (United States)

    Cannon, Jeffrey S; Zou, Lufeng; Liu, Peng; Lan, Yu; O'Leary, Daniel J; Houk, K N; Grubbs, Robert H

    2014-05-01

    The mechanism of C-H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C-H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation-deprotonation mechanism with ΔG(‡)(298K) = 22.2 ± 0.1 kcal·mol(-1) for the parent N-adamantyl-N'-mesityl complex. An experimentally determined ΔS(‡) = -5.2 ± 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp(3))-H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 ± 1.7), agree closely with a computed six-membered carboxylate-assisted C-H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment.

  17. Facilitation of peptide fibre formation by arginine-phosphate/carboxylate interactions

    Indian Academy of Sciences (India)

    K Krishna Prasad; Sandeep Verma

    2008-01-01

    This study describes peptide fibre formation in a hexapeptide, derived from the V3 loop of HIV-1, mediated by the interactions between arginine residues and phosphate/carboxylate anions. This charge neutralization approach was further confirmed when the deletion of arginine residue from the hexapeptide sequence resulted in fibre formation, which was studied by a combination of microscopic techniques.

  18. Carboxylic Group Embedded Carbon Balls as a New Supported Catalyst for Hydrogen Economic Reactions.

    Science.gov (United States)

    Bordoloi, Ankur

    2016-03-01

    Carboxylic group functionalized carbon balls have been successfully synthesized by using a facile synthesis method and well characterized with different characterization techniques such as XPS, MAS NMR, SEM, ICP and N2 physi-sorption analysis. The synthesized material has been effectively utilized as novel support to immobilized ruthenium catalyst for hydrogen economic reactions.

  19. Ab Initio Molecular Dynamics Study on the Interactions between Carboxylate Ions and Metal Ions in Water.

    Science.gov (United States)

    Mehandzhiyski, Aleksandar Y; Riccardi, Enrico; van Erp, Titus S; Trinh, Thuat T; Grimes, Brian A

    2015-08-20

    The interaction between a carboxylate anion (deprotonated propanoic acid) and the divalent Mg(2+), Ca(2+), Sr(2+), Ba(2+) metal ions is studied via ab initio molecular dynamics. The main focus of the study is the selectivity of the carboxylate-metal ion interaction in aqueous solution. The interaction is modeled by explicitly accounting for the solvent molecules on a DFT level. The hydration energies of the metal ions along with their diffusion and mobility coefficients are determined and a trend correlated with their ionic radius is found. Subsequently, a series of 16 constrained molecular dynamics simulations for every ion is performed, and the interaction free energy is obtained from thermodynamic integration of the forces between the metal ion and the carboxylate ion. The results indicate that the magnesium ion interacts most strongly with the carboxylate, followed by calcium, strontium, and barium. Because the interaction free energy is not enough to explain the selectivity of the reaction observed experimentally, more detailed analysis is performed on the simulation trajectories to understand the steric changes in the reaction complex during dissociation. The solvent dynamics appear to play an important role during the dissociation of the complex and also in the observed selectivity behavior of the divalent ions.

  20. ANTI-CORROSION PROPERTIES OF CARBOXYLIC ACID IN WATER-GLYCOL SOLUTIONS

    Directory of Open Access Journals (Sweden)

    BASHKIRCEVA N.Y.

    2012-01-01

    Full Text Available Sodium salts of carboxylic acids were investigated to evaluate the corrosion properties of the water-glycol solutions. Corrosion tests were performed by methods of gravimetry and galvanostatic dissolution with metals used in cooling systems. The compositions of anticorrosion systems and their concentration that provide the most effective inhibition of metals were determined.

  1. Highly Efficient Diastereoselective Synthesis of Tetrahydro-isoquinoline-3- carboxylate Ester Analogs from L-DOPA

    Institute of Scientific and Technical Information of China (English)

    WANG Ye; LIU Zhan-Zhu; CHEN Shi-Zhi; LIANG Xiao-Tian

    2003-01-01

    @@ Tetrahydroisoquinoline-3-carboxylate esters are an important motif of naturally occurring bioactive alkaloids and pharmacophores. They are generally regarded as neurotoxic compounds and are putatively involved in a variety of pathologic conditions of central nervous system, including alcoholism, phenylketonuria, and neurodegenerative disorders such as Parkinson's disease.

  2. Multilayer Film Fabrication and Photoelectric Conversion Property of Two Pyrrolidinofullerene Carboxylic Acid Derivatives

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Two multilayer films of pyrrolidinofullerene carboxylic acid derivatives, which exhibit photoelectric conversion property, are reported here. The first monolayers were fabricated on hydrophilic indium-tin-oxide (ITO), quartz, and mica by esterification reaction. The multilayers were characterized by contact angle and UV spectrum. The photoelectric conversion properties of both multilayer films were studied.

  3. One-pot synthesis of arene-fused 2-acylcyclohexenones from propargylic carboxylates

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    From readily available propargylic carboxylates, two sequential transformations―gold-catalyzed tandem reactions and Sc(OTf)3-catalyzed cyclization―in a one-pot process led to the formation of 2-acylcyclohexenones with an electron-rich arene ring fused at the 4,5-positions.

  4. One-pot synthesis of arene-fused 2-acylcyclohexenones from propargylic carboxylates

    Institute of Scientific and Technical Information of China (English)

    CAO SanSan; ZHANG LiMing

    2009-01-01

    From readily available propargylic carboxylates,two sequential transformations-gold-catalyzed tandem reactions and ScOTf3-catalyzed cyclization-in a one-pot process led to the formation of 2-acylcyclohexenones with an electron-rich arene ring fused at the 4,5-positions.

  5. Effect of hydrogen and carbon dioxide on carboxylic acids patterns in mixed culture fermentation

    NARCIS (Netherlands)

    Arslan, D.; Steinbusch, K.J.J.; Diels, L.; Wever, De H.; Buisman, C.J.N.; Hamelers, H.V.M.

    2012-01-01

    This study investigated the carboxylate spectrum from mixed culture fermentation of three organic waste streams after supplying 2 bar hydrogen and carbon dioxide or a mixture of these two gases to the headspace. Under any modified headspace, propionate production was ceased and butyrate, caproate an

  6. Extraction and solubility characteristics of metal aliphatic carboxylates in a hexane medium

    International Nuclear Information System (INIS)

    Extractions of 30 metal ions with aliphatic carboxylic acids into hexane were carried out to understand their extraction behavior. Results were expressed in an area-graph form for metal partitions among the three (aqueous, organic and/or solid) phases in the range pH 1-9. The difference in half-extraction pH (pH1/2) between various metals can be explained by the electrostatic effect (hard acids) and the polarizability. According to the solubility of the metal complexes into organic phase, the thirty metal ions were divided into two groups. The metal ions with high ionic potential (group A) were generally extractable by every carboxylic acid tested. The large size metal ions (group B) precipitated at the liquid/liquid interface by n-aliphatic carboxylic acids and were perfectly extracted by 2-ethylhexanoic acid. We propose that this difference in the group B is caused by interface-coagulation through inter-molecular hydrophobic bond formation in the former, while the branched chain in the carboxylic acid weakens the interaction in the latter. For group A, therefore, most of the extracted species would be origomers so that no coagulation would occur. (author)

  7. Effects of intermediate metabolite carboxylic acids of TCA cycle on Microcystis with overproduction of phycocyanin.

    Science.gov (United States)

    Bai, Shijie; Dai, Jingcheng; Xia, Ming; Ruan, Jing; Wei, Hehong; Yu, Dianzhen; Li, Ronghui; Jing, Hongmei; Tian, Chunyuan; Song, Lirong; Qiu, Dongru

    2015-04-01

    Toxic Microcystis species are the main bloom-forming cyanobacteria in freshwaters. It is imperative to develop efficient techniques to control these notorious harmful algal blooms (HABs). Here, we present a simple, efficient, and environmentally safe algicidal way to control Microcystis blooms, by using intermediate carboxylic acids from the tricarboxylic acid (TCA) cycle. The citric acid, alpha-ketoglutaric acid, succinic acid, fumaric acid, and malic acid all exhibited strong algicidal effects, and particularly succinic acid could cause the rapid lysis of Microcystis in a few hours. It is revealed that the Microcystis-lysing activity of succinic acid and other carboxylic acids was due to their strong acidic activity. Interestingly, the acid-lysed Microcystis cells released large amounts of phycocyanin, about 27-fold higher than those of the control. On the other hand, the transcription of mcyA and mcyD of the microcystin biosynthesis operon was not upregulated by addition of alpha-ketoglutaric acid and other carboxylic acids. Consider the environmental safety of intermediate carboxylic acids. We propose that administration of TCA cycle organic acids may not only provide an algicidal method with high efficiency and environmental safety but also serve as an applicable way to produce and extract phycocyanin from cyanobacterial biomass.

  8. Mapping of Fab-1:VEGF Interface Using Carboxyl Group Footprinting Mass Spectrometry

    Science.gov (United States)

    Wecksler, Aaron T.; Kalo, Matt S.; Deperalta, Galahad

    2015-12-01

    A proof-of-concept study was performed to demonstrate that carboxyl group footprinting, a relatively simple, bench-top method, has utility for first-pass analysis to determine epitope regions of therapeutic mAb:antigen complexes. The binding interface of vascular endothelial growth factor (VEGF) and the Fab portion of a neutralizing antibody (Fab-1) was analyzed using carboxyl group footprinting with glycine ethyl ester (GEE) labeling. Tryptic peptides involved in the binding interface between VEGF and Fab-1 were identified by determining the specific GEE-labeled residues that exhibited a reduction in the rate of labeling after complex formation. A significant reduction in the rate of GEE labeling was observed for E93 in the VEGF tryptic peptide V5, and D28 and E57 in the Fab-1 tryptic peptides HC2 and HC4, respectively. Results from the carboxyl group footprinting were compared with the binding interface identified from a previously characterized crystal structure (PDB: 1BJ1). All of these residues are located at the Fab-1:VEGF interface according to the crystal structure, demonstrating the potential utility of carboxyl group footprinting with GEE labeling for mapping epitopes.

  9. A Novel Metal-free Reductive Esterification of N-Tosylhydrazones with Carboxylic Acids

    Institute of Scientific and Technical Information of China (English)

    周安坤; 吴磊; 李大志; 陈庆庆; 张晓; 夏吾炯

    2012-01-01

    A novel method for the synthesis of esters via reductive coupling of N-tosylhydrazones with carboxylic acids under metal-free conditions has been developed. Various functional groups were found to be tolerable under the re- action conditions to afford low to good yields.

  10. Carboxylate-assisted C(sp³)-H activation in olefin metathesis-relevant ruthenium complexes.

    Science.gov (United States)

    Cannon, Jeffrey S; Zou, Lufeng; Liu, Peng; Lan, Yu; O'Leary, Daniel J; Houk, K N; Grubbs, Robert H

    2014-05-01

    The mechanism of C-H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C-H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation-deprotonation mechanism with ΔG(‡)(298K) = 22.2 ± 0.1 kcal·mol(-1) for the parent N-adamantyl-N'-mesityl complex. An experimentally determined ΔS(‡) = -5.2 ± 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp(3))-H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 ± 1.7), agree closely with a computed six-membered carboxylate-assisted C-H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment. PMID:24731019

  11. Substituted Amides of Pyrazine-2-carboxylic acids: Synthesis and Biological Activity

    Directory of Open Access Journals (Sweden)

    Katarina Kralova

    2002-03-01

    Full Text Available Condensation of 6-chloro-, 5-tert-butyl- or 6-chloro-5-tert-butylpyrazine-2-carboxylic acid chloride with ring substituted anilines yielded a series of amides, which were tested for their in vitro antimycobacterial, antifungal and photosynthesis-inhibiting activities. The highest antituberculotic activity (72% inhibition against Mycobacterium tuberculosis and the highest lipophilicity (log P = 6.85 were shown by the 3,5-bistrifluoromethylphenyl amide of 5-tert-butyl-6-chloropyrazine-2-carboxylic acid (2o. The 3-methylphenyl amides of 6-chloro- and 5-tert-butyl-6-chloro-pyrazine-2-carboxylic acid (2d and 2f exhibited only a poor in vitro antifungal effect (MIC = 31.25-500 μmol·dm-3 against all strains tested, although the latter was the most active antialgal compound (IC50 = 0.063 mmol·dm-3. The most active inhibitor of oxygen evolution rate in spinach chloroplasts was the (3,5-bis-trifluoromethylphenylamide of 6-chloropyrazine-2-carboxylic acid (2m, IC50 = 0.026 mmol·dm-3.

  12. Li-Carboxylate Anode Structure-Property Relationships from Molecular Modeling

    KAUST Repository

    Burkhardt, Stephen E.

    2013-01-22

    The full realization of a renewable energy strategy hinges upon electrical energy storage (EES). EES devices play a key role in storing energy from renewable sources (which are inherently intermittent), to efficient transmission (e.g., grid load-leveling), and finally into the electrification of transportation. Organic materials represent a promising class of electrode active materials for Li-ion and post-Li-ion batteries. Organics consist of low-cost, lightweight, widely available materials, and their properties can be rationally tuned using the well-established principles of organic chemistry. Within the class of organic EES materials, carboxylates distinguish themselves for Li-ion anode materials based on their observed thermal stability, rate capability, and high cyclability. Further, many of the carboxylates studied to date can be synthesized from renewable or waste feedstocks. This report begins with a preliminary molecular density-functional theory (DFT) study, in which the calculated molecular properties of a set of 12 known Li-ion electrode materials based on carboxylate and carbonyl redox couples are compared to literature data. Based on the agreement between theoretical and experimental data, an expanded study was undertaken to identify promising materials and establish design principles for anodes based on Li-carboxylate salts. Predictive computational studies represent an important step forward for the identification of organic anode materials. © 2012 American Chemical Society.

  13. Significant improvement in the pore properties of SBA-15 brought about by carboxylic acids and hydrothermal treatment

    Indian Academy of Sciences (India)

    Milan Kanti Naskar; M Eswaramoorthy

    2008-01-01

    A comparative study of the pore properties of SBA-15 samples prepared under nonhydrothermal and hydrothermal conditions, in the absence and presence of carboxylic acids such as succinic, tartaric and citric acids has been carried out. In the absence of carboxylic acid, flake-like and spheroid particles were generally obtained irrespective of the preparative procedures. On the other hand, stirring of the pre-mix induces a rod-like morphology in presence of carboxylic acids. The samples prepared under non-hydrothermal conditions exhibit a higher degree of silicate condensation compared to those synthesized under hydrothermal conditions. SBA-15 samples prepared under hydrothermal conditions show higher values of the d (100) spacing independent of the presence of carboxylic acids. Presence of carboxylic acids as well as hydrothermal treatment improves the pore properties of SBA-15.

  14. Synthesis of 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives

    International Nuclear Information System (INIS)

    Quinolin derivatives are a group of compounds known to possess a wide range of biological activities. The chemistry of quinolines together with their corresponding aldehydes were dealt with in chapter one of this study. Special emphasis was given to the chemistry of benzaldehyde. Twenty five 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives together with their corresponding intermediates were prepared in this work. Basically, the synthetic design of these compounds arise from the appropriate disconnections of the target 2-phenyl and 2,3-diphenyl-quinolin-4-carboxylic acids. The retro synthesis analysis of these compounds reveals pyruvic acid, aromatic amine and benzaldehyde or phenyl pyruvic acid, aromatic amine and benzaldehyde as possible logical precursors for 2-phenyl-and 2,3-diphenyl- quinoline-4-carboxylic acids respectively. The purity and identities of the synthesized compounds were elucidated through chromatographic and spectroscopic techniques. The compounds were heavily subjected to spectroscopic analysis (UV, IR, GC/MS, 1H-and 13C- NMR). The appropriate disconnections and the mechanisms of the corresponding reactions were given and discussed in chapter three. The spectral data were interpreted and correlated with the target structures. The prepared 2-phenyl- and 2,3-diphenyl-quinoline-4-carboxylic acid derivatives were screened for their antibacterial activity. The compounds were tested against the standard bacterial organisms B. subtilis, S. aureus, E. coli and P. vulgaris. Some of these compounds were devoid of antibacterial activity against S. aureus and P. vulgaris, while others showed moderate activity. All of the tested compounds showed an activity against B. subtilis and E. coli. 2,3-diphenyl -6-sulphanilamide-quinolin-4-carboxylic acid showed the highest activity against the four standard tested organisms.(Author)

  15. Floral Benzenoid Carboxyl Methyltransferases: From in Vitro to in Planta Function

    Energy Technology Data Exchange (ETDEWEB)

    Effmert,U.; Saschenbrecker, S.; Ross, J.; Negre, F.; Fraser, C.; Noel, J.; Dudareva, N.; Piechulla, B.

    2005-01-01

    Benzenoid carboxyl methyltransferases synthesize methyl esters (e.g., methyl benzoate and methyl salicylate), which are constituents of aromas and scents of many plant species and play important roles in plant communication with the surrounding environment. Within the past five years, eleven such carboxyl methyltransferases were isolated and most of them were comprehensively investigated at the biochemical, molecular and structural level. Two types of enzymes can be distinguished according to their substrate preferences: the SAMT-type enzymes isolated from Clarkia breweri, Stephanotis floribunda, Antirrhinum majus, Hoya carnosa, and Petunia hybrida, which have a higher catalytic efficiency and preference for salicylic acid, while BAMT-type enzymes from A. majus, Arabidopsis thaliana, Arabidopsis lyrata, and Nicotiana suaveolens prefer benzoic acid. The elucidation of C. breweri SAMT's three-dimensional structure allowed a detailed modelling of the active sites of the carboxyl methyltransferases and revealed that the SAM binding pocket is highly conserved among these enzymes while the methyl acceptor binding site exhibits some variability, allowing a classification into SAMT-type and BAMT-type enzymes. The analysis of expression patterns coupled with biochemical characterization showed that these carboxyl methyltransferases are involved either in floral scent biosynthesis or in plant defense responses. While the latter can be induced by biotic or abiotic stress, the genes responsible for floral scent synthesis exhibit developmental and rhythmic expression pattern. The nature of the product and efficiency of its formation in plants depend on the availability of substrates, the catalytic efficiency of the enzyme toward benzoic acid and/or salicylic acid, and the transcriptional, translational, and post-translational regulation at the enzyme level. The biochemical properties of benzenoid carboxyl methyltransferases suggest that the genes involved in plant defenses

  16. Carboxyl terminus-truncated α1D-adrenoceptors inhibit the ERK pathway.

    Science.gov (United States)

    Alfonzo-Méndez, Marco A; Castillo-Badillo, Jean A; Romero-Ávila, M Teresa; Rivera, Richard; Chun, Jerold; García-Sáinz, J Adolfo

    2016-08-01

    Human α1D-adrenoceptors are G protein-coupled receptors that mediate adrenaline/noradrenaline actions. There is a growing interest in identifying regulatory domains in these receptors and determining how they function. In this work, we show that the absence of the human α1D-adrenoceptor carboxyl tail results in altered ERK (extracellular signal-regulated kinase) and p38 phosphorylation states. Amino terminus-truncated and both amino and carboxyl termini-truncated α1D-adrenoceptors were transfected into Rat-1, HEK293, and B103 cells, and changes in the phosphorylation state of extracellular signal-regulated kinase was assessed using biochemical and biophysical approaches. The phosphorylation state of other protein kinases (p38, MEK1, and Raf-1) was also studied. Noradrenaline-induced ERK phosphorylation in Rat-1 fibroblasts expressing amino termini-truncated α1D-adrenoceptors. However, in cells expressing receptors with both amino and carboxyl termini truncations, noradrenaline-induced activation was abrogated. Interestingly, ERK phosphorylation that normally occurs through activation of endogenous G protein-coupled receptors, EGF receptors, and protein kinase C, was also decreased, suggesting that downstream steps in the mitogen-activated protein kinase pathway were affected. A similar effect was observed in B103 cells but not in HEK 293 cells. Phosphorylation of Raf-1 and MEK1 was also diminished in Rat-1 fibroblasts expressing amino- and carboxyl-truncated α1D-adrenoceptors. Our data indicate that expression of carboxyl terminus-truncated α1D-adrenoceptors alters ERK and p38 phosphorylation state. PMID:27146292

  17. ANALYSIS OF AIRBORNE CARBOXYLIC ACIDS AND PHENOLS AS THEIR PENTAFLUOROBENZYL DERIVATIVES: GAS CHROMATOGRAPHY/ION TRAP MASS SPECTROMETRY WITH A NOVEL CHEMICAL IONIZATION REAGENT, PFBOH. (R826247)

    Science.gov (United States)

    The complex photochemical transformations of biogenichydrocarbons such as isoprene and of anthropogenichydrocarbons such as aromatics are an important sourceof carboxylic acids in the troposphere. Theidentificationof unknown carboxylic acids can be difficul...

  18. Cyclopentane-1,3-dione: A Novel Isostere for the Carboxylic Acid Functional Group. Application to the Design of Potent Thromboxane (A2)-Receptor Antagonists

    OpenAIRE

    Ballatore, Carlo; Soper, James; Piscitelli, Francesco; James, Michael; Huang, Longchuan; Atasoylu, Onur; Huryn, Donna M.; Trojanowski, John Q.; Lee, Virginia M.-Y.; Brunden, Kurt R.; Smith, Amos B.

    2011-01-01

    Cyclopentane-1,3-diones are known to exhibit pKa values typically in the range of carboxylic acids. To explore the potential of the cyclopentane-1,3-dione unit as a carboxylic acid isostere, the physical-chemical properties of representative congeners were examined and compared with similar derivatives bearing carboxylic acid or tetrazole residues. These studies suggested that cyclopentane-1,3-diones may effectively substitute for the carboxylic acid functional group. To demonstrate the use o...

  19. Rapid and selective derivatizatin method for the nitrogen-sensitive detection of carboxylic acids in biological fluids prior to gas chromatographic analysis

    NARCIS (Netherlands)

    Lingeman, H.; Haan, H.B.P.; Hulshoff, A.

    1984-01-01

    A rapid and selective derivatization procedure is described for the pre-column labelling of carboxylic acids with a nitrogen-containing label. The carboxylic acid function is activated with 2-bromo-1-methylpyridinium iodide and the activated carboxylic acid function reacts with a primary or a second

  20. Electron-transfer fluorescence quenching processes in coaggregates between excited N-alkylcarbazoles as electron donors and 2, 4-dinitrophenyl carboxylates or pentafiuorophenyl carboxylates as acceptors

    Institute of Scientific and Technical Information of China (English)

    SHI, Ji-Liang; YI, Hu-Nan; XU, Jia-Yi; JIANG, Xi-Kui

    2000-01-01

    Electron-transfer processes facilitated by hydrophobiclipophilic interaction (HLI) between excited N-alkylcarbazoles (1-n, n=4, 8, 12, 16) as electron donors and 2,4dinnrophenyl carboxylates (2-n, n = 4, 8, 12, 16) or pentafluorophenyl carboxylates (3-n, n = 4, 8, 12, 16) as electron acceptors have been investigated by means of fluorescence spectroscopy in aqueous or aquiorgano binary mixtures.The fluorescence quenching of-n* by2-n or-n indicates that preassociation precedes the electron transfer. The extent of HLI-drtven coaggregation of the acceptor and the donor may be assessed from the B value of the equation I0/I = A + B [Q]. The chain-length effect and possibly also a chain-foldability effect, as well as the solvent aggregating power (SAgP)effect have been observed. Comparison of the quenching constants ( B ) for 1-n* /2-n combinations and 1-n* / 3-n combinations shows that the order of increasing B values for the quenching processes is 3-n < 2-n.

  1. Inhibition by 1-aminocyclobutane-1-carboxylate of the activity of 1-aminocyclopropane-1-carboxylate oxidase obtained from senescing petals of carnation (Dianthus caryophyllus L.) flowers.

    Science.gov (United States)

    Kosugi, Y; Oyamada, N; Satoh, S; Yoshioka, T; Onodera, E; Yamada, Y

    1997-03-01

    We partially purified 1-aminocyclopropane-1-carboxylate (ACC) oxidase from senescing petals of carnation (Dianthus caryophyllus L. cv. Nora) flowers and investigated its general characteristics, and, in particular, the inhibition of its activity by ACC analogs. The enzyme had an optimum pH at 7-7.5 and required Fe2+, ascorbate and NaHCO3 for its maximal activity. The Km for ACC was calculated as 111-125 microM in the presence of NaHCO3. Its M(r) was estimated to be 35 and 36 kDa by gel-filtration chromatography on HPLC and SDS-PAGE, respectively, indicating that the enzyme exists in a monomeric form. These properties were in agreement with those reported previously with ACC oxidases from different plant tissues including senescing carnation petals. Among six ACC analogs tested, 1-aminocyclobutane-1-carboxylate (ACBC) inhibited most severely the activity of ACC oxidase from carnation petals. ACBC acted as a competitive inhibitor with the Ki of 20-30 microM. The comparison between the Km for ACC and the Ki for ACBC indicated that ACBC had an affinity which was ca. 5-fold higher than that of ACC. Whereas ACC inactivated carnation ACC oxidase in a time-dependent manner during incubation, ACBC did not cause the inactivation of the enzyme. Preliminary experiments showed that ACBC and its N-substituted derivatives delayed the onset of senescence in cut carnation flowers.

  2. A Strained Disilane-Promoted Carboxylation of Organic Halides with CO2 under Transition-Metal-Free Conditions.

    Science.gov (United States)

    Mita, Tsuyoshi; Suga, Kenta; Sato, Kaori; Sato, Yoshihiro

    2015-11-01

    By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency.

  3. Arginine-responsive terbium luminescent hybrid sensors triggered by two crown ether carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Lasheng [Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Tang, Ke; Ding, Xiaoping [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Wang, Qianming, E-mail: qmwang@scnu.edu.cn [Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Zhou, Zhan; Xiao, Rui [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China)

    2013-12-01

    Crown ether carboxylic acids constitute main building blocks for the synthesis of terbium containing covalent cross-linked luminescent materials. Both the complexes and the hybrid nanomaterials could exhibit remarkable green emissions in pure water. More importantly, they were found to have a profound effect on the luminescence responses to arginine compared with glutamic acid, histidine, tryptophan, threonine, tyrosine and phenylalanine in aqueous environment. The present study provided the possibility of using a host–guest mechanism as a way of signal transduction based on lanthanide supramolecular hybrid materials. - Highlights: • Crown ether carboxylic acids were found to sensitize terbium ions among a group of ethers. • The complexes and silica hybrid materials were both prepared and characterized. • They could exhibit remarkable green emissions in pure water.

  4. Influence of a Hydrophobic Environment on the Structure of Arginine—Carboxylate Salt Bridge

    Institute of Scientific and Technical Information of China (English)

    封勇; 刘磊; 穆廷巍; 郭庆祥

    2002-01-01

    The exact structure of an arginine-carboxylate salt bridge in different chemical environments remains a controversial problem.In the present work,the zwitterionic and neutral forms of arginine-carboxylate salt bridge were studied by the B3LYP/6-311G(d,p)//PM3 method.It turns out that the neutral forms are more stable than the zwitterionic coumterparts in gas phase.However,whnen bound by α-cyclodextrin,the zwitterionic forms become more stable than the corresponding neutral ones.It is suggested that the hydrophobic environment provided by the cyclodextrin cavity leads to such behavior.Therefore,the salt bridge still could be in a zwitterionic form in the hydrophobic interior of the real proteins.

  5. Influence of a Hydrophobic Environment on the Structure of Arginine-Carboxylate Salt Bridge

    Institute of Scientific and Technical Information of China (English)

    FENG,Yong(封勇); LIU,Lei(刘磊); MU,Ting-Wei(穆廷巍); GUO,Qing-Xiang(郭庆祥)

    2002-01-01

    The exact structure of an arginine-carboxylate salt bridge in different chemical environments remains a controversial problem. In the present work, the zwitterionic and neutral forms of arginine-carboxylate salt bridge were studied by the B3LYP/6-311G(d,p)//PM3 method. It turns out that the neutral forms are more stable than the zwitterionic counterparis in gas phase.However, when bound by c-cyclodextrin, the zwitterionic forms become more stable than the corresponding neutral ones.It is suggested that the hydrophobic environment provided by the cyclodextrin cavity leads to such behavior. Tnerefore, the salt bridge still could be in a zwitterionic form in the hydrophobic interior of the real proteins.

  6. Controlled Electrochemical Carboxylation of Graphene To Create a Versatile Chemical Platform for Further Functionalization

    DEFF Research Database (Denmark)

    Bjerglund Pedersen, Emil; Kongsfelt, Mikkel S.; Shimizu, Kyoko;

    An electrochemical approach is introduced for the versatile carboxylation of multilayered graphene in 0.1 M Bu4NBF4/MeCN. First, the graphene substrate is negatively charged at −1.9 V vs. Ag/AgI to allow for intercalation of Bu4N+. In the second step, the strongly activated and nucleophilic graph...... in a multi-layered but expanded structure accessible for functionalization. On a more general level, this approach will provide a versatile way of forming new hybrid materials based on intimate bond coupling to graphene via carboxylate groups....... throughout the multilayered graphene structure, independent of the number of graphene sheets. This is assumed to be due to an opening of the entire graphene structure in response to the intercalation of Bu4N+. Hence, this electrochemical method offers a versatile procedure to make all graphene sheets...

  7. Adsorption Profile of Basic Dye onto Novel Fabricated Carboxylated Functionalized Co-Polymer Nanofibers

    Directory of Open Access Journals (Sweden)

    Marwa F. Elkady

    2016-04-01

    Full Text Available Acrylonitrile-Styrene co-polymer was prepared by solution polymerization and fabricated into nanofibers using the electrospinning technique. The nanofiber polarization was enhanced through its surface functionalization with carboxylic acid groups by simple chemical modification. The carboxylic groups’ presence was dedicated using the FT-IR technique. SEM showed that the nanofiber attains a uniform and porous structure. The equilibrium and kinetic behaviors of basic violet 14 dye sorption onto the nanofibers were examined. Both Langmuir and Temkin models are capable of expressing the dye sorption process at equilibrium. The intraparticle diffusion and Boyd kinetic models specified that the intraparticle diffusion step was the main decolorization rate controlling the process.

  8. Factors influencing the rate of non-enzymatic activation of carboxylic and amino acids by ATP

    Science.gov (United States)

    Mullins, D. W., Jr.; Lacey, J. C., Jr.

    1981-01-01

    The nonenzymatic formation of adenylate anhydrides of carboxylic and amino acids is discussed as a necessary step in the origin of the genetic code and protein biosynthesis. Results of studies are presented which have shown the rate of activation to depend on the pKa of the carboxyl group, the pH of the medium, temperature, the divalent metal ion catalyst, salt concentration, and the nature of the amino acid. In particular, it was found that of the various amino acids investigated, phenylalanine had the greatest affinity for the adenine derivatives adenosine and ATP. Results thus indicate that selective affinities between amino acids and nucleotides were important during prebiotic chemical evolution, and may have played a major role in the origin of protein synthesis and genetic coding.

  9. Ruthenium(II) multi carboxylic acid complexes: chemistry and application in dye sensitized solar cells.

    Science.gov (United States)

    Shahroosvand, Hashem; Nasouti, Fahimeh; Sousaraei, Ahmad

    2014-04-01

    Novel ruthenium multi carboxylic complexes (RMCCs) have been synthesized by using ruthenium nitrosyl nitrate, 1,2,4,5-benzenetetracarboxylic acid (H4btec) and 4,7-diphenyl-1,10-phenanthroline (BPhen) as photosensitizers for titanium dioxide semiconductor solar cells. The complexes were characterized by (1)H-NMR, FT-IR, UV-Vis, ICP and CHN analyses. The reaction details and features were then described. SEM analysis revealed that the penetration of dyes into the pores of the nanocrystalline TiO2 surface was improved by increasing the number of btec units. The solar energy to electricity conversion efficiency of complexes shows that the number of attached carboxylates on a dye has an influence on the photoelectrochemical properties of the dye-sensitized electrode. An incident photon-to-current conversion efficiency (IPCE) of 13% at 510 nm was obtained for ruthenium complexes with three btec units. PMID:24500312

  10. Redshift or adduct stabilization -- a computational study of hydrogen bonding in adducts of protonated carboxylic acids

    DEFF Research Database (Denmark)

    Olesen, Solveig Gaarn; Hammerum, Steen

    2009-01-01

    not always yield consistent predictions, as illustrated by the hydrogen bonds formed by the E and Z OH groups of protonated carboxylic acids. The delta-PA and the stabilization of a series of hydrogen bonded adducts indicate that the E OH group forms the stronger hydrogen bonds, whereas the bond length...... carboxylic acids are different. The OH bond length and IR redshift afford the better measure of hydrogen bond strength.......It is generally expected that the hydrogen bond strength in a D-H-A adduct is predicted by the difference between the proton affinities of D and A, measured by the adduct stabilization, and demonstrated by the IR redshift of the D-H bond stretching vibrational frequency. These criteria do...

  11. Preparation and reactivity of carboxylic acid-terminated boron-doped diamond electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Niedziolka-Joensson, Joanna [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France); Boland, Susan; Leech, Donal [School of Chemistry, National University of Irland, Galway (Ireland); Boukherroub, Rabah [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France); Szunerits, Sabine, E-mail: sabine.szunerits@iri.univ-lille1.f [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France)

    2010-01-01

    The paper reports on the formation of carboxy-terminated boron-doped diamond (BDD) electrodes. The carboxylic acid termination was prepared in a controlled way by reacting photochemically oxidized BDD with succinic anhydride. The resulting interface was readily employed for the linking of an amine-terminated ligand such as an osmium complex bearing an amine terminal group. The interfaces were characterized using X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). Contact angle measurements were used to follow the changes in surface wetting properties due to surface functionalization. The chemical reactivity of the carboxyl-terminated BDD was investigated by covalent coupling of the acid groups to an amine-terminated osmium complex.

  12. Preparation and characterization of nonferrous oxide ceramics from metal carboxylates dissolved in organic solvent

    International Nuclear Information System (INIS)

    The solvent extraction system used widely in hydrometallurgy metal-loaded carboxylate extractant was applied to prepare nonferrous oxide powders. When contacted with pure water at temperatures between 130 deg C and 240 deg C, tertiary carboxylate solutions of Ce(lll), Zr(lV), and Cu(ll) were hydrolyzed and precipitated CeO2 ZrO2 and Cu2O respectively. Characterization of the powders demonstrated that these precipitates were crystalline fine particles and were free from contamination by the organic starting material. The extent of precipitation of the oxide products was markedly dependent on process conditions such as temperature and organic phase compositions. For the processing of CeO2 vigorous stirring of the starting solution produced finer particles. (authors)

  13. Preparation and properties of fine hematite powders by hydrolysis of iron carboxylate solutions

    Science.gov (United States)

    Konishi, Yasuhiro; Kawamura, Takeshi; Asai, Satoru

    1994-04-01

    Submicrometer, crystalline hematite (α-Fe2O3) particles were prepared by hydrolysis of organic iron carboxylate solutions using water at 175 °C for 30 minutes. The particle size of hematite was significantly dependent on the liquid-phase stirring speed and the organic compositions. The precipitation rate of hematite from the organic solution followed first-order kinetics. The precipitation rate increased markedly with increasing temperature, and the activation energy for the process was 94.6 kJ mol-1. At 220 °C, the hydrolysis of iron carboxylate solution led to a mixture of hematite and magnetite (Fe3O4). The iron oxides prepared at 175 °C to 220 °C were found to be free from organic contamination by the starting material.

  14. Supramolecular Coordination Assemblies Constructed From Multifunctional Azole-Containing Carboxylic Acids

    Directory of Open Access Journals (Sweden)

    Yuheng Deng

    2010-05-01

    Full Text Available This paper provides a brief review of recent progress in the field of metal coordination polymers assembled from azole-containing carboxylic acids and gives a diagrammatic summary of the diversity of topological structures in the resulting infinite metal-organic coordination networks (MOCNs. Azole-containing carboxylic acids are a favorable kind of multifunctional ligand to construct various metal complexes with isolated complexes and one, two and three dimensional structures, whose isolated complexes are not the focus of this review. An insight into the topology patterns of the infinite coordination polymers is provided. Analyzed topologies are compared with documented topologies and catalogued by the nature of nodes and connectivity pattern. New topologies which are not available from current topology databases are described and demonstrated graphically.

  15. A database study of intermolecular NH...O hydrogen bonds for carboxylates, sulfonates and monohydrogen phosphonates

    International Nuclear Information System (INIS)

    A search of the Cambridge Structural Database (CSD, version 5.05, 1993) was performed in order to compare the geometrical features of the hydrogen bonds involving on the one hand amino groups and on the other hand carboxylates, sulfonates or monohydrogen phosponates. Phosphonates were not considered because only four entries containing amino and phosphonate moieities were located in the CSD. The hydroxylic group of monohydrogen phosphonates primarily acts as a hydrogen-bond donor. The three moieties under study show NH..O hydrogen bonds with similar geometrical features. This statistical analysis has focused on the hydrogen-bond distances and angles and on the distributions of the H atoms around the acceptor O atoms of carboxylates, sulfonates or monohydrogen phosphonates. (orig.)

  16. 2-Carboxyquinolinium–2,4,6-trinitrobenzenesulfonate–quinolinium-2-carboxylate (1/1/1

    Directory of Open Access Journals (Sweden)

    Graham Smith

    2008-01-01

    Full Text Available The structure of the title adduct compound, C10H8NO2+·C6H2N3O9S−·C10H7NO2, from the reaction of 2,4,6-trinitrobenzenesulfonic acid (picrylsulfonic acid with quinoline-2-carboxylic acid (quinaldic acid in 2-propanol–water, has been determined at 130 (2 K. The cation and the adduct species form a twisted cyclic hydrogen-bonded R22(10 pseudo-dimer which is extended into a one-dimensional chain structure through short head-to-tail carboxylic acid O—H...Ocarboxyl associations [O...O = 2.4711 (19 Å]. The picrylsulfonate anions are attached peripherally by single N—H...Osulfonate hydrogen bonds [N...O = 2.8643 (19 Å].

  17. Synthesis and Properties of Triphenylgermanium Heteroaromatic Carboxylates and Crystal Structure of Triphenylgermanium 2-Furoate

    Institute of Scientific and Technical Information of China (English)

    YIN,Han-Dong(尹汉东); WANG,Chuan-Hua(王传华); WANG,Yong(王勇); ZHANG,Ru-Fen(张如芬); MA,Chun-Lin(马春林); TAO,Xu-Quan(陶绪全)

    2001-01-01

    Ten triphenylgermaanium heteroaromatic carboxylates Ph3GeO2CR ( where R = 2-furanyl, 2-furanvinyl, 2-(5-tert-butyl) furonyl, 2-thiophenyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-indolyl, 3-indolyhnethyl, 3-indolylpropyl) were synthesized by the reaction of sodium heteroaromatic carboxylates with the triphenylgermanium chloride. All compounds were characterized by elemental analysis, 1H NMR and MS spectra. The empounds were tested against two human tumour cell lines: MCF-7 and WiDr. The results showed that they had high activities. The crystal structure of triphenyler-mananium 2-furoate was determined by X-ray single crystal diffration. The crystal belongs to monoclinic with space grop P 21/c, a=1.1945(4), t=0.9934(3), c=1.6284(5)nm, β=91.59(5), Z=4. In this crystal, the structure consists of discrete molecule containing four-cnordinate germanimm atom in a distored tetrahedron.

  18. Dielectric properties of supramolecular ionic structures obtained from multifunctional carboxylic acids and amines

    DEFF Research Database (Denmark)

    Gonzalez, Lidia; Yu, Liyun; Hvilsted, Søren;

    2014-01-01

    ), are investigated. Here the relative dielectric permittivities of the supramolecular ionic structures formed with the multifunctional carboxylic acids were lower than those from the supramolecular ionic structures formed with the two carboxymethyl ether-terminated poly(ethylene glycol)s.......The dielectric properties of several supramolecular ionic polymers and networks, linked by the ammonium salts of hexamethylene diamine (HMDA), tris(2-aminoethyl)amine (TAEA), poly(propylene imine) (PPI) dendrimers and two short bis carboxymethyl ether-terminated poly(ethylene glycol)s (Di...... networks, formed by mixing multifunctional carboxylic acids such as citric acid (CA), tricarballylic acid (TCAA), trimesic acid (TMA), ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DETPA) with two di ff erent Je ff amine polyetheramines (designated as D400 and D2000...

  19. Chemical Analysis and Transplacental Transfer of Oseltamivir and Oseltamivir Carboxylic Acid in Pregnant Rats

    OpenAIRE

    Lin, Chia-Chun; Yen, Jiin-Cherng; Wu, Yu-Tse; Lin, Lie-Chwen; Tsai, Tung-Hu

    2012-01-01

    In view of the limited information on the pharmacokinetics of oseltamivir (OSE) during pregnancy, this study aims to evaluate the placental transportation of OSE and its active metabolite oseltamivir carboxylic acid (OCA) in rats. A validated liquid chromatography-tandem mass spectrometry (LC-MS/MS) system coupled to an in vivo transplacental model has been developed to determine OSE and OCA in the placenta, amniotic fluids and fetus of 13-day pregnant Sprague-Dawley rats. Concentrations of O...

  20. Carboxyl multiwalled carbon nanotubes modified polypyrrole (PPy) aerogel for enhanced electromagnetic absorption

    Science.gov (United States)

    Zhang, Kun; Xie, Aming; Wu, Fan; Jiang, Wanchun; Wang, Mingyang; Dong, Wei

    2016-05-01

    Polypyrrole (PPy) aerogel is a low-cost and lightweight material with high-performance electromagnetic absorption (EA). However, it does not always meet the requirements of practical applications. In this study, we used trace amounts of carboxyl multiwalled carbon nanotubes to regulate the dielectric property of PPy aerogel, thus enhancing the EA performance. Furthermore, the reason for enhanced EA performance can be elaborated by an electron blocking mechanism.

  1. A new and efficient method for the synthesis of isoquinoline-3-carboxylate

    Institute of Scientific and Technical Information of China (English)

    Xiang Wei Liao; Bao He Guan; Zhan Zhu Liu

    2008-01-01

    An isoquinoline-3-carboxylate compound 3 was obtained with a moderate yield of 40% when N-acetyl-(3'-hydroxy-4'-methoxy-5'-methyl)phenylalanine methyl ester 1 was refluxed in HMTA/TFA. However, the anticipated product N-acetyl-(3'-hydroxy-4'-rnethoxy-5'-methyl-6'-formyl)phenylalanine methyl ester 2 could not be found. The possible mechanism was discussed in this article.

  2. Aminolysis of resin-bound N-nosylaziridine-2-carboxylic acids

    DEFF Research Database (Denmark)

    Olsen, Christian A; Christensen, Caspar; Nielsen, Birgitte;

    2006-01-01

    [Structure: see text] Solid-phase synthesis is a rapidly developing area of organic chemistry, of particular importance for medicinal chemistry and chemical biology. Aziridines have previously only rarely been applied in solid-phase synthesis. In the present work, aminolysis of resin-bound, sprin......-loaded N-nitrobenzenesulfonyl-activated aziridine-2-carboxylic acids has been optimized and employed in the synthesis of a number of open-chain and heterocyclic scaffolds, including enantiopure products....

  3. Heterogeneous and homogeneous catalysis for the hydrogenation of carboxylic acid derivatives: history, advances and future directions.

    Science.gov (United States)

    Pritchard, James; Filonenko, Georgy A; van Putten, Robbert; Hensen, Emiel J M; Pidko, Evgeny A

    2015-06-01

    The catalytic reduction of carboxylic acid derivatives has witnessed a rapid development in recent years. These reactions, involving molecular hydrogen as the reducing agent, can be promoted by heterogeneous and homogeneous catalysts. The milestone achievements and recent results by both approaches are discussed in this Review. In particular, we focus on the mechanistic aspects of the catalytic hydrogenation and highlight the bifunctional nature of the mechanism that is preferred for supported metal catalysts as well as homogeneous transition metal complexes.

  4. Transition-Metal-Free Decarboxylative Photoredox Coupling of Carboxylic Acids and Alcohols with Aromatic Nitriles.

    Science.gov (United States)

    Lipp, Benjamin; Nauth, Alexander M; Opatz, Till

    2016-08-01

    A transition-metal-free protocol for the redox-neutral light-induced decarboxylative coupling of carboxylic acids with (hetero)aromatic nitriles at ambient temperature is presented. A broad scope of acids and nitriles is accepted, and alcohols can be coupled in a similar fashion through their oxalate half esters. Various inexpensive sources of UV light and even sunlight can be used to achieve this C-C bond formation proceeding through a free radical mechanism. PMID:27399619

  5. Temperature dependence of C-terminal carboxylic group IR absorptions in the amide I' region.

    Science.gov (United States)

    Anderson, Benjamin A; Literati, Alex; Ball, Borden; Kubelka, Jan

    2015-01-01

    Studies of structural changes in peptides and proteins using IR spectroscopy often rely on subtle changes in the amide I' band as a function of temperature. However, these changes can be obscured by the overlap with other absorptions, namely the side-chain and terminal carboxylic groups. The former were the subject of our previous report (Anderson et al., 2014). In this paper we investigate the IR spectra of the asymmetric stretch of α-carboxylic groups for amino acids representing all major types (Gly, Ala, Val, Leu, Ser, Thr, Asp, Glu, Lys, Asn, His, Trp, Pro) as well as the C-terminal groups of three dipeptides (Gly-Gly, Gly-Ala, Ala-Gly) in D₂O at neutral pH. Experimental temperature dependent IR spectra were analyzed by fitting of both symmetric and asymmetric pseudo-Voigt functions. Qualitatively the spectra exhibit shifts to higher frequency, loss in intensity and narrowing with increased temperature, similar to that observed previously for the side-chain carboxylic groups of Asp. The observed dependence of the band parameters (frequency, intensity, width and shape) on temperature is in all cases linear: simple linear regression is therefore used to describe the spectral changes. The spectral parameters vary between individual amino acids and show systematic differences between the free amino acids and dipeptides, particularly in the absolute peak frequencies, but the temperature variations are comparable. The relative variations between the dipeptide spectral parameters are most sensitive to the C-terminal amino acid, and follow the trends observed in the free amino acid spectra. General rules for modeling the α-carboxylic IR absorption bands in peptides and proteins as the function of temperature are proposed.

  6. Temperature dependence of C-terminal carboxylic group IR absorptions in the amide I‧ region

    Science.gov (United States)

    Anderson, Benjamin A.; Literati, Alex; Ball, Borden; Kubelka, Jan

    2015-01-01

    Studies of structural changes in peptides and proteins using IR spectroscopy often rely on subtle changes in the amide I‧ band as a function of temperature. However, these changes can be obscured by the overlap with other absorptions, namely the side-chain and terminal carboxylic groups. The former were the subject of our previous report (Anderson et al., 2014). In this paper we investigate the IR spectra of the asymmetric stretch of α-carboxylic groups for amino acids representing all major types (Gly, Ala, Val, Leu, Ser, Thr, Asp, Glu, Lys, Asn, His, Trp, Pro) as well as the C-terminal groups of three dipeptides (Gly-Gly, Gly-Ala, Ala-Gly) in D2O at neutral pH. Experimental temperature dependent IR spectra were analyzed by fitting of both symmetric and asymmetric pseudo-Voigt functions. Qualitatively the spectra exhibit shifts to higher frequency, loss in intensity and narrowing with increased temperature, similar to that observed previously for the side-chain carboxylic groups of Asp. The observed dependence of the band parameters (frequency, intensity, width and shape) on temperature is in all cases linear: simple linear regression is therefore used to describe the spectral changes. The spectral parameters vary between individual amino acids and show systematic differences between the free amino acids and dipeptides, particularly in the absolute peak frequencies, but the temperature variations are comparable. The relative variations between the dipeptide spectral parameters are most sensitive to the C-terminal amino acid, and follow the trends observed in the free amino acid spectra. General rules for modeling the α-carboxylic IR absorption bands in peptides and proteins as the function of temperature are proposed.

  7. Hydrolytic activity of -alkoxide/acetato-bridged binuclear Cu(II) complexes towards carboxylic acid ester

    Indian Academy of Sciences (India)

    Weidong Jiang; Bin Xu; Zhen Xiang; Shengtian Huang; Fuan Liu; Ying Wang

    2013-09-01

    Two -alkoxide/acetate-bridged small molecule binuclear copper(II) complexes were synthesized, and used to promote the hydrolysis of a classic carboxylic acid ester, -nitrophenyl picolinate (PNPP). Both binuclear complexes exhibited good hydrolytic reactivity, giving rise to . 15547- and 17462-fold acceleration over background value for PNPP hydrolysis at neutral conditions, respectively. For comparing, activities of the other two mononuclear analogues were evaluated, revealing that binuclear complexes show approximately 150- and 171-fold kinetic advantage over their mononuclear analogues.

  8. Synthesis, structure and masnetic properties of two new coordination polymers with carboxylate-substituted benzoimidazole lisands

    Institute of Scientific and Technical Information of China (English)

    HU BoWen; ZHAO JiongPeng; YANG Qian; ZHANG XiaoFeng; BU XianHe

    2009-01-01

    This paper reports two new coordination polymers formed by carboxylate-substituted benzoimidazole and formate ligands:[Mn(L)-(HCO2)]n (1) and [Co(L)·(HCO2)]n (2) (L = benzoimidazol-1-yl-acetate).Complexes 1 and 2 are isomorphous and adopt a new 3,6-connected three-nodal topology showing interesting magnetic properties:spin canted antiferromagnetism for Mn11 complex 1,but simple antiferromagnetic coupling for CoⅡ complex 2.

  9. Structure–anticancer activity relationships among 4-azolidinone-3-carboxylic acids derivatives

    OpenAIRE

    Lesyk R. B.; Kaminskyy D. V.

    2010-01-01

    The aim of present research was investigation of anticancer activity of 4-azolidinone-3-carboxylic acids derivatives, and studies of structure–activity relationships (SAR) aspects. Methods. Organic synthesis; spectral methods; anticancer screening was performed according to the US NCI protocol (Developmental Therapeutic Program). Results. The data of new 4-thiazolidinone-3-alkanecarboxylic acids derivatives in vitro anticancer activity were described. The most active compounds which belong to...

  10. Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids.

    Science.gov (United States)

    Bandar, Jeffrey S; Ascic, Erhad; Buchwald, Stephen L

    2016-05-11

    A new method for the enantioselective reductive coupling of aryl alkenes with activated carboxylic acid derivatives via copper hydride catalysis is described. Dual catalytic cycles are proposed, with a relatively fast enantioselective hydroacylation cycle followed by a slower diastereoselective ketone reduction cycle. Symmetrical aryl carboxyclic anhydrides provide access to enantioenriched α-substituted ketones or alcohols with excellent stereoselectivity and functional group tolerance. PMID:27121395

  11. Novel 5-substituted benzyloxy-2-arylbenzofuran-3-carboxylic acids as calcium activated chloride channel inhibitors

    OpenAIRE

    Kumar, Satish; Namkung, Wan; A S Verkman; Sharma, Pawan K

    2012-01-01

    Transmembrane protein 16A (TMEM16A) channels are recently discovered membrane proteins that functions as a calcium activated chloride channel (CaCC). CaCCs are major regulators of various physiological processes, such as sensory transduction, epithelial secretion, smooth muscle contraction and oocyte fertilization. Thirty novel 5-substituted benzyloxy-2-arylbenzofuran-3-carboxylic acids (B01–B30) were synthesized and evaluated for their TMEM16A inhibitory activity by using short circuit curre...

  12. Carboxyl-Functionalized Task-Specific Ionic Liquids for Solubilizing Metal Oxides

    OpenAIRE

    Nockemann, Peter; Thijs, Ben; Parac-Vogt, Tatjana; Van Hecke, Kristof; Van Meervelt, Luc; Tinant, Bernard; Hartenbach, Ingo; Schleid, Thomas; Vu Thi, Ngan; Nguyen, Minh Tho; Binnemans, Koen

    2008-01-01

    Imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium, and quaternary ammonium bis(trifluoromethylsulfonyl)imide salts were functionalized with a carboxyl group. These ionic liquids are useful for the selective dissolution of metal oxides and hydroxides. Although these hydrophobic ionic liquids are immiscible with water at room temperature, several of them form a single phase with water at elevated temperatures. Phase separation occurs upon cooling. This thermomorphic behavior ha...

  13. Effect of Alkyl Chain Length on Carboxylic Acid SAMs on Ti-6Al-4V

    OpenAIRE

    Buckholtz, Gavin A.; Gawalt, Ellen S.

    2012-01-01

    The formation of methyl-terminated carboxylic acid self-assembled monolayers (SAMs) with even numbers of carbons, from eighteen to thirty, was investigated on the oxide surface of Ti-6Al-4V and component metal oxides. Modified surfaces were characterized using diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) and contact angle analysis. Infrared spectroscopy indicated that using aero...

  14. Ciprofloxacin, a quinolone carboxylic acid compound active against aerobic and anaerobic bacteria.

    OpenAIRE

    Chin, N X; Neu, H C

    1984-01-01

    The in vitro activity of ciprofloxacin, a quinolone-carboxylic acid derivative, was compared with those of norfloxacin, cefotaxime, cephalexin, ceftazidime, moxalactam, amoxicillin, and methicillin and other agents, as appropriate. The MICs of ciprofloxacin for 90% of members of the family Enterobacteriaceae and for Pseudomonas aeruginosa, Neisseria spp., and Bacteroides fragilis were between 0.005 and 0.8 micrograms/ml, whereas streptococci and staphylococci were all inhibited by less than o...

  15. A novel application of horseradish peroxidase: Oxidation of alcohol ethoxylate to alkylether carboxylic acid

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A novel application of horseradish peroxidase (HRP) in the oxidation of alcohol ethoxylate to alkylether carboxylie acid in the present of H2O2 was reported in this paper. We propose the mechanism for the catalytic oxidation reaction is that the hydrogen transfers from the substrate to the ferryl oxygen to form the a-hydroxy carbon radical intermediate. The reaction offers a new approach for further research structure and catalytic mechanism of HRP and production of alkylether carboxylic acid.

  16. Preparation and characterization of amino or carboxyl-functionalized ionic liquids

    Institute of Scientific and Technical Information of China (English)

    Yue Qin Cai; Feng Lu; Yan Qing Peng; Gong Hua Song

    2007-01-01

    New functionalized ionic liquids, 1-carboxylmethyl-3-methylimimidazolium hexafluorophosphate or fluoborate and l-aminoethyl-3-methylimimidazolium hexafluorophosphate or fluoborate have been synthesized and investigated. The obtained amino or carboxyl-functionalized ionic liquids were all characterized by FT-IR, 1H NMR and MS (ESI) and their properties such as freezing point, viscosity, solubility, specific gravity, surface tension, and interfacial tension were also determined.

  17. Synthesis, structure and magnetic properties of two new coordination polymers with carboxylate-substituted benzoimidazole ligands

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    This paper reports two new coordination polymers formed by carboxylate-substituted benzoimidazole and formate ligands: [Mn(L)·(HCO2)]n (1) and [Co(L)·(HCO2)]n (2) (L = benzoimidazol-1-yl-acetate). Com-plexes 1 and 2 are isomorphous and adopt a new 3,6-connected three-nodal topology showing inter-esting magnetic properties: spin canted antiferromagnetism for MnⅡ complex 1, but simple antiferro-magnetic coupling for CoⅡ complex 2.

  18. Process for recovering carboxylic acids from sugar cane industry by-products

    OpenAIRE

    Albet, Joël; Pislor, Emilie; Pontalier, Pierre-Yves

    2009-01-01

    Food industry by-products such as molasses and vinasses may provide an important source of organic acids. The aim of this study is to compare three processes, precipitation, chromatography and liquid-liquid extraction, for the recovery of carboxylic acids from sugarcane molasses from Réunion Island. Precipitation was performed with different temperatures by addition of calcium chloride. The results revealed that precipitation can recover aconitic acid efficiently from molasses. Liquid-liquid ...

  19. Pancreatic carboxyl ester lipase: a circulating enzyme that modifies normal and oxidized lipoproteins in vitro.

    OpenAIRE

    Shamir, R; Johnson, W. J.; Morlock-Fitzpatrick, K; Zolfaghari, R; Li, L; mas, e; Lombardo, D.; Morel, D W; Fisher, E A

    1996-01-01

    Pancreatic carboxyl ester lipase (CEL) hydrolyzes cholesteryl esters (CE), triglycerides (TG), and lysophospholipids, with CE and TG hydrolysis stimulated by cholate. Originally thought to be confined to the gastrointestinal system, CEL has been reported in the plasma of humans and other mammals, implying its potential in vivo to modify lipids associated with LDL, HDL (CE, TG), and oxidized LDL (lysophosphatidylcholine, lysoPC). We measured the concentration of CEL in human plasma as 1.2+/-0....

  20. Pyrazole carboxamides and carboxylic acids as protein kinase inhibitors in aberrant eukaryotic signal transduction

    DEFF Research Database (Denmark)

    Persson, Tobias; Yde, Christina W.; Rasmussen, Jakob Ewald;

    2007-01-01

    Densely functionalised pyrazole carboxamides and carboxylic acids were synthesised in an expedient manner through saponification and transamidation, respectively, of ester-functionalised pyrazoles. This synthetic protocol allowed for three diversifying steps in which appendages on the pyrazole...... potential biological activity, MCF-7 human breast cancer cells were incubated with the most promising derivatives. Two analogues caused changes in MCF-7 cell growth, one of them through cell cycle arrest demonstrated by cell cycle analysis....

  1. Synthesis and physicochemical properties of unsaturated trifluoromethylated sodium carboxylates in aqueous media.

    Science.gov (United States)

    Damas, Christine; Carcenac, Yvan; Abarbri, Mohamed; Coudert, Robert

    2013-04-01

    Structural modifications of unsaturated sodium carboxylate surfactants in terms of trifluoromethylation associated with the hydrocarbon chain length have been studied, the synthesis is described, and aggregation properties have been examined by conductimetry and vapor pressure osmometry between 30°C and 45°C. No strong effect of adding a CF3 group was observed on the Critical Micellar Concentrations. However, the thermodynamic study shows the specific effect exerted by the CF3 group through the enhancement of the entropic contribution.

  2. Low-molecular-weight poly-carboxylate as crystal growth modifier in biomineralization

    Indian Academy of Sciences (India)

    Ballav Moni Borah; Bhaskar Jyoti Bhuyan; Gopal Das

    2006-11-01

    Construction of modified inorganic mineral with controlled mineralization analogues of those produced by nature is now of current interest for understanding the mechanism of the in vivo biomineralization processes, as well as looking for fresh industrial and technological applications. Lowmolecular-weight chiral poly-carboxylate ligands derived from naturally occurring L--amino acids have been used as model systems to study the effect of molecular properties on crystal growth modification.

  3. Determination of the thermodynamic quantities of complexation between Eu(III) and carboxylic acids by microcalorimetry

    International Nuclear Information System (INIS)

    Potentiometric and microcalorimetric titration techniques were applied to determine the Gibbs free energies and enthalpies of the protonation of some carboxylic acids (acetic, glycolic, malonic and malic acids) and their complexation with Eu(III) in 1.0 M NaClO4 solution at 25 C, where Eu(III) was used as a chemical analogue of radiologically important Am(III). By using the values of ΔG determined by potentiometric titrations, the results of calorimetric titrations were analyzed to give the values of ΔH and ΔS. To support the discussion on the obtained thermodynamic quantities, the hydration numbers of Eu(III) in the complexes were obtained by TRLFS measurement, where the luminescence lifetime of Eu(III) excited by 394 nm laser was measured. A few to several kJ/mol of enthalpies were determined for the reactions within the uncertainties of ±0.01 to ±0.4. These enthalpy values indicated that the protonation of these carboxylates were entropy-driven, that is, vertical stroke - TΔS vertical stroke >> vertical stroke ΔH vertical stroke in ΔG = ΔH - TΔS. The complexations of Eu(III) were also shown to be controlled mainly by entropy term. The results of TRLFS measurement revealed that the number of dehydrated water molecule increased with the degree of complexation. A linear relation was found between total entropy change of the system (ΔST) and the net number of released molecules from the central Eu(III) ion. However, the values of ΔST for the hydroxy-carboxylates were smaller than that for simple carboxylates at the same net number of molecules released from Eu(III), suggesting that the dehydration occurred not only in the cation but also in the anion. (orig.)

  4. Substituted Amides of Pyrazine-2-carboxylic acids: Synthesis and Biological Activity

    OpenAIRE

    Katarina Kralova; Jiri Kunes; Miroslav Miletin; Martin Dolezal

    2002-01-01

    Condensation of 6-chloro-, 5-tert-butyl- or 6-chloro-5-tert-butylpyrazine-2-carboxylic acid chloride with ring substituted anilines yielded a series of amides, which were tested for their in vitro antimycobacterial, antifungal and photosynthesis-inhibiting activities. The highest antituberculotic activity (72% inhibition) against Mycobacterium tuberculosis and the highest lipophilicity (log P = 6.85) were shown by the 3,5-bistrifluoromethylphenyl amide of 5-tert-butyl-6-chloropyrazine-2-carbo...

  5. On the formation of niacin (vitamin B3) and pyridine carboxylic acids in interstellar model ices

    Science.gov (United States)

    McMurtry, Brandon M.; Turner, Andrew M.; Saito, Sean E. J.; Kaiser, Ralf I.

    2016-06-01

    The formation of pyridine carboxylic acids in interstellar ice grains was simulated by electron exposures of binary pyridine (C5H5N)-carbon dioxide (CO2) ice mixtures at 10 K under contamination-free ultrahigh vacuum conditions. Chemical processing of the pristine ice and subsequent warm-up phase was monitored on line and in situ via Fourier transform infrared spectroscopy to probe for the formation of new radiation induced species. In the infrared spectra of the irradiated ice, bands assigned to nicotinic acid (niacin; vitamin B3; m-C5H4NCOOH) along with 2,3-, 2,5-, 3,4-, and 3,5-pyridine dicarboxylic acid (C5H3N(COOH)2) were unambiguously identified along with the hydroxycarbonyl (HOCO) radical. Our study suggests that the reactive pathway responsible for pyridine carboxylic acids formation involves a HOCO intermediate, which forms through the reaction of suprathermal hydrogen ejected from pyridine with carbon dioxide. The newly formed pyridinyl radical may then undergo radical-radical recombination with a hydroxycarbonyl radical to form a pyridine carboxylic acid.

  6. Statistical investigation of lead removal with various functionalized carboxylate ferroxane nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Moattari, Rozita M.; Rahimi, Safoora [Polymer Research Lab., Department of Chemical Engineering, College of Engineering, Razi University, Kermanshah (Iran, Islamic Republic of); Rajabi, Laleh, E-mail: laleh.rajabii@gmail.com [Polymer Research Lab., Department of Chemical Engineering, College of Engineering, Razi University, Kermanshah (Iran, Islamic Republic of); Derakhshan, Ali Ashraf [Young Researchers Club, Kermanshah Branch, Islamic Azad University, Kermanshah (Iran, Islamic Republic of); Keyhani, Mohammad [Polymer Research Lab., Department of Chemical Engineering, College of Engineering, Razi University, Kermanshah (Iran, Islamic Republic of)

    2015-02-11

    Graphical abstract: - Highlights: • Four new carboxylate ferroxane nanostructures were synthesized and characterized. • Carboxylate ferroxanes were used as nanosorbents for lead removal. • Taguchi method was used to design the experiments. • Statistical analyses evaluated the three model responses [R%, Logit (R%), C{sub ratio}]. • Maleate ferroxane performed the best of the four nanosorbents studied. - Abstract: Four new types of carboxylate-ferroxane nanoparticles, namely; maleate ferroxane (MF), fumarateferroxane (FF), para-amino benzoate ferroxane (PABF) and para-hydroxy benzoate ferroxane (PHBF) were synthesized, characterized and used for lead removal from aqueous solutions. Lepidocrocite nanoparticles were also synthesized and characterized asa precursorforcarboxylate-ferroxanes. FTIR, SEM and DLS analysis characterized the synthesized samplesand final Pb(II) concentration were analysed using inductively coupled plasma atomic emission spectrometer. Performance evaluation of the nanoparticlesin adsorption process was achieved using Taguchi experimental design. Variables in adsorption process were initial pH, contact time, adsorbent dose, adsorbent typeand initial concentration of Pb{sup 2+} ions. The initial Pb(II) concentration was the most influential factor in the adsorption process among the five factors. Adsorption of lead was performed through two possible mechanisms; ion exchange and complex formation. Maleate ferroxane performed the best lead removal efficiency among the four types of ferroxane nanostructures studied. The adsorption kinetic data described well with a pseudo-second-order model and the equilibrium data fitted well to the Frendlich isotherm.

  7. Solution-processable carboxylate-capped CuO nanoparticles obtained by a simple solventless method

    Energy Technology Data Exchange (ETDEWEB)

    Estruga, Marc [Universitat Autonoma de Barcelona, Department of Chemistry (Spain); Roig, Anna; Domingo, Concepcion [CSIC, Institut de Ciencia de Materials de Barcelona (Spain); Ayllon, Jose A., E-mail: joseantonio.ayllon@uab.es [Universitat Autonoma de Barcelona, Department of Chemistry (Spain)

    2012-08-15

    Carboxylate-capped CuO nanoparticles were obtained via a simple solventless route, based on the thermal decomposition at 120 Degree-Sign C of solid precursors. The reaction mixture consisted of copper acetate monohydrate, acting as the CuO precursor, and different organic carboxylic acids (lauric, phenylvaleric or 3,6,9-trioxadecanoic acid) used as the capping agent. The proposed method, in good agreement with environmentally friendly practices, produced dry nanoparticles, thereby totally eliminating the need of washing, filtration, or other downstream steps. Transmission electron micrographs show crystalline roughly spherical CuO nanoparticles with average diameters between 3.1 and 5.5 nm depending on the capping ligand. The laurate-capped CuO nanoparticles showed a paramagnetic behaviour at room temperature, while a weak ferromagnetic component was detected at low temperature (<40 K). It was also proved that the chemical structure of the carboxylic acid tail enabled the straightforward dispersibility of nanoparticles in common solvents and assisted in the deposition of the material as thin films.

  8. Carboxylated magnetic nanoparticles as MRI contrast agents: Relaxation measurements at different field strengths

    Energy Technology Data Exchange (ETDEWEB)

    Jedlovszky-Hajdu, Angela, E-mail: angela.hajdu@net.sote.hu [Laboratory of Nanochemistry, Department of Biophysics and Radiation Biology, Semmelweis University, Nagyvarad Sq 4, H-1089 Budapest (Hungary); Tombacz, Etelka, E-mail: tombacz@chem.u-szeged.hu [Department of Physical Chemistry and Material Science, University of Szeged, Aradi Vt. Sq 1, Szeged 6720 (Hungary); Banyai, Istvan, E-mail: banyai.istvan@science.unideb.hu [Department of Colloid and Environmental Chemistry, University of Debrecen (Hungary); Babos, Magor, E-mail: babosmagor@yahoo.com [Euromedic Diagnostics Szeged Ltd., Semmelweis St 6, Szeged 6720 (Hungary); Palko, Andras, E-mail: palko@radio.szote.u-szeged.hu [Faculty of Medicine, Department of Radiology, University of Szeged (Hungary)

    2012-09-15

    At the moment the biomedical applications of magnetic fluids are the subject of intensive scientific interest. In the present work, magnetite nanoparticles (MNPs) were synthesized and stabilized in aqueous medium with different carboxylic compounds (citric acid (CA), polyacrylic acid (PAA), and sodium oleate (NaOA)), in order to prepare well stabilized magnetic fluids (MFs). The magnetic nanoparticles can be used in the magnetic resonance imaging (MRI) as contrast agents. Magnetic resonance relaxation measurements of the above MFs were performed at different field strengths (i.e., 0.47, 1.5 and 9.4 T) to reveal the field strength dependence of their magnetic responses, and to compare them with that of ferucarbotran, a well-known superparamagnetic contrast agent. The measurements showed characteristic differences between the tested magnetic fluids stabilized by carboxylic compounds and ferucarbotran. It is worthy of note that our magnetic fluids have the highest r2 relaxivities at the field strength of 1.5 T, where the most of the MRI works in worldwide. - Highlights: Black-Right-Pointing-Pointer Magnetic resonance relaxation measurements were done at different field strengths. Black-Right-Pointing-Pointer Results show characteristic differences between the tested carboxylated MFs. Black-Right-Pointing-Pointer r1 and r2 relaxivities depend on the thickness of the protecting layer. Black-Right-Pointing-Pointer MFs have high r2/r1 ratios at each magnetic field.

  9. Carboxylic Acid Fullerene (C60) Derivatives Attenuated Neuroinflammatory Responses by Modulating Mitochondrial Dynamics

    Science.gov (United States)

    Ye, Shefang; Zhou, Tong; Cheng, Keman; Chen, Mingliang; Wang, Yange; Jiang, Yuanqin; Yang, Peiyan

    2015-05-01

    Fullerene (C60) derivatives, a unique class of compounds with potent antioxidant properties, have been reported to exert a wide variety of biological activities including neuroprotective properties. Mitochondrial dynamics are an important constituent of cellular quality control and function, and an imbalance of the dynamics eventually leads to mitochondria disruption and cell dysfunctions. This study aimed to assess the effects of carboxylic acid C60 derivatives (C60-COOH) on mitochondrial dynamics and elucidate its associated mechanisms in lipopolysaccharide (LPS)-stimulated BV-2 microglial cell model. Using a cell-based functional screening system labeled with DsRed2-mito in BV-2 cells, we showed that LPS stimulation led to excessive mitochondrial fission, increased mitochondrial localization of dynamin-related protein 1 (Drp1), both of which were markedly suppressed by C60-COOH pretreatment. LPS-induced mitochondria reactive oxygen species (ROS) generation and collapse of mitochondrial membrane potential (Δ Ψm) were also significantly inhibited by C60-COOH. Moreover, we also found that C60-COOH pretreatment resulted in the attenuation of LPS-mediated activation of nuclear factor (NF)-κB and mitogen-activated protein kinase (MAPK) signaling, as well as the production of pro-inflammatory mediators. Taken together, these findings demonstrated that carboxylic acid C60 derivatives may exert neuroprotective effects through regulating mitochondrial dynamics and functions in microglial cells, thus providing novel insights into the mechanisms of the neuroprotective properties of carboxylic acid C60 derivatives.

  10. Gas-Phase Amidation of Carboxylic Acids with Woodward's Reagent K Ions

    Science.gov (United States)

    Peng, Zhou; Pilo, Alice L.; Luongo, Carl A.; McLuckey, Scott A.

    2015-06-01

    Gas-phase amidation of carboxylic acids in multiply-charged peptides is demonstrated via ion/ion reactions with Woodward's reagent K (wrk) in both positive and negative mode. Woodward's reagent K, N-ethyl-3-phenylisoxazolium-3'-sulfonate, is a commonly used reagent that activates carboxylates to form amide bonds with amines in solution. Here, we demonstrate that the analogous gas-phase chemistry occurs upon reaction of the wrk ions and doubly protonated (or doubly deprotonated) peptide ions containing the carboxylic acid functionality. The reaction involves the formation of the enol ester intermediate in the electrostatic complex. Upon collisional activation, the ethyl amine on the reagent is transferred to the activated carbonyl carbon on the peptide, resulting in the formation of an ethyl amide (addition of 27 Da to the peptide) with loss of a neutral ketene derivative. Further collision-induced dissociation (CID) of the products and comparison with solution-phase amidation product confirms the structure of the ethyl amide.

  11. Synthesis of antimony tris(mercaptoethyl carboxylates) as thermal stabilizer for polyvinyl chloride

    Institute of Scientific and Technical Information of China (English)

    舒万艮; 刘又年; 陈启元

    2002-01-01

    A novel type of thermal stabilizers-antimony tris(mercaptoethyl carboxylates) (Sb(SCH2CH2OOCR) 3), was synthesized from carboxylic acid, antimony trioxide and 2-mercaptoethanol in two steps. The experimental results show that the molar ratio of carboxylic acid to antimony tris(2-hydroxyethyl mercaptide) is 1.2, when adding 0.6% tetra-n-butyl titanate as catalyst and xylene as isotropic solvent, heating and refluxing for about 2~4h. The thermal stability was measured by heat-aging oven test. The thermal stability time is about 8~40min(at 200℃) when adding 2% tetra-n-butyl titanate in polyvinyl chloride(PVC). Among these stabilizers, antimony tris(mercaptoethyl stearate) has best thermal stability. Its thermal stability is better than that of Ca-Zn complex and basic lead stabilizers, and equal to that of organotin. In addition, the stabilization mechanism of this kind of stabilizers for PVC was discussed briefly.

  12. Gas Permeable Membranes Composed of Carboxylated Poly(vinyl chloride) and Polyurethane

    International Nuclear Information System (INIS)

    Gas-permeable polymeric membranes containing carboxyl groups which are suitable for enzyme immobilization were investigated in order to use them as gas electrode membranes in biosensors. Carboxylated polyurethane (CPU) was synthesized via a reaction between 2,2-bis(hydroxymethyl)propionic acid as a chain extender and prepolymers prepared from polycarprolactone (Mn=2,000) and 4,4'-diphenylmethane diisocynate. It was difficult to prepare membranes from the pure CPU because of its high elasticity and cohesion. However, transparent free-standing membranes were easily prepared from the blend solutions of CPU and carboxylated poly(vinyl chloride) (CPVC) in tetrahydrofuran. Both elasticity and cohesion of the CPU/CPVC membranes were decreased with increasing the content of CPVC. DSC experiment suggests that CPU and CPVC may be well mixed. Permeability coefficients for O2 and CO2 (PO2 and PCO2) in the membranes increased as the proportion of CPU increased. The addition of dioctyl phthalate (DOP), a plasticizer, significantly enhanced the PO2 and PCO2 which were 4.4 and 30 Barrer, respectively, in the CPU/CPVC (80/20 wt/wt) membranes containing 20% of DOP at 25 .deg. C and 100 psi. Thus this type of membranes may have a potential for the use as gas electrode membranes in biosensors

  13. Gas Permeable Membranes Composed of Carboxylated Poly(vinyl chloride) and Polyurethane

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Chun Won; Kim, Chai Gyun; Kim, Wan Young; Jeong, Yong Seob; Lee, Youn Sik [Chonbuk National University, Jeonju (Korea, Republic of)

    1999-06-15

    Gas-permeable polymeric membranes containing carboxyl groups which are suitable for enzyme immobilization were investigated in order to use them as gas electrode membranes in biosensors. Carboxylated polyurethane (CPU) was synthesized via a reaction between 2,2-bis(hydroxymethyl)propionic acid as a chain extender and prepolymers prepared from polycarprolactone (Mn=2,000) and 4,4'-diphenylmethane diisocynate. It was difficult to prepare membranes from the pure CPU because of its high elasticity and cohesion. However, transparent free-standing membranes were easily prepared from the blend solutions of CPU and carboxylated poly(vinyl chloride) (CPVC) in tetrahydrofuran. Both elasticity and cohesion of the CPU/CPVC membranes were decreased with increasing the content of CPVC. DSC experiment suggests that CPU and CPVC may be well mixed. Permeability coefficients for O{sub 2} and CO{sub 2} (P{sub O2} and P{sub CO2}) in the membranes increased as the proportion of CPU increased. The addition of dioctyl phthalate (DOP), a plasticizer, significantly enhanced the P{sub O2} and P{sub CO2} which were 4.4 and 30 Barrer, respectively, in the CPU/CPVC (80/20 wt/wt) membranes containing 20% of DOP at 25 .deg. C and 100 psi. Thus this type of membranes may have a potential for the use as gas electrode membranes in biosensors

  14. Surface complexation of carboxylate adheres Cryptosporidium parvum oocysts to the hematite-water interface

    Science.gov (United States)

    Gao, X.; Metge, D.W.; Ray, C.; Harvey, R.W.; Chorover, J.

    2009-01-01

    The interaction of viable Cryptosporidium parvum ??ocysts at the hematite (??-Fe2O3)-water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed ??ocysts showed distinctchangesin carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. In NaCl solution, ??ocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, ??ocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions. ?? 2009 American Chemical Society.

  15. Carboxylic acid functionalization of halloysite nanotubes for sustained release of diphenhydramine hydrochloride

    Energy Technology Data Exchange (ETDEWEB)

    Zargarian, S. Sh.; Haddadi-Asl, V., E-mail: haddadi@aut.ac.ir; Hematpour, H. [Amirkabir University of Technology, Department of Polymer Engineering and Color Technology (Iran, Islamic Republic of)

    2015-05-15

    Halloysite nanotubes (HNT) (cylindrical shape with external diameter and length in the range of 30–80 nm and 0.2–1 µm, respectively) were functionalized with 3-aminopropyltriethoxysilane (APTES) from hydroxyl groups by a coupling reaction. Subsequently, maleic anhydride was attached to the APTES moieties to yield carboxylic acid-functionalized HNT. Loading and subsequent release of a model drug molecule diphenhydramine hydrochloride (DPH) on modified and unmodified nanotubes were investigated. Morphology of HNT was studied by electron microscopy. Successful attachment of APTES and carboxylic acid groups to halloysite and drug loading were evaluated by Fourier transform infrared spectroscopy. The amount of surface modification and drug adsorption capacity were calculated via thermogravimetric analysis. The ordered crystal structure of loaded drug was evaluated by X-ray diffraction. UV–Visible spectrophotometer was used to study drug release from modified and unmodified samples. Carboxylated halloysite exhibits higher loading capacity and prolonged release of DPH as compared to that of the natural halloysite.

  16. High salinity in molasses wastewaters shifts anaerobic digestion to carboxylate production.

    Science.gov (United States)

    De Vrieze, Jo; Coma, Marta; Debeuckelaere, Matthias; Van der Meeren, Paul; Rabaey, Korneel

    2016-07-01

    Biorefinery wastewaters are often treated by means of anaerobic digestion to produce biogas. Alternatively, these wastewaters can be fermented, leading to the formation of carboxylates. Here, we investigated how lab-scale upflow anaerobic sludge blanket reactors could be shifted to fermentation by changing organic loading rate, hydraulic retention time, pH, and salinity. A strong increase in volatile fatty acid concentration up to 40 g COD L(-1) was achieved through increasing salinity above 30 mS cm(-1), as well as a decrease in methane production by more than 90%, which could not be obtained by adjusting the other parameters, thus, indicating a clear shift from methane to carboxylate production. Microbial community analysis revealed a shift in bacterial community to lower evenness and richness values, following the increased salinity and VFA concentration during the fermentation process. A selective enrichment of the hydrogenotrophic Methanomicrobiales took place upon the shift to fermentation, despite a severe decrease in methane production. Particle size distribution revealed a strong degranulation of the sludge in the reactor, related to the high salinity, which resulted in a wash-out of the biomass. This research shows that salinity is a key parameter enabling a shift from methane to carboxylate production in a stable fermentation process. PMID:27110885

  17. Unique adsorption behaviors of carboxylic acids at rutile TiO2(110)

    Science.gov (United States)

    Yu, Yan-Yan; Gong, Xue-Qing

    2015-11-01

    The coverage-dependent adsorption behavior of acetic acid (CH3COOH) on rutile TiO2(110) was investigated by means of density functional theory (DFT) calculations, corrected by on-site Coulomb corrections and long-range dispersion interactions. The p(2 × 1) and c(2 × 2) domains of dissociatively adsorbed acetic acid under different coverages have been studied in detail regarding their structural and energetic properties. Adsorptions of formic acid (HCOOH) and carbonic acid (H2CO3) were also considered for better understanding the adsorption behaviors of carboxylic acids. Our calculation results show that carboxylic acids prefer to dissociatively adsorb in bridging bidentate configuration, and it induces significant surface relaxation at the adsorption site, which also affects other surface atoms nearby. Interestingly, we have shown that such adsorption-induced relaxations still maintain bond symmetries for surface Ti cations within the p(2 × 1) domain while they are drastically broken within the c(2 × 2) domain, giving rise to unstable Ti cations at the surface. This work not only explains the long-lasting puzzle of the preferable occurrence of p(2 × 1) domain for the adsorbed carboxylic acids at rutile TiO2(110), it also proposes a novel scheme that metal oxide surfaces may follow when they are involved in the processes like surface functionalization and self-assembly.

  18. Biocatalytic carboxylation of phenol derivatives: kinetics and thermodynamics of the biological Kolbe-Schmitt synthesis.

    Science.gov (United States)

    Pesci, Lorenzo; Glueck, Silvia M; Gurikov, Pavel; Smirnova, Irina; Faber, Kurt; Liese, Andreas

    2015-04-01

    Microbial decarboxylases, which catalyse the reversible regioselective ortho-carboxylation of phenolic derivatives in anaerobic detoxification pathways, have been studied for their reverse carboxylation activities on electron-rich aromatic substrates. Ortho-hydroxybenzoic acids are important building blocks in the chemical and pharmaceutical industries and are currently produced via the Kolbe-Schmitt process, which requires elevated pressures and temperatures (≥ 5 bar, ≥ 100 °C) and often shows incomplete regioselectivities. In order to resolve bottlenecks in view of preparative-scale applications, we studied the kinetic parameters for 2,6-dihydroxybenzoic acid decarboxylase from Rhizobium sp. in the carboxylation- and decarboxylation-direction using 1,2-dihydroxybenzene (catechol) as starting material. The catalytic properties (K(m), V(max)) are correlated with the overall thermodynamic equilibrium via the Haldane equation, according to a reversible random bi-uni mechanism. The model was subsequently verified by comparing experimental results with simulations. This study provides insights into the catalytic behaviour of a nonoxidative aromatic decarboxylase and reveals key limitations (e.g. substrate oxidation, CO2 pressure, enzyme deactivation, low turnover frequency) in view of the employment of this system as a 'green' alternative to the Kolbe-Schmitt processes.

  19. Investigation of Carboxylic Acid-Neodymium Conversion Films on Magnesium Alloy

    Science.gov (United States)

    Cui, Xiufang; Liu, Zhe; Lin, Lili; Jin, Guo; Wang, Haidou; Xu, Binshi

    2015-01-01

    The new carboxylic acid-neodymium anhydrous conversion films were successfully prepared and applied on the AZ91D magnesium alloy surface by taking absolute ethyl alcohol as solvent and four kinds of soluble carboxylic acid as activators. The corrosion resistance of the coating was measured by potentiodynamic polarization test in 3.5 wt.% NaCl solution in pH 7.0. The morphology, structure, and constituents of the coating were observed by scanning electron microscope, energy dispersivespectrum, x-ray photoelectron spectrum, and Fourier infrared spectrometer. Results show that corrosion resistance properties of samples coated with four different anhydrous conversion films were improved obviously. The corrosion potential increased, corrosion current density decreased, and polarization resistance increased. Among these four kinds of conversion films the one added with phytic exhibits the best corrosion resistant property. The mechanism of anhydrous-neodymium conversion film formation is also analyzed in this paper. It reveals that the gadolinium conversion coating is mainly composed of stable Nd2O3, MgO, Mg(OH)2, and carboxylate of Nd. And that the sample surface is rich in organic functional groups.

  20. Effects of carboxylic acids on the uptake of non-transferrin-bound iron by astrocytes.

    Science.gov (United States)

    Keenan, Belinda M; Robinson, Stephen R; Bishop, Glenda M

    2010-01-01

    The concentrations of non-transferrin-bound iron are elevated in the brain during pathological conditions such as stroke and Alzheimer's disease. Astrocytes are specialised for sequestering this iron, however little is known about the mechanisms involved. Carboxylates, such as citrate, have been reported to facilitate iron uptake by intestinal cells. Citrate binds iron and limits its redox activity. The presence of high citrate concentrations in the interstitial fluid of the brain suggests that citrate may be an important ligand for iron transport by astrocytes. This study investigates whether iron accumulation by cultured rat astrocytes is facilitated by citrate or other carboxylates. Contrary to expectations, citrate, tartrate and malate were found to block iron accumulation in a concentration-dependent manner; alpha-ketoglutarate had limited effects, while fumarate, succinate and glutarate had no effect. This blockade was not due to an inhibition of ferric reductase activity. Instead, it appeared to be related to the capacity of these carboxylates to bind iron, since phosphate, which also binds iron, diminished the capacity of citrate, tartrate and malate to block the cellular accumulation of iron. These findings raise the possibility that citrate may have therapeutic potential in the management of neurodegenerative conditions that involve cellular iron overload.

  1. Adsorption of gaseous formaldehyde and carboxylic acids by ammonium-ion-exchanged alpha-zirconium phosphate.

    Science.gov (United States)

    Hayashi, A; Fujimoto, Y; Ogawa, Y; Nakayama, H; Tsuhako, M

    2005-03-01

    Ammonium-ion-exchanged alpha-Zr(HPO(4))(2)H(2)O (alpha-ZrP) was obtained as a single phase with the interlayer distance of 9.4 A by the ion-exchange of proton with ammonium ion. The ammonium ion-exchanged alpha-ZrP could adsorb ill-smelling gases, such as formaldehyde and carboxylic acids (formic acid, acetic acid, propionic acid, and butyric acid). The adsorption amounts of carboxylic acids increased in the order, butyric acidadsorption amount of formaldehyde was the same as that of butyric acid. It was cleared that the adsorbed formaldehyde was partially decomposed to formic acid and methanol by self oxidation-reduction reaction in the interlayer region as evidenced by solid-state NMR. Thereby the interlayer distance after the adsorption of formaldehyde expanded to 14.4 A. In the case of formic acid, it was cointercalated into the interlayer region, and the interlayer distance expanded to 11.1 A. On the other hand, the interlayer distance of the other carboxylic acid-adsorbed compounds decreased to 7.6 A due to release by the evacuation.

  2. (Benzoato-κ2O,O′(quinoline-2-carboxylato-κ2N,O(quinoline-2-carboxylic acid-κ2N,Omanganese(II

    Directory of Open Access Journals (Sweden)

    Nuno D. Martins

    2008-01-01

    Full Text Available The crystal structure of the title compound, [Mn(C7H5O2(C10H6NO2(C10H7NO2], contains manganese(II ions six-coordinated in a distorted octahedral environment. The equatorial plane is occupied by four O atoms, two from the carboxylate group of the benzoate ion, the other two from carboxylate/carboxyl groups of the quinaldate/quinaldic acid molecules. The axial positions are occupied by the N atoms of the quinoline ring systems. The metal ion lies on a twofold rotation axis that bisects the benzoate ligand; the quinaldate and quinaldic acid ligands are therefore equivalent by symmetry, and the carboxylate/carboxyl groups are disordered. The complexes are joined together by hydrogen bonds between the carboxylate/carboxyl groups of adjacent quinaldate/quinaldic acid molecules, forming zigzag chains that run along the c axis.

  3. Using the Chiral Organophosphorus Derivatizing Agents for Determination of the Enantiomeric Composition of Chiral Carboxylic Acids by 31PNMR Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    Chao CHE; Zhong Ning ZHANG; Gui Lan HUANG; Xin Xing WANG; Zhao Hai QIN

    2004-01-01

    The use of chiral organophosphorus derivatizing agents prepared in situ from chiral tartrate or chiral diamine for the 31PNMR determination of the enantiomeric composition of chiral carboxylic acids is described. The method is accurate, reliable and convenient.

  4. Nano-graphene oxide carboxylation for efficient bioconjugation applications: a quantitative optimization approach

    Energy Technology Data Exchange (ETDEWEB)

    Imani, Rana; Emami, Shahriar Hojjati, E-mail: semami@aut.ac.ir [Amirkabir University of Technology, Department of Biomedical Engineering (Iran, Islamic Republic of); Faghihi, Shahab, E-mail: shahabeddin.faghihi@mail.mcgill.ca, E-mail: sfaghihi@nigeb.ac.ir [National Institute of Genetic Engineering and Biotechnology, Tissue Engineering and Biomaterials Division (Iran, Islamic Republic of)

    2015-02-15

    A method for carboxylation of graphene oxide (GO) with chloroacetic acid that precisely optimizes and controls the efficacy of the process for bioconjugation applications is proposed. Quantification of COOH groups on nano-graphene oxide sheets (NGOS) is performed by novel colorimetric methylene blue (MB) assay. The GO is synthesized and carboxylated by chloroacetic acid treatment under strong basic condition. The size and morphology of the as-prepared NGOS are characterized by scanning electron microscopy, transmission electron microscopy (TEM), and atomic force microscopy (AFM). The effect of acid to base molar ratio on the physical, chemical, and morphological properties of NGOS is analyzed by Fourier-transformed infrared spectrometry (FTIR), UV–Vis spectroscopy, X-ray diffraction (XRD), AFM, and zeta potential. For evaluation of bioconjugation efficacy, the synthesized nano-carriers with different carboxylation ratios are functionalized by octaarginine peptide sequence (R8) as a biomolecule model containing amine groups. The quantification of attached R8 peptides to graphene nano-sheets’ surface is performed with a colorimetric-based assay which includes the application of 2,4,6-Trinitrobenzene sulfonic acid (TNBS). The results show that the thickness and lateral size of nano-sheets are dramatically decreased to 0.8 nm and 50–100 nm after carboxylation process, respectively. X-ray analysis shows the nano-sheets interlaying space is affected by the alteration of chloroacetic acid to base ratio. The MB assay reveals that the COOH groups on the surface of NGOS are maximized at the acid to base ratio of 2 which is confirmed by FTIR, XRD, and zeta potential. The TNBS assay also shows that bioconjugation of the optimized carboxylated NGOS sample with octaarginine peptide is 2.5 times more efficient compared to bare NGOS. The present work provides evidence that treatment of GO by chloroacetic acid under an optimized condition would create a functionalized high

  5. Glutathione Regulates 1-Aminocyclopropane-1-Carboxylate Synthase Transcription via WRKY33 and 1-Aminocyclopropane-1-Carboxylate Oxidase by Modulating Messenger RNA Stability to Induce Ethylene Synthesis during Stress.

    Science.gov (United States)

    Datta, Riddhi; Kumar, Deepak; Sultana, Asma; Hazra, Saptarshi; Bhattacharyya, Dipto; Chattopadhyay, Sharmila

    2015-12-01

    Glutathione (GSH) plays a fundamental role in plant defense-signaling network. Recently, we have established the involvement of GSH with ethylene (ET) to combat environmental stress. However, the mechanism of GSH-ET interplay still remains unexplored. Here, we demonstrate that GSH induces ET biosynthesis by modulating the transcriptional and posttranscriptional regulations of its key enzymes, 1-aminocyclopropane-1-carboxylate synthase (ACS) and 1-aminocyclopropane-1-carboxylate oxidase (ACO). Transgenic Arabidopsis (Arabidopsis thaliana) plants with enhanced GSH content (AtECS) exhibited remarkable up-regulation of ACS2, ACS6, and ACO1 at transcript as well as protein levels, while they were down-regulated in the GSH-depleted phytoalexin deficient2-1 (pad2-1) mutant. We further observed that GSH induced ACS2 and ACS6 transcription in a WRKY33-dependent manner, while ACO1 transcription remained unaffected. On the other hand, the messenger RNA stability for ACO1 was found to be increased by GSH, which explains our above observations. In addition, we also identified the ACO1 protein to be a subject for S-glutathionylation, which is consistent with our in silico data. However, S-glutathionylation of ACS2 and ACS6 proteins was not detected. Further, the AtECS plants exhibited resistance to necrotrophic infection and salt stress, while the pad2-1 mutant was sensitive. Exogenously applied GSH could improve stress tolerance in wild-type plants but not in the ET-signaling mutant ethylene insensitive2-1, indicating that GSH-mediated resistance to these stresses occurs via an ET-mediated pathway. Together, our investigation reveals a dual-level regulation of ET biosynthesis by GSH during stress.

  6. Rational design of carboxyl groups perpendicularly attached to a graphene sheet: a platform for enhanced biosensing applications.

    Science.gov (United States)

    Bonanni, Alessandra; Chua, Chun Kiang; Pumera, Martin

    2014-01-01

    Graphene oxide (GO)-based materials offer great potential for biofunctionalization with applications ranging from biosensing to drug delivery. Such biofunctionalization utilizes specific functional groups, typically a carboxyl moiety, as anchoring points for biomolecule. However, due to the fact that the exact chemical structure of GO is still largely unknown and poorly defined (it was postulated to consist of various oxygen-containing groups, such as epoxy, hydroxyl, carboxyl, carbonyl, and peroxy in varying ratios), it is challenging to fabricate highly biofunctionalized GO surfaces. The predominant anchoring sites (i.e., carboxyl groups) are mainly present as terminal groups on the edges of GO sheets and thus account for only a fraction of the oxygen-containing groups on GO. Herein, we suggest a direct solution to the long-standing problem of limited abundance of carboxyl groups on GO; GO was first reduced to graphene and consequently modified with only carboxyl groups grafted perpendicularly to its surface by a rational synthesis using free-radical addition of isobutyronitrile with subsequent hydrolysis. Such grafted graphene oxide can contain a high amount of carboxyl groups for consequent biofunctionalization, at which the extent of grafting is limited only by the number of carbon atoms in the graphene plane; in contrast, the abundance of carboxyl groups on "classical" GO is limited by the amount of terminal carbon atoms. Such a graphene platform embedded with perpendicularly grafted carboxyl groups was characterized in detail by X-ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy, and its application was exemplified with single-nucleotide polymorphism detection. It was found that the removal of oxygen functionalities after the chemical reduction enhanced the electron-transfer rate of the graphene. More importantly, the introduction of carboxyl groups promoted a more efficient immobilization of DNA probes on the

  7. Tuning metal–carboxylate coordination in crystalline metal–organic frameworks through surfactant media

    International Nuclear Information System (INIS)

    Although it has been widely demonstrated that surfactants can efficiently control the size, shape and surface properties of micro/nanocrystals of metal–organic frameworks (MOFs) due to the strong interactions between surfactants and crystal facets of MOFs, the use of surfactants as reaction media to grow MOF single crystals is unprecedented. In addition, compared with ionic liquids, surfactants are much cheaper and can have multifunctional properties such as acidic, basic, neutral, cationic, anionic, or even block. These factors strongly motivate us to develop a new synthetic strategy: growing crystalline MOFs in surfactants. In this report, eight new two-dimensional (2D) or three-dimensional (3D) MOFs have been successfully synthesized in an industrially-abundant and environmentally-friendly surfactant: polyethylene glycol-200 (PEG-200). Eight different coordination modes of carboxylates, ranging from monodentate η1 mode to tetra-donor coordination µ3-η1:η2:η1 mode, have been founded in our research. The magnetic properties of Co-based MOFs were investigated and MOF NTU-Z6b showed a phase transition with a Curie temperature (Tc) at 5 K. Our strategy of growing crystalline MOFs in surfactant could offer exciting opportunities for preparing novel MOFs with diverse structures and interesting properties. - Graphical abstract: Surfactants have been used as reaction media to grow MOF single crystals for the first time. Eight new two-dimensional or three-dimensional MOFs were successfully synthesized in surfactant polyethylene glycol-200 (PEG-200). Coordination modes of carboxylates up to eight were founded. Our strategy of growing crystalline MOFs in surfactant could offer exciting opportunities for preparing novel MOFs with diverse structures and interesting properties. Display Omitted - Highlights: • Surfactant-thermal synthesis of crystalline metal–organic frameworks. • Eight new 2-D or 3-D metal–organic frameworks. • Eight different metal–carboxylate

  8. Carbon dioxide utilization via carbonate-promoted C-H carboxylation

    Science.gov (United States)

    Banerjee, Aanindeeta; Dick, Graham R.; Yoshino, Tatsuhiko; Kanan, Matthew W.

    2016-03-01

    Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO32-) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)—a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO32--promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

  9. Neuron-astrocyte interactions, pyruvate carboxylation and the pentose phosphate pathway in the neonatal rat brain.

    Science.gov (United States)

    Morken, Tora Sund; Brekke, Eva; Håberg, Asta; Widerøe, Marius; Brubakk, Ann-Mari; Sonnewald, Ursula

    2014-01-01

    Glucose and acetate metabolism and the synthesis of amino acid neurotransmitters, anaplerosis, glutamate-glutamine cycling and the pentose phosphate pathway (PPP) have been extensively investigated in the adult, but not the neonatal rat brain. To do this, 7 day postnatal (P7) rats were injected with [1-(13)C]glucose and [1,2-(13)C]acetate and sacrificed 5, 10, 15, 30 and 45 min later. Adult rats were injected and sacrificed after 15 min. To analyse pyruvate carboxylation and PPP activity during development, P7 rats received [1,2-(13)C]glucose and were sacrificed 30 min later. Brain extracts were analysed using (1)H- and (13)C-NMR spectroscopy. Numerous differences in metabolism were found between the neonatal and adult brain. The neonatal brain contained lower levels of glutamate, aspartate and N-acetylaspartate but similar levels of GABA and glutamine per mg tissue. Metabolism of [1-(13)C]glucose at the acetyl CoA stage was reduced much more than that of [1,2-(13)C]acetate. The transfer of glutamate from neurons to astrocytes was much lower while transfer of glutamine from astrocytes to glutamatergic neurons was relatively higher. However, transport of glutamine from astrocytes to GABAergic neurons was lower. Using [1,2-(13)C]glucose it could be shown that despite much lower pyruvate carboxylation, relatively more pyruvate from glycolysis was directed towards anaplerosis than pyruvate dehydrogenation in astrocytes. Moreover, the ratio of PPP/glucose-metabolism was higher. These findings indicate that only the part of the glutamate-glutamine cycle that transfers glutamine from astrocytes to neurons is operating in the neonatal brain and that compared to adults, relatively more glucose is prioritised to PPP and pyruvate carboxylation. Our results may have implications for the capacity to protect the neonatal brain against excitotoxicity and oxidative stress.

  10. Effects of temperature and sodium carboxylate additives on mineralization of calcium oxalate in silica gel systems

    Institute of Scientific and Technical Information of China (English)

    OUYANG Jianming; DENG Suiping; LI Xiangping; TAN Yanhua; Bernd Tieke

    2004-01-01

    The effects of temperature and multifunctional sodium carboxylate additives on the phase composition and morphology of calcium oxalate (CaOxa) crystals grown in silica gel system were systematically investigated using scanning electron microscopy (SEM), powder X-ray diffraction (XRD), and Fourier-transform infrared spectra (FT-IR). The sodium carboxylates investigated include: monocarboxylate sodium acetate (NaAc), disodium tartrate (Na2tart), trisodium citrate (Na3cit), and the disodium salt of ethylenediaminetetraacetic acid (Na2edta). The temperature range was from 7℃ to 67℃. The crystallization temperature affects the phase compositions, the growth rate, and the morphology of CaOxa. First, the logarithm of the percentage of calcium oxalate dihydrate (COD) formed at a certain temperature (T) is proportional to the reciprocal of temperature (1/T). Second, the weight of CaOxa crystals decreases as decreasing the temperature. At a given temperature, the ability of the sodium carboxylates to induce COD follows the order: Na2edta > Na3cit > Na2tart >> NaAc. Third, the multicarboxylates can decrease the surface area of calcium oxalate monohydrate (COM).It makes the edges and tips of COM crystals blunt and oval. All the three changes, an increase of the content of COD, a decrease of the weight of CaOxa crystals, and a decrease of the surfacearea of COM crystals,can inhibit the formation of CaOxa stones. These results support the clinical use of citrates and may be helpful in elucidating the mechanisms of the formation of CaOxa calculus.

  11. Self-assembled metalla-bowls for selective sensing of multi-carboxylate anions.

    Science.gov (United States)

    Mishra, Anurag; Vajpayee, Vaishali; Kim, Hyunuk; Lee, Min Hyung; Jung, Hyunji; Wang, Ming; Stang, Peter J; Chi, Ki-Whan

    2012-01-28

    Two new tetranuclear cationic metalla-bowls 4 and 5 were self-assembled from a bis-pyridine amide ligand (H(2)L) (1) and arene-ruthenium acceptors, [(Ru(2)(μ-η(4)-C(2)O(4))(η(6)-p-cymene)(2)](O(3)SCF(3))(2) (2) and [Ru(2)(dhnd)(η(6)-p-cymene)(2)](O(3)SCF(3))(2) (dhnd = 6,11-dihydroxy-5,12-naphthacenedionato) (3), respectively. The metalla-bowls were characterized by multinuclear NMR, ESI-MS, UV-Vis spectroscopy, and single crystal X-ray diffraction study of 4. The crystal structure of 4 reveals unambiguous proof for the molecular shape of the metalla-bowl and the encapsulation of one triflate anion in the cavity through hydrogen bonding. The metalla-bowl 5 has been evaluated for anion binding studies by use of amide ligand as a hydrogen bond donor and arene-Ru acceptor as a signalling unit. UV-Vis titration studies showed that 5 selectively binds with multi-carboxylate anions such as oxalate, tartrate and citrate in a 1 : 1 fashion with high binding constants of 4.0-5.5 × 10(4) M(-1). Furthermore, the addition of multi-carboxylate anions into a solution of 5 gave rise to a large enhancement of fluorescence intensity attributable to the blocking of a photo-induced electron transfer process from the arene-ruthenium moiety to the amidic donor in 5. However, the fluorescence intensity almost remains unchanged upon addition of other anions including F(-), Cl(-), PF(6)(-), MeCOO(-), NO(3)(-) and PhCOO(-), as identically seen in the UV-Vis titration experiments, pointing to the high selectivity of 5 for the sensing of multi-carboxylate anions.

  12. Carbon dioxide utilization via carbonate-promoted C-H carboxylation.

    Science.gov (United States)

    Banerjee, Aanindeeta; Dick, Graham R; Yoshino, Tatsuhiko; Kanan, Matthew W

    2016-03-10

    Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO3(2-)) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)--a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO3(2-)-promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

  13. Effect of side chain length on intrahelical interactions between carboxylate- and guanidinium-containing amino acids.

    Science.gov (United States)

    Kuo, Hsiou-Ting; Yang, Po-An; Wang, Wei-Ren; Hsu, Hao-Chun; Wu, Cheng-Hsun; Ting, Yu-Te; Weng, Ming-Huei; Kuo, Li-Hung; Cheng, Richard P

    2014-08-01

    The charge-containing hydrophilic functionalities of encoded charged amino acids are linked to the backbone via different numbers of hydrophobic methylenes, despite the apparent electrostatic nature of protein ion pairing interactions. To investigate the effect of side chain length of guanidinium- and carboxylate-containing residues on ion pairing interactions, α-helical peptides containing Zbb-Xaa (i, i + 3), (i, i + 4) and (i, i + 5) (Zbb = carboxylate-containing residues Aad, Glu, Asp in decreasing length; Xaa = guanidinium residues Agh, Arg, Agb, Agp in decreasing length) sequence patterns were studied by circular dichroism spectroscopy (CD). The helicity of Aad- and Glu-containing peptides was similar and mostly pH independent, whereas the helicity of Asp-containing peptides was mostly pH dependent. Furthermore, the Arg-containing peptides consistently exhibited higher helicity compared to the corresponding Agp-, Agb-, and Agh-containing peptides. Side chain conformational analysis by molecular mechanics calculations showed that the Zbb-Xaa (i, i + 3) and (i, i + 4) interactions mainly involved the χ 1 dihedral combinations (g+, g+) and (g-, g+), respectively. These low energy conformations were also observed in intrahelical Asp-Arg and Glu-Arg salt bridges of natural proteins. Accordingly, Asp and Glu provides variation in helix characteristics associated with Arg, but Aad does not provide features beyond those already delivered by Glu. Importantly, nature may have chosen the side chain length of Arg to support helical conformations through inherent high helix propensity coupled with stabilizing intrahelical ion pairing interactions with the carboxylate-containing residues.

  14. Structural Studies of the Serine-Carboxyl Proteinase Kumamolisin and the Metallopeptidase Peptidyl-Dipeptidase Dcp

    OpenAIRE

    Comellas Bigler, Mireia

    2007-01-01

    The crystal structure of the serine-carboxyl proteinase kumamolisin was solved in native form and in complex with two aldehyde inhibitors. The structures show a subtilisin-like fold with a modified catalytic triad (Ser-Glu-Asp), which allows proteolytic activity at acidic pH. The crystal structure analysis of the full-length prokumamolisin S278A exhibits an uncleaved linker segment that extends along the active-site cleft in a substrate-like manner. This evidence points to an autocatalytic cl...

  15. ZnO-coated carbon nanotubes: inter-diffusion of carboxyl groups and enhanced photocurrent generation.

    Science.gov (United States)

    Hung, Chia-I; Wen, Hua-Chiang; Lai, Yao-Cheng; Chang, Shih-Hsin; Chou, Wu-Ching; Hsu, Wen-Kuang

    2015-03-16

    ZnO is a defect-governed oxide and emits light at both visible and UV regimes. This work employs atomic layer deposition to produce oxide particles on oxygenated carbon nanotubes, and the composites only show emission profiles at short wavelengths. The quenching of defect-related emissions at long wavelengths is verified, owing to carboxyl diffusion into oxygen vacancies, and doping is supported by ZnCO3 formation in oxide lattice. Fully coated tubes display an increased photocurrent and the quantum efficiency increases by 22 % relative to the bare nanotubes. PMID:25572260

  16. Unusual transient absorption dynamics of silver nanoparticles in solutions of carboxylated amine complexons

    Science.gov (United States)

    Shevchenko, G. P.; Zhuravkov, V. A.; Tretyak, E. V.; Tikhomirov, S. A.; Buganov, O. V.; Ponyavina, A. N.; Pham, Hong Minh; Do, Hoang Tung; Duong Pham, Van; Nguyen, Dai Hung

    2016-09-01

    We present the results of research on fast relaxation dynamics in the electronic excitation of silver nanoparticles synthesized in the presence of carboxylated amine complexons (NTA, Na2EDTA, DTPA) without any reductant or polymeric stabilizer. Unusual transient absorption dynamics in these objects after femtosecond laser irradiation was found, manifesting as the appearance of an additional long-lived bleaching band. The effect may be assigned to the inhomogeneous and porous shell of silver nanoparticles synthesized by such a procedure, as the consequence of a partial fragmentation of this shell due to heating under femtosecond laser excitation of plasmonic nanoparticles and subsequent electron-phonon energy relaxation.

  17. Synthesis, Structure and Catalytic Activity of NHC-Ag(I) Carboxylate Complexes.

    Science.gov (United States)

    Wong, Valerie H L; Vummaleti, Sai V C; Cavallo, Luigi; White, Andrew J P; Nolan, Steven P; Hii, King Kuok Mimi

    2016-09-01

    A general synthetic route was used to prepare 15 new N-heterocyclic carbene (NHC)-Ag(I) complexes bearing anionic carboxylate ligands [Ag(NHC)(O2 CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand-accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC-Au and pyridyl-Ag(I) complexes. PMID:27483036

  18. Cationic zinc (II) dimers and one dimensional coordination polymer from ionic carboxylic acid

    Indian Academy of Sciences (India)

    Paladugu Suresh; Ganesan Prabusankar

    2014-09-01

    A rare example of chelating two tetra cationic paddle-wheel zinc dimers were synthesized from the reaction between flexible imidazolium carboxylate (LH2Br2) and corresponding zinc precursors. A zinc coordination polymer was synthesised by treating in situ generation of 2 in the presence of 4,4′-bipyridine. These new molecules, dimers and polymer, were characterized by FT-IR, NMR, UV-vis, fluorescent and single crystal X-ray diffraction techniques. Zinc polymer is the first example of 1D coordination polymer constructed by tetra cationic zinc dimer as a secondary building unit in coordination polymer.

  19. Spectrophotometric determination of ruthenium using 1-pentyl 4,6-dihydroxy-5-nitrosopyridine-3-carboxylate

    International Nuclear Information System (INIS)

    A method of spectrophotometric analysis for ruthenium, using the reagent 1-pentyl 4,6-dihydroxy-5-nitrosopyridine-3-carboxylate, has been developed. Several interferences are removed by extraction prior to the development of the purple color formed between PDNHPC and ruthenium. The molar absorptivity of the PDHNPC-ruthenium complex is 4.2 x 104 at 535 nm. The complex forms at a 3 : 1 ligand-metal ratio. This procedure provides the most sensitive colorimetric method for the determination of ruthenium. (author)

  20. ELECTROSTATIC INTERACTION HYBRIDS FROM WATER-BORNE CONDUCTIVE POLYANILINE AND INORGANIC PRECURSOR CONTAINING CARBOXYL GROUP

    Institute of Scientific and Technical Information of China (English)

    Jing Luo; Xian-hong Wang; Ji Li; Xiao-jiang Zhao; Fo-song Wang

    2007-01-01

    Electrostatic interaction conductive hybrids were prepared in water/ethanol solution by the sol-gel process from inorganic sol containing carboxyl group and water-borne conductive polyaniline(cPANI).The electrostatic interaction hybrids film displayed 1-2 orders of magnitude higher electrical conductivity in comparison with common hybrids film,showing remarkable conductivity stability against water soaking.Most strikingly,it displayed ideal electrochemical activity even in a solution with pH=14,which enlarged the conducting polyaniline application window to strong alkaline media.

  1. Requirement of the Carboxyl Terminus of a Bacterial Chemoreceptor for Its Targeted Proteolysis

    Science.gov (United States)

    Alley, M. R. K.; Maddock, Janine R.; Shapiro, Lucille

    1993-03-01

    The bacterium Caulobacter crescentus yields two different progeny at each cell division; a chemotactically competent swarmer cell and a sessile stalked cell. The chemotaxis proteins are synthesized in the predivisional cell and then partition only to the swarmer cell upon division. The chemoreceptors that were newly synthesized were located at the nascent swarmer pole of the predivisional cell, an indication that asymmetry was established prior to cell division. When the swarmer cell differentiated into a stalked cell, the chemoreceptor was specifically degraded by virtue of an amino acid sequence located at its carboxyl terminus. Thus, a temporally and spatially restricted proteolytic event was a component of this differentiation process.

  2. CATALYTIC ESTERIFICATION OF CARBOXYLIC ACIDS WITH ALCOHOLS BY SULFO—POLYVINYL CHLORIDE

    Institute of Scientific and Technical Information of China (English)

    YuShanxin; ZHAOZongbao; 等

    1993-01-01

    Polyvinyl Chloride reacted with chlorosulfonic acid to from a polymer catalyst PVC-SO3H.This polymer catalyst was found to have high activity for resterification reaction between carboxylic acids and alcohols.This paper deals with the conditions in synthesis of n-butlyacetate catalyzed with PVC-SO3H.The PVC-SO3H was used as a catalyst for preparing 11 esters of acetic acid,propionic acid and butyric acid with the yields of 82-92%.

  3. Aldehydes, ketones, and carboxylic acids formed radiolytically in aqueous solutions of cyanides and simple nitriles

    International Nuclear Information System (INIS)

    A systematic search for aldehydes, ketones, and carboxylic acids was carried out in aqueous solutions of HCN, NH4CN, CH3CN, and C2H4CN, that had received multikilogray doses of 60Co γ radiation. About 30 radiolytic products were identified, among them a large variety of dicarboxylic and tricarboxylic acids. Some of them might be of significant interest in molecular evolution studies of prebiotic processes. They originate in the free-radical-initiated chemical reactions where the additional oligomerization processes are particularly important. Most of the radiolytic products appear in both cyanides and nitriles and point to the importance of reactions involving the carbon-nitrogen triple bond

  4. Wind tunnel investigations on the retention of carboxylic acids during riming

    Science.gov (United States)

    Jost, Alexander; Szakáll, Miklós; Diehl, Karoline; Mitra, Subir K.; Borrmann, Stephan

    2015-04-01

    In mid-latitudes, precipitation is mainly initiated via the ice phase in mixed phase clouds. In such clouds the ice particles grow to precipitation sizes at the expense of liquid drops through riming which means that supercooled droplets collide with ice particles and subsequently freeze. Water-soluble trace substances present in the liquid phase might remain only fractionally in the ice phase after freezing. This fractionation is called retention and is an important ratio which quantifies the partitioning of atmospheric trace substances between the phases. Laboratory experiments were carried out at the Mainz vertical wind tunnel to determine the retention of lower mono- and di-carboxylic acids during riming. Due to their low molecular weight and their polarity these acids are water-soluble. In the atmosphere formic acid and acetic acid are the most abundant mono-carboxylic acids in the gas and aqueous phase, thus, they represent the major fraction of carboxylic acids in cloud water. Oxalic and malonic acid are common coatings on aerosol particles because of their relatively low saturation vapor pressure. These di-carboxylic acids might therefore promote the aerosol particles to act as cloud condensation nuclei and additionally contribute to the aqueous phase chemistry in cloud droplets. The conditions during the riming experiments in the wind tunnel were similar to those in atmospheric mixed phase clouds, i.e. temperatures from -18°C to -6 °C, liquid water contents between 0.5 and 1.5 g/m3, and liquid drop radii between 10 and 20 μm. The liquid phase concentrations ranged from 3 to 5 mg/l (4.1 water was analyzed by ion chromatography and the retention coefficients, i.e. the fractions of the species which remained in the ice phase were determined. Average retention coefficients of formic acid and acetic acid were 0.73 ± 0.07 and 0.62 ± 0.12, respectively; both oxalic and malonic acids had average retention coefficients of 0.98 ± 0.04. These variations can be

  5. Metal Carboxylate Nanorods and Metal Oxide Nanoparticles Synthesized Using Reverse Micelles

    Institute of Scientific and Technical Information of China (English)

    Ashok.K.Ganguli(Department; of; Chemistry; Indian; Institute; of; Technology

    2007-01-01

    1 Results Nanorods of transition metal (Cu,Ni,Mn,Zn,Co and Fe) carboxylates (oxalates and succinates) have been synthesized using a reverse-micellar technique[1-3].These oxalate nanorods have been shown to be an ideal source for obtaining monophasic and homogeneous nanoparticles of transition metal oxides at low temperatures of 450 ℃.Grain size of oxide nanoparticles could be controlled by optimizing the nature of non-polar solvent and surfactant.The metal oxalate precursor could be decomposed in suitab...

  6. Visible-Light-Induced Decarboxylative Functionalization of Carboxylic Acids and Their Derivatives.

    Science.gov (United States)

    Xuan, Jun; Zhang, Zhao-Guo; Xiao, Wen-Jing

    2015-12-21

    Visible-light-induced radical decarboxylative functionalization of carboxylic acids and their derivatives has recently received considerable attention as a novel and efficient method to create CC and CX bonds. Generally, this visible-light-promoted decarboxylation process can smoothly occur under mild reaction conditions with a broad range of substrates and an excellent functional-group tolerance. The radical species formed from the decarboxylation step can participate in not only single photocatalytic transformations, but also dual-catalytic cross-coupling reactions by combining photoredox catalysis with other catalytic processes. Recent advances in this research area are discussed herein. PMID:26509837

  7. Synthesis and Structural Characterization of 1- and 2-Substituted Indazoles: Ester and Carboxylic Acid Derivatives

    OpenAIRE

    Isabel Bento; Teresa Duarte, M.; M. João M. Curto; Inês F. Antunes; Hélène Ramos; Fátima C. Teixeira

    2006-01-01

    A series of indazoles substituted at the N-1 and N-2 positions with ester-containing side chains -(CH2)nCO2R of different lengths (n = 0-6, 9, 10) are described.Nucleophilic substitution reactions on halo esters (X(CH2)nCO2R) by 1H-indazole inalkaline solution lead to mixtures of N-1 and N-2 isomers, in which the N-1 isomerpredominates. Basic hydrolysis of the ester derivatives allowed the synthesis of thecorresponding indazole carboxylic acids. All compounds were fully characterised bymultin...

  8. The First General Electron Transfer Reductions of Carboxylic Acid Derivatives Using Samarium Diiodide

    OpenAIRE

    Spain, Malcolm Peter

    2014-01-01

    The development of new methods for the reduction of carboxylic acid derivatives is described. The ability to reduce these carbonyl derivatives through radical intermediates provides an orthogonal approach as compared with hydride based reductions.Initial experiments focused on the development of the SmI2–H2O system, where we have shown that chelation effects can be utilised to facilitate reduction of cyclic esters. Furthermore, a revised mechanism for the SmI2–H2O mediated reduction of lacton...

  9. Synthesis, growth, structural, thermal and optical studies of pyrrolidinium-2-carboxylate-4-nitrophenol single crystals

    Science.gov (United States)

    Swarna Sowmya, N.; Sampathkrishnan, S.; Vidyalakshmi, Y.; Sudhahar, S.; Mohan Kumar, R.

    2015-06-01

    Organic nonlinear optical material, pyrrolidinium-2-carboxylate-4-nitrophenol (PCN) was synthesized and single crystals were grown by slow evaporation solution growth method. Single crystal X-ray diffraction analysis confirmed the structure and lattice parameters of PCN crystals. Infrared, Raman and NMR spectral analyses were used to elucidate the functional groups present in the compound. The thermal behavior of synthesized compound was studied by thermogravimetric and differential scanning calorimetry (TG-DSC) analyses. The photoluminescence property was studied by exciting the crystal at 360 nm. The relative second harmonic generation (SHG) efficiency of grown crystal was estimated by using Nd:YAG laser with fundamental wavelength of 1064 nm.

  10. Hydrolysis of carboxylate ester catalyzed by a new artificial abzyme based on molecularly imprinted polymer

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A new kind of artificial abzyme MIP-3, which contains N-phenyl benzonic amide group and “nanochannel” formed by embedded ZnO nano materials, and is imprinted by a transition-state analogue of p-nitrophenyl methyphosphonate in the hydrolysis of p-nitrophenyl acetate, was prepared by radical co-polymerization. Hydrolytic kinetics of p-nitrophenyl carboxylate catalyzed by MIP-3 was investigated. The results showed that the artificial abzyme exhibited notable substructure selectivity and strong catalytic ability in hydrolysis of p-nitrophenyl acetate

  11. catena-Poly[[(pyrimidine-2-carboxylic acidiron(II]-μ-oxalato

    Directory of Open Access Journals (Sweden)

    Jiong-Peng Zhao

    2010-09-01

    Full Text Available In the title complex, [Fe(C2O4(C5H4N2O4]n, the FeII ion is coordinated by two oxalate anions and a pyrimidine-2-carboxylic acid ligand in a slightly distorted octahedral geometry. Each oxalate anion chelates to two FeII ions, forming chains along the a axis. The chains are further connected by O—H...O and C—H...O hydrogen bonds, stabilizing the structure. An intramolecular O—H...N interaction results in a five-membered ring.

  12. A Convenient, General Synthesis of 1,1-Dimethylallyl Esters as Protecting Groups for Carboxylic Acids

    Science.gov (United States)

    Sedighi, Minoo; Lipton, Mark A.

    2006-01-01

    Carboxylic acids were converted in high yield to their 1,1-dimethylallyl (DMA) esters in two steps. Palladium-catalyzed deprotection of DMA esters was shown to be compatible with tert-butyl, benzyl and Fmoc protecting groups, and Fmoc deprotection could be carried out selectively in the presence of DMA esters. DMA esters were also shown to be resistant to nucleophilic attack, suggesting that they will serve as alternatives to tert-butyl esters when acidic deprotection conditions need to be avoided. PMID:15816730

  13. A convenient, general synthesis of 1,1-dimethylallyl esters as protecting groups for carboxylic acids.

    Science.gov (United States)

    Sedighi, Minoo; Lipton, Mark A

    2005-04-14

    [reaction: see text] Carboxylic acids were converted in high yield to their 1,1-dimethylallyl (DMA) esters in two steps. Palladium-catalyzed deprotection of DMA esters was shown to be compatible with tert-butyl, benzyl, and Fmoc protecting groups, and Fmoc deprotection could be carried out selectively in the presence of DMA esters. DMA esters were also shown to be resistant to nucleophilic attack, suggesting that they will serve as alternatives to tert-butyl esters when acidic deprotection conditions need to be avoided.

  14. STRUCTURAL FEATURE AND EXCHANGE KINETICS OF CARBOXYLATED POLYPROPYLENE ION EXCHANGE RESIN

    Institute of Scientific and Technical Information of China (English)

    WU Chinyung; YANG Chaoshiung; YANG Chong

    1987-01-01

    The present article deals with the exchange process of bivalent metal ions, such as Zn2 +, Cd2 + and Hg2+, etc., taken up by non-crosslinked carboxylated polypropylene (CPP) resin. The control factor of the exchange rate deduced from the kinetic data is governed basically by the chemical reaction rather than the mass transfer effect particle diffusion and/or liquid film diffusion. In solution, all the graft chains in the outer shell ofa CPP resin could form a "quasi-macromolecular solution" domain. This opinion further demonstrates the structural pattern of CPP resin proposed in earlier paper[1].

  15. Reinforcement of hydrogenated carboxylated nitrile-butadiene rubber by multi-walled carbon nanotubes

    International Nuclear Information System (INIS)

    Hydrogenated carboxylated acrylonitrile-butadiene rubber (HXNBR) and multi-walled carbon nanotubes (MWCNT) composites were prepared. The dispersion of MWCNT in HXNBR matrix was evaluated by field emission scanning electron microscopy. HXNBR/MWCNT composite had shorter scorch time and optimum curing time compared with that of unfilled HXNBR. The tensile strength and modulus of HXNBR/MWCNT composites increased with increasing MWCNT content. Mooney-Rivlin equation was used to describe the stress-strain behavior of unfilled HXNBR and the strain amplification factor was taken into account for HXNBR/MWCNT composites. The Mullins effect and dynamic mechanical properties of HXNBR/MWCNT composite were also investigated.

  16. Controlled Electrochemical Carboxylation of Graphene To Create a Versatile Chemical Platform for Further Functionalization

    DEFF Research Database (Denmark)

    Bjerglund Pedersen, Emil; Kongsfelt, Mikkel; Shimizu, Kyoko;

    2014-01-01

    An electrochemical approach is introduced for the versatile carboxylation of multi-layered graphene in 0.1 M Bu4NBF4/MeCN. First, the graphene substrate (i.e., graphene chemically vapor-deposited on Ni) is negatively charged at -1.9 V versus Ag/AgI in a degassed solution to allow for intercalation......, this electrochemical method offers a versatile procedure to make all graphene sheets in a multi-layered but expanded structure accessible for functionalization. On a more general level, this approach will provide a versatile way of forming new hybrid materials based on intimate bond coupling to graphene via...

  17. Carboxylic multi-walled carbon nanotubes as immobilized stationary phase in capillary electrochromatography.

    Science.gov (United States)

    Sombra, Lorena; Moliner-Martínez, Yolanda; Cárdenas, Soledad; Valcárcel, Miguel

    2008-09-01

    Carboxylic multi-walled carbon nanotubes (c-MWNT) have been immobilized into a fused-silica capillary for capillary electrochromatography. The c-MWNT were successfully incorporated after the silanization and coupling with glutaraldehyde on the inner surface of the capillary. The electrochromatographic features of the c-MWNT immobilized stationary phase have been evaluated for the analysis of different compounds of pharmaceutical interest. The results indicated high electrochromatographic resolution, good capillary efficiency and retention factors. In addition, highly reproducible results between runs, days and capillaries were obtained.

  18. The Structure-Activity Relationship of an Ozonide Carboxylic Acid (OZ78) Against Fasciola hepatica

    OpenAIRE

    Zhao, Qingjie; Vargas, Mireille; Dong, Yuxiang; ZHOU, Lin; Wang, Xiaofang; Sriraghavan, Kamaraj; Keiser, Jennifer; Vennerstrom, Jonathan L.

    2010-01-01

    In this paper, we describe the SAR of ozonide carboxylic acid OZ78 (1) as the first part of our search for a trematocidal synthetic peroxide drug development candidate. We found that relatively small structural changes to 1 resulted most commonly in loss of activity against Fasciola hepatica in vivo. A spiroadamantane substructure and acidic functional group (or ester prodrug) were required for activity. Of twenty-six new compounds administered at single 100 mg/kg oral doses to F. hepatica-in...

  19. Dynamic and structural correlations in nanocomposites of silica with modified surface and carboxylated nitrile rubber.

    Science.gov (United States)

    Sala, Renata L; Oliveira Xavier, Tatielih P; Venâncio, Tiago; Arantes, Tatiane Moraes; Paranhos, Caio M; Camargo, Emerson R

    2016-03-15

    Distinct affinities between the organic and inorganic phases were observed in nanocomposites prepared through a colloidal route with carboxylated nitrile rubber and modified silica nanoparticles, which resulted in variable mechanical properties and improved thermal stability. Nanoparticles with modified surface affected the macromolecular arrangements of the elastomeric matrix, changing the final mechanical behavior of the nanocomposite, which could be predicted by the spin-lattice relaxation time measured by solid-state NMR. It was also possible to identify how each different nanoparticle affected the molecular dynamic of nanocomposite, correlating the dynamic-mechanical analysis with the NMR data of the saturated carbons of the elastomer. PMID:26745740

  20. Cyclic Comonomers for the Synthesis of Carboxylic Acid and Amine Functionalized Poly(l-Lactic Acid

    Directory of Open Access Journals (Sweden)

    Markus Heiny

    2015-03-01

    Full Text Available Degradable aliphatic polyesters such as poly(lactic acid are widely used in biomedical applications, however, they lack functional moieties along the polymer backbone that are amenable for functionalization reactions or could be the basis for interactions with biological systems. Here we present a straightforward route for the synthesis of functional α-ω epoxyesters as comonomers for lactide polymerization. Salient features of these highly functionalized epoxides are versatility in functionality and a short synthetic route of less than four steps. The α-ω epoxyesters presented serve as a means to introduce carboxylic acid and amine functional groups into poly(lactic acid polymers via ring-opening copolymerization.

  1. Kinetics of the esterification of active pharmaceutical ingredients containing carboxylic Acid functionality in polyethylene glycol

    DEFF Research Database (Denmark)

    Schou-Pedersen, Anne Marie V; Hansen, Steen Honoré; Moesgaard, Birthe;

    2014-01-01

    Polyethylene glycols (PEGs) are attractive as excipients in the manufacture of drug products because they are water soluble and poorly immunogenic. They are used in various pharmaceutical preparations. However, because of their terminal hydroxyl groups, PEGs can participate in esterification...... reactions. In this study, kinetics of two active pharmaceutical ingredients, cetirizine and indomethacin possessing carboxylic acid functionality, has been studied in PEG 400 and PEG 1000 at 50°C, 60°C, 70°C, and 80°C. HPLC-UV was applied for the determination of concentrations in the kinetic studies...

  2. Application of thermodynamic models to study micellar properties of sodium perfluoroalkyl carboxylates in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Perez, Alfredo [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain)], E-mail: alf@usc.es; Ruso, Juan M. [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Romero, Maria J. [Department of Inorganic Chemistry, Faculty of Chemistry, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Blanco, Elena [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Prieto, Gerardo [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Sarmiento, Felix [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain)

    2005-06-27

    Sodium perfluoroalkyl carboxylates (CnFONa) with n = 6, 9, 10 have been studied by conductivity measurements at different temperatures. The Krafft point was determined for C9FONa and C10FONa at the highest concentration studied by measuring the temperature dependence of the specific conductivity. The critical micelle concentration (cmc) and the ionization degree of the micelle ({beta}) were estimated from conductivity vs. molality plots at different temperatures. Using these data and previous results on temperature dependence of cmc and {beta} of sodium perfluoroheptanoate and perfluorooctanoate, different models were applied to obtain the thermodynamic properties of micellization. The results are discussed in terms of alkyl chain length.

  3. Simultaneous determination of C2-C22 non-esterified fatty acids and other metabolically relevant carboxylic acids in biological material by gas chromatography of their benzyl esters.

    Science.gov (United States)

    Schatowitz, B; Gercken, G

    1988-03-18

    A method for the simultaneous determination of non-esterified short-, medium- and long-chain fatty acids and other types of metabolically relevant carboxylic acids such as hydroxy, keto, aromatic and dicarboxylic acids in biological material by capillary gas chromatography of benzyl ester derivatives is described. Sample preparation avoiding incomplete isolation of carboxylic acids consisted of deproteinization and extraction with ethanol, fixation of carboxylic acids as carboxylates, removal of interfering compounds such as neutral lipids by hexane extraction and amino acids, acyl carnitines and other cations by cation-exchange chromatography, derivatization of keto groups of ketocarboxylic acids into O-methyl oximes and benzyl ester formation by reaction of the potassium carboxylates with benzyl bromide via crown ether catalysis. The sample preparation conditions were investigated, showing the usefulness of this method for quantitative determinations. Chromatograms obtained from human serum, human urine and rat heart ventricle and concentrations of carboxylic acids in these specimens are presented. PMID:3372640

  4. Calixarene based chiral solvating agents for α-hydroxy carboxylic acids

    Science.gov (United States)

    Bozkurt, Selahattin

    2013-09-01

    Novel chiral calix[4]arene derivatives functionalized at the lower rim have been prepared from the reaction of p-tert-butylcalix[4]arene diamine derivative with N-Phthaloyl-L-phenylalanine or (2S)-2-((benzyloxy)carbonyl)amino)-3-hydroxypropanoic acid or (2S,3R)-2-((benzyloxy)carbonyl)amino-3-hydroxybutanoic acid in 63-81% yield. The structures of these receptors were characterized by FTIR, 1H, 13C and 2D COSY NMR spectroscopy. The enantioselective recognition of these receptors towards the enantiomers of racemic carboxylic acids was studied by 1H NMR spectroscopy. The molar ratios of the chiral compounds with each of the enantiomers of guests were determined by using Job plots. The Job plots indicate that the hosts form 1:2 instantaneous complexes with all guests. The receptors exhibited different chiral recognition abilities toward the enantiomers of racemic guests. NMR studies demonstrated that the receptors function as highly effective chiral shift reagents for determining the enantiomeric purity of a series of carboxylic acids.

  5. Functionalization of carboxylated multiwall nanotubes with imidazole derivatives and their toxicity investigations

    Directory of Open Access Journals (Sweden)

    Javad Azizian

    2010-11-01

    Full Text Available Javad Azizian1, Hasan Tahermansouri1, Esmaeil Biazar2, Saeed Heidari3, Davood Chobfrosh Khoei11Department of Chemistry, Science and Research branch, Islamic Azad University, Ponak, Tehran, Iran; 2Young researchers club – Islamic Azad University, Tonekabon Branch, Iran; 3Proteomics Research Center, Faculty of Paramedical Sciences, Shahid Beheshty University of Medical Sciences,Tehran, IranAbstract: Imidazoles and their derivatives are compounds with chemotherapeutic applications. In this study, we investigated the chemical functionalization of carboxylated multiwalled carbon nanotubes (MWNT–COOH by 1,2-phenylendiamine. Multiwalled nanotube (MWNT–benzimidazole was obtained by an MWNT–amide reaction with POCl3 after 72 hours, which was confirmed by Fourier transform infrared, scanning electron microscopy, thermal gravimetric analysis, and elemental analysis. These functionalizations were chosen due to -NH2 and NHCO active sites in MWNT–amide for future application. Toxicity assays with fibroblast cells and MTT test for measurement of viable cell numbers were also performed. Cellular results did not show any toxicity change in modified samples from that of the reference samples.Keywords: functionalization, 1,2-phenylendiamine, carboxylated multiwall nanotubes, toxicity

  6. Effects of long and short carboxylated or aminated multiwalled carbon nanotubes on blood coagulation.

    Directory of Open Access Journals (Sweden)

    Jie Meng

    Full Text Available In this work the effects of four different multiwalled carbon nanotubes (MWCNTs, including long carboxylated (L-COOH, short carboxylated (S-COOH, long aminated (L-NH(2 and short aminated (S-NH(2 ones, on the integrity of red blood cells, coagulation kinetics and activation of platelets were investigated with human whole blood. We found that the four MWCNTs induced different degrees of red blood cell damage as well as a mild level of platelet activation (10-25%. L-COOH and L-NH(2 induced a higher level of platelet activation than S-COOH and S-NH(2 respectively; meanwhile L-NH(2 caused marked reductions in platelet viability. The presence of the four MWCNTs led to earlier fibrin formation, L-NH(2 increased the clots hardness significantly, while L-COOH and S-NH(2 made the clots become softer. It was concluded that the four MWCNTs affected blood coagulation process and the clots mechanical properties; they also altered the integrity of the red blood cells and the viability of the platelets, as well as induced platelets activation. The effects of MWCNTs depended on the size and chemistry of the nanotubes and the type of cells they contacted.

  7. Adsorption of Co(II) by a carboxylate-functionalized polyacrylamide grafted lignocellulosics.

    Science.gov (United States)

    Shibi, I G; Anirudhan, T S

    2005-02-01

    A new adsorbent (PGBS-COOH) having carboxylate functional group at the chain end was synthesized by graft copolymerization of acrylamide onto banana stalk, BS (Musa Paradisiaca) using ferrous ammonium sulphate/H2O2 redox initiator system. The efficiency of the adsorbent in the removal of cobalt [Co(II)] from water was investigated using batch adsorption technique. The adsorbent exhibits very high adsorption potential for Co(II) and under optimum conditions more than 99% removal was achieved. The maximum adsorption capacity was observed at the pH range 6.5-9.0. The equilibrium isotherm data were analysed using three isotherm models, Langmuir, Freundlich and Scatchard, to determine the best fit equation for the sorption of Co(II) on the PGBS-COOH. A comparative study with a commercial cation exchanger, Ceralite IRC-50, having carboxylate functional group showed that PGBS-COOH is 2.8 times more effective compared to Ceralite IRC-50 at 30 degrees C. Synthetic nuclear power plant coolant water samples were also treated by the adsorbent to demonstrate its efficiency in removing Co(II) from water in the presence of other metal ions. Acid regeneration was tried for several cycles to recover the adsorbed metal ions and also to restore the sorbent to its original state.

  8. Recovery of carboxylic acids at pH greater than pK{sub a}

    Energy Technology Data Exchange (ETDEWEB)

    Tung, L.A.

    1993-08-01

    Economics of producing carboxylic acids by fermentation is often dominated, not by the fermentation cost, but by the cost of recovering and purifying the acids from dilute aqueous solutions. Experiments were performed to measure uptakes of lactic and succinic acids as functions of pH by basic polymeric sorbents; sorbent regeneration was also tested. Performance at pH > pK{sub a} and regenerability depend on sorbent basicity; apparent pK{sub a} and monomer pK{sub a} can be used to predict sorbent performance. Two basic amine extractants, Alamine 336 and Amberlite LA-2, in were also studied; they are able to sustain capacity to higher pH in diluents that stabilize the acid-amine complex through H bonding. Secondary amines perform better than tert-amines in diluents that solvate the additional proton. Competitive sulfate and phosphate, an interference in fermentation, are taken up by sorbents more strongly than by extractants. The third step in the proposed fermentation process, the cracking of the trimethylammonium (TMA) carboxylate, was also examined. Because lactic acid is more soluble and tends to self-esterify, simple thermal cracking does not remove all TMA; a more promising approach is to esterify the TMA lactate by reaction with an alcohol.

  9. Penarines A-F, (nor-)sesquiterpene carboxylic acids from Hygrophorus penarius (Basidiomycetes).

    Science.gov (United States)

    Otto, Alexander; Porzel, Andrea; Schmidt, Jürgen; Wessjohann, Ludger; Arnold, Norbert

    2014-12-01

    Five sesquiterpene carboxylic acids (1-5) and one nor-sesquiterpene carboxylic acid (6) of the very rare ventricosane type, named penarines A-F, were isolated from fruiting bodies of the basidiomycete Hygrophorus penarius (Hygrophoraceae). This is the first report of (nor)-sesquiterpenes isolated from basidiocarps of the family Hygrophoraceae. Their structures were elucidated on the basis of extensive 1D ((1)H, (13)C) and 2D (HSQC, HMBC, COSY, ROESY) NMR spectroscopic analyses as well as high-resolution mass spectrometry studies. Additionally, the only known member of this rare type of sesquiterpenes, ventricos-7(13)-ene (7), could be identified via headspace GC-MS analysis in a fruiting body of H. penarius. Compounds 1-6 were devoid of remarkable antifungal activity against Cladosporium cucumerinum. Additionally, the cytotoxic activities of compounds 1 and 2 were evaluated against the human prostate cancer cell line PC-3 and the colon cancer cell line HT-29 showing no significant cytotoxic activity. PMID:25269661

  10. Coordination polymers: trapping of radionuclides and chemistry of tetravalent actinides (Th, U) carboxylates

    International Nuclear Information System (INIS)

    The use of nuclear energy obviously raises the question of the presence of radionuclides in the environment. Currently, their mitigation is a major issue associated with nuclear chemistry. This thesis focuses on both the trapping of radionuclides by porous solids called Metal-Organic Frameworks (MOF) and the crystal chemistry of the carboxylate of tetravalent actinides (AnIV). The academic knowledge of the reactivity of carboxylate of AnIV could help the understanding of actinides speciation in environment. We focused on the sequestration of iodine by aluminum based MOF. The functionalization (electron-donor group) of the MOF drastically enhances the iodine capture capacity. The removal of light actinides (Th and U) from aqueous solution was also investigated as well as the stability of (Al)-MOF under γ radiation. More than twenty coordination polymers based on tetravalent actinides have been synthesized and characterized by single crystal X-ray diffraction. The use of controlled hydrolysis promotes the formation of coordination polymers exhibiting polynuclear cluster ([U4], [Th6], [U6] and [U38]). In order to understand the formation of the largest cluster, the ex-situ study of the solvo-thermal synthesis of compound {U38} has also been investigated. (author)

  11. Novel carboxylated PEG-coating on magnetite nanoparticles designed for biomedical applications

    International Nuclear Information System (INIS)

    Fabrication of PEG coating on magnetite nanoparticles (MNPs) is one of the most favoured ways to ensure biocompatibility. Surface modification of magnetite by an own-prepared comb-like PEG-copolymer (PEGA-AA) was compared with two commercially available ones (carboxy-PEG (PEG-C) and phosphate-PEG (PEG-P)). ATR FT-IR data revealed that all polymers form complexes on the surface of MNPs. Electrophoresis and dynamic light scattering (DLS) experiments showed that both the type and quantity of the polymers' anchoring groups influence the aggregation of coated nanomagnets. PEG-C shell does not provide excess negative charges, so magnetite particles became aggregated. However PEG-P and PEGA-AA gradually modify the surface: neutralizing the originally positively charged MNPs below loading 0.5 mmol/g, while above it a polyanionic layer forms on nanomagnets dispersing them in salty media at pH ~6.5. The PEGA-AA comb-like copolymer is more efficient for MNPs PEGylation due to the uniform distribution of carboxylates and PEG chains along the carbon skeleton. - Highlights: • PEG-polymers were adsorbed through surface complexation on magnetite. • Increasing load of functionalized PEGs gradually modifies the MNP's surface. • MNPs coated completely by polyanionic shell can be dispersed in salty media at pH ~6.5. • Carboxylated comb-like PEG copolymer provides the most efficient biocompatible coating

  12. Novel carboxylated PEG-coating on magnetite nanoparticles designed for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Illés, Erzsébet, E-mail: illese@chem.hu [Department of Physical Chemistry and Materials Science, University of Szeged, Aradi Vt. 1, H-6720 Szeged (Hungary); Tombácz, Etelka, E-mail: tombacz@chem.u-szeged.hu [Department of Physical Chemistry and Materials Science, University of Szeged, Aradi Vt. 1, H-6720 Szeged (Hungary); Szekeres, Márta; Tóth, Ildikó Y. [Department of Physical Chemistry and Materials Science, University of Szeged, Aradi Vt. 1, H-6720 Szeged (Hungary); Szabó, Ákos; Iván, Béla [Department of Polymer Chemistry, Research Centre for Natural Sciences, HAS, P.O. Box 286, H-1519 Budapest (Hungary)

    2015-04-15

    Fabrication of PEG coating on magnetite nanoparticles (MNPs) is one of the most favoured ways to ensure biocompatibility. Surface modification of magnetite by an own-prepared comb-like PEG-copolymer (PEGA-AA) was compared with two commercially available ones (carboxy-PEG (PEG-C) and phosphate-PEG (PEG-P)). ATR FT-IR data revealed that all polymers form complexes on the surface of MNPs. Electrophoresis and dynamic light scattering (DLS) experiments showed that both the type and quantity of the polymers' anchoring groups influence the aggregation of coated nanomagnets. PEG-C shell does not provide excess negative charges, so magnetite particles became aggregated. However PEG-P and PEGA-AA gradually modify the surface: neutralizing the originally positively charged MNPs below loading 0.5 mmol/g, while above it a polyanionic layer forms on nanomagnets dispersing them in salty media at pH ~6.5. The PEGA-AA comb-like copolymer is more efficient for MNPs PEGylation due to the uniform distribution of carboxylates and PEG chains along the carbon skeleton. - Highlights: • PEG-polymers were adsorbed through surface complexation on magnetite. • Increasing load of functionalized PEGs gradually modifies the MNP's surface. • MNPs coated completely by polyanionic shell can be dispersed in salty media at pH ~6.5. • Carboxylated comb-like PEG copolymer provides the most efficient biocompatible coating.

  13. Carboxyl group (-CO2 H) functionalized coordination polymer nanoparticles as efficient platforms for drug delivery.

    Science.gov (United States)

    Novio, Fernando; Lorenzo, Julia; Nador, Fabiana; Wnuk, Karolina; Ruiz-Molina, Daniel

    2014-11-17

    Functionalization of nanoparticles can significantly influence their properties and potential applications. Although researchers can now functionalize metal, metal oxide, and organic polymer nanoparticles with a high degree of precision, controlled surface functionalization of nanoscale coordination polymer particles (CPPs) has remained a significant challenge. The lack of methodology is perhaps one of the greatest roadblocks to the advancement of CPPs into high added-value drug delivery applications. Here, we report having achieved this goal through a stepwise formation and functionalization protocol. We fabricated robust nanoparticles with enhanced thermal and colloidal stabilities by incorporation of carboxyl groups and these surface carboxyl groups could be subsequently functionalized through well-known peptide coupling reactions. The set of chemistries that we employed as proof-of-concept enabled a plethora of new functional improvements for the application of CPPs as drug delivery carriers, including enhanced colloidal stabilities and the incorporation of additional functional groups such as polyethylene glycol (PEG) or fluorescent dyes that enabled tracking of their cellular uptake. Finally, we ascertained the cytotoxicity of the new CPP nanoparticles loaded with camptothecin to human breast adenocarcinoma (MCF-7). Efflux measurements show that the encapsulation of camptothecin enhances the potency of the drug 6.5-fold and increases the drug retention within the cell.

  14. Effect of carboxylic acids as compatibilizer agent on mechanical properties of thermoplastic starch and polypropylene blends.

    Science.gov (United States)

    Martins, Andréa Bercini; Santana, Ruth Marlene Campomanes

    2016-01-01

    In this work, polypropylene/thermoplastic starch (PP/TPS) blends were prepared as an alternative material to use in disposable packaging, reducing the negative polymeric environmental impact. Unfortunately, this material displays morphological characteristics typical of immiscible polymer blends and a compatibilizer agent is needed. Three different carboxyl acids: myristic (C14), palmitic (C16) and stearic acids (C18) were used as natural compatibilizer agent (NCA). The effects of NCA on the mechanical, physical, thermal and morphological properties of PP/TPS blends were investigated and compared against PP/TPS with and without PP-grafted maleic anhydride (PPgMA). When compared to PP/TPS, blends with C18, PPgMA and C14 presented an improvement of 25, 22 and 17% in tensile strength at break and of 180, 194 and 259% in elongation at break, respectively. The highest increase, 54%, in the impact strength was achieved with C14 incorporation. Improvements could be seen, through scanning electron microscopy (SEM) images, in the compatibility between the immiscible components by acids incorporation. These results showed that carboxylic acids, specifically C14, could be used as compatibilizer agent and could substitute PPgMA. PMID:26453854

  15. Chemo-enzymatic epoxidation of olefins by carboxylic acid esters and hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Ruesch gen. Klaas, M.; Warwel, S. [Inst. for Biochemistry and Technology of Lipids, H.P. Kaufmanm-Inst., Federal Centre for Cereal, Potato and Lipid Research, Muenster (Germany)

    1998-12-31

    Ethylen and, recently, butadiene can be epoxidized directly with oxygen and for the epoxidation of propylene, the use of heterogeneous transition metals and organic peroxides (Halcon-Process) is the major player. But, beside from those notable exceptions, all other epoxidations, including large ones like the epoxidation of plant oils as PVC-stabilizers (about 200.000 t/year), are carried out with peroxy acids. Because mcpba is far to expensive for most applications, short chain peracids like peracetic acid are used. Being much less stable than mcpba and thus risky handled in large amounts and high concentrations, these peroxy acids were preferably prepared in-situ. However, conventional in-situ formation of peracids has the serious drawback, that a strong acid is necessary to catalyze peroxy acid formation from the carboxylic acid and hydrogen peroxide. The presence of a strong acid in the reaction mixture often results in decreased selectivity because of the formation of undesired by-products by opening of the oxirane ring. Therefore, we propose a new method for epoxidation based on the in-situ preparation of percarboxylic acids from carboxylic acid esters and hydrogen peroxide catalyzed by a commercial, immobilized lipase. (orig.)

  16. Ionic elastomers based on carboxylated nitrile rubber (XNBR and magnesium aluminum layered double hydroxide (hydrotalcite

    Directory of Open Access Journals (Sweden)

    A. Laskowska

    2014-06-01

    Full Text Available The presence of carboxyl groups in carboxylated nitrile butadiene rubber (XNBR allows it to be cured with different agents. This study considers the effect of crosslinking of XNBR by magnesium aluminum layered double hydroxide (MgAl-LDH, known also as hydrotalcite (HT, on rheometric, mechano-dynamical and barrier properties. Results of XNBR/HT composites containing various HT loadings without conventional curatives are compared with XNBR compound crosslinked with commonly used zinc oxide. Hydrotalcite acts as an effective crosslinking agent for XNBR, as is particularly evident from rheometric and Fourier transform infrared spectroscopy (FTIR studies. The existence of ionic crosslinks was also detected by dynamic mechanical analysis (DMA of the resulting composites. DMA studies revealed that the XNBR/HT composites exhibited two transitions – one occurring at low temperature is associated to the Tg of elastomer and the second at high temperature corresponds to the ionic transition temperature Ti. Simultaneous application of HT as a curing agent and a filler may deliver not only environmentally friendly, zinc oxide-free rubber product but also ionic elastomer composite with excellent mechanical, barrier and transparent properties.

  17. Optimization and characterization of a homogeneous carboxylic surface functionalization for silicon-based biosensing.

    Science.gov (United States)

    Chiadò, Alessandro; Palmara, Gianluca; Ricciardi, Serena; Frascella, Francesca; Castellino, Micaela; Tortello, Mauro; Ricciardi, Carlo; Rivolo, Paola

    2016-07-01

    A well-organized immobilization of bio-receptors is a crucial goal in biosensing, especially to achieve high reproducibility, sensitivity and specificity. These requirements are usually attained with a controlled chemical/biochemical functionalization that creates a stable layer on a sensor surface. In this work, a chemical modification protocol for silicon-based surfaces to be applied in biosensing devices is presented. An anhydrous silanization step through 3-aminopropylsilane (APTES), followed by a further derivatization with succinic anhydride (SA), is optimized to generate an ordered flat layer of carboxylic groups. The properties of APTES/SA modified surface were compared with a functionalization in which glutaraldehyde (GA) is used as crosslinker instead of SA, in order to have a comparison with an established and largely applied procedure. Moreover, a functionalization based on the controlled deposition of a plasma polymerized acrylic acid (PPAA) thin film was used as a reference for carboxylic reactivity. Advantages and drawbacks of the considered methods are highlighted, through physico-chemical characterizations (OCA, XPS, and AFM) and by means of a functional Protein G/Antibody immunoassay. These analyses reveal that the most homogeneous, reproducible and active surface is achieved by using the optimized APTES/SA coupling. PMID:27022864

  18. Low-line edge roughness extreme ultraviolet photoresists of organotin carboxylates

    Science.gov (United States)

    Del Re, Ryan; Passarelli, James; Sortland, Miriam; Cardineau, Brian; Ekinci, Yasin; Buitrago, Elizabeth; Neisser, Mark; Freedman, Daniel A.; Brainard, Robert L.

    2015-10-01

    Pure thin films of organotin compounds have been lithographically evaluated using extreme ultraviolet lithography (EUVL, 13.5 nm). Twenty compounds of the type R2Sn) were spin-coated from solutions in toluene, exposed to EUV light, and developed in organic solvents. Exposures produced negative-tone contrast curves and dense-line patterns using interference lithography. Contrast-curve studies indicated that the photosensitivity is linearly related to the molecular weight of the carboxylate group bound to tin. Additionally, photosensitivity was found to be linearly related to free radical stability of the hydrocarbon group bound directly to tin (R=phenyl, butyl, and benzyl). Dense-line patterning capabilities varied, but two resists in particular show exceptionally good line edge roughness (LER). A resist composed of an amorphous film of )SnCC)2 (1) achieved 1.4 nm LER at 22-nm half-pitch patterning and a resist composed of )Sn) (2) achieved 1.1 nm LER at 35-nm half-pitch at high exposure doses (600 mJ/cm2). Two photoresists that use olefin-based carboxylates, )SnCCH (3) and )SnCC (4), demonstrated better photospeeds (5 mJ/cm2 and 27 mJ/cm2) but worse LER.

  19. A comparative study of the interaction of Tamiflu and Oseltamivir carboxylate with bovine serum albumin.

    Science.gov (United States)

    Vishkaee, Tahereh Sadigh; Mohajerani, Niloufar; Nafisi, Shohreh

    2013-02-01

    Oseltamivir phosphate (Tamiflu) is a pro-drug that is metabolized to its active form (Oseltamivir carboxylate), after oral administration. OC inhibits influenza A and B neuraminidases in vitro and OP inhibits influenza virus infection and replication in vitro. Serum albumin is the most abundant of the proteins in the circulatory system of a wide variety of organisms and plays an important role in the transport and deposition of many drugs. The aim of this study was to examine the interaction of BSA with Tamiflu and Oseltamivir carboxylate in aqueous solution at physiological conditions, using a constant protein concentration and various drug contents. FTIR, UV-Vis spectroscopic methods were used to determine the drugs binding mode, the binding constant and the effects of drug complexation on protein secondary structure. Structural analysis showed that OP and OC bind BSA with overall binding constants of K(OP-BSA)=1.88 (±0.16)×10(4)M(-1) and K(OC-BSA)=5.7 (±0.09)×10(2)M(-1). Drug complexation alters protein conformation by major reduction of α-helix and random coil and increase of β-sheet and turn structures that indicate a partial protein destabilization. The results suggest that BSA might act as carrier proteins for OP in delivering it to target molecules. PMID:23353784

  20. Effect of Alkyl Chain Length on Carboxylic Acid SAMs on Ti-6Al-4V

    Directory of Open Access Journals (Sweden)

    Gavin A. Buckholtz

    2012-07-01

    Full Text Available The formation of methyl-terminated carboxylic acid self-assembled monolayers (SAMs with even numbers of carbons, from eighteen to thirty, was investigated on the oxide surface of Ti-6Al-4V and component metal oxides. Modified surfaces were characterized using diffuse reflectance infrared Fourier transform spectroscopy (DRIFT, matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS and contact angle analysis. Infrared spectroscopy indicated that using aerosol spray deposition techniques, stable, all-trans SAMs of octacosanoic (28 carbons and triacontanoic (30 carbons acids were formed on the alloy. Films were similarly formed on titanium and aluminum oxide. The surface of vanadium oxide exhibited limited reactivity. MALDI-TOF MS confirmed that formed films were monolayers, without multilayers or aggregates present. Water contact angles are indicative of the presence of hydrophobic methyl groups at the interface. This stable carboxylic acid SAM formation could be a useful alternative to phosphonic acid SAMs for corrosion and other applications.

  1. Carboxylic acid terminated, solution exfoliated graphite by organic acylation and its application in drug delivery

    Indian Academy of Sciences (India)

    KOUSHIK BHOWMIK; AMRITA CHAKRAVARTY; U MANJU; GOUTAM DE; ARNAB MUKHERJEE

    2016-09-01

    Graphite nanosheets are considered as a promising material for a range of applications from flexible electronics to functional nanodevices such as biosensors, intelligent coatings and drug delivery. Chemical functionalizationof graphite nanosheets with organic/inorganic materials offers an alternative approach to control the electronic properties of graphene, which is a zero band gap semiconductor in pristine form. In this paper, we report the aromatic electrophilic substitution of solution exfoliated graphite nanosheets (SEGn). The highly conjugated π-electronic system of graphite nanosheets enable it to have an amphiphilic characteristic in aromatic substitution reactions. The substitution was achieved through Friedel–Crafts (FC) acylation reaction under mild conditions using succinic anhydride as acylating agent and anhydrous aluminum chloride as Lewisacid. Such reaction renders towards the carboxylic acid terminated graphite nanosheets (SEGn–FC) that usually requires harsh reaction conditions. The product thus obtained was characterized using various spectroscopicand microscopic techniques. Highly stable water-dispersed sodium salt of carboxylic acid terminated graphite nanosheets (SEGn–FC-Na) was also prepared. A comparative sheet-resistance measurements of SEGn, SEGn–FC and SEGn–FC-Na were also done. Finally, the anticancer drug doxorubicin (DOX) was loaded on water dispersible SEGn–FC-Na with a loading capacity of 0.266 mg mg−1 of SEGn–FC-Na and the release of DOX from this water-soluble DOX-loaded SEGn–FC-Na at two different temperatures was found to be strongly pHdependent.

  2. Carboxylic Acid Photochemistry is a Marine Source of Glyoxal and Other Aldehydes

    Science.gov (United States)

    Chiu, R.; Gonzalez, L.; Tinel, L.; George, C.; Volkamer, R. M.

    2015-12-01

    Glyoxal is a highly water-soluble precursor in secondary organic aerosol (SOA) formation. Over land, glyoxal is known to be produced by the oxidation of volatile organic carbon (VOC) from both anthropogenic and natural sources. However, marine sources are still not well understood. Previous studies above the remote Pacific Ocean have detected typical glyoxal mixing ratios of 30-40 pptv, concentrations too high to be explained with current chemical understanding or atmospheric models. Because the lifetime of glyoxal is very short, the glyoxal found must have originated from, rather than been transported to, the open ocean. Furthermore, eddy covariance measurements indicate that an organic surface microlayer may be producing the glyoxal by as yet unknown processes. Here we present laboratory studies of the formation of glyoxal from carboxylic acids. Nonanoic, octanoic, and heptanoic acids floated on water and subjected to ultraviolet light are converted into their equivalent alkenals. Subsequent ozonolysis of the alkenals leads to the formation of glyoxal. We employ a PTR-MS to detect the alkenals, and a cavity-enhanced DOAS to detect the glyoxal. Considering the ubiquitous occurrence of carboxylic acids and their derivatives in the environment, this mechanism has the potential to be a significant source of glyoxal in the atmosphere.

  3. Self-assembly of indole-2-carboxylic acid at graphite and gold surfaces

    Science.gov (United States)

    De Marchi, Fabrizio; Cui, Daling; Lipton-Duffin, Josh; Santato, Clara; MacLeod, Jennifer M.; Rosei, Federico

    2015-03-01

    Model systems are critical to our understanding of self-assembly processes. As such, we have studied the surface self-assembly of a small and simple molecule, indole-2-carboxylic acid (I2CA). We combine density functional theory gas-phase (DFT) calculations with scanning tunneling microscopy to reveal details of I2CA assembly in two different solvents at the solution/solid interface, and on Au(111) in ultrahigh vacuum (UHV). In UHV and at the trichlorobenzene/highly oriented pyrolytic graphite (HOPG) interface, I2CA forms epitaxial lamellar structures based on cyclic OH⋯O carboxylic dimers. The structure formed at the heptanoic acid/HOPG interface is different and can be interpreted in a model where heptanoic acid molecules co-adsorb on the substrate with the I2CA, forming a bicomponent commensurate unit cell. DFT calculations of dimer energetics elucidate the basic building blocks of these structures, whereas calculations of periodic two-dimensional assemblies reveal the epitaxial effects introduced by the different substrates.

  4. In Vitro Reactivity of Carboxylic Acid-CoA Thioesters with Glutathione

    DEFF Research Database (Denmark)

    Sidenius, Ulrik; Skonberg, Christian; Olsen, Jørgen;

    2004-01-01

    was to investigate whether a correlation could be found between the structure of acyl-CoA thioesters and their reactivities toward the tripeptide, glutathione (ç- Glu-Cys-Gly).  The  acyl-CoA  thioesters  of  eight  carboxylic  acids  (ibuprofen,  clofibric  acid, indomethacin,  fenbufen,  tolmetin,  salicylic  acid......The chemical reactivity of acyl-CoA thioesters toward nucleophiles has been demonstrated in several recent studies. Thus, intracellularly formed acyl-CoAs of xenobiotic carboxylic acids may react covalently with endogenous proteins and potentially lead to adverse effects. The purpose of this study......,  2-phenoxypropionic  acid,  and  (4-chloro-2-methyl-phenoxy)acetic  acid  (MCPA))  were  synthesized,  and  each  acyl-CoA  (0.5  mM)  was incubated with glutathione (5.0 mM) in 0.1 M potassium phosphate (pH 7.4, 37 °C). All of the acyl-CoAs reacted with glutathione to form the respective acyl...

  5. (19)F NMR study of ligand dynamics in carboxylate-bridged diiron(II) complexes supported by a macrocyclic ligand.

    Science.gov (United States)

    Minier, Mikael A; Lippard, Stephen J

    2015-11-01

    A series of asymmetrically carboxylate-bridged diiron(ii) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe2(PIM)(Ar(4F-Ph)CO2)2] (10), [Fe2(F2PIM)(Ar(Tol)CO2)2] (11), and [Fe2(F2PIM)(Ar(4F-Ph)CO2)2] (12), were prepared and characterized by X-ray crystallography, Mössbauer spectroscopy, and VT (19)F NMR spectroscopy. These complexes are part of a rare family of syn N-donor diiron(ii) compounds, [Fe2(X2PIM)(RCO2)2], that are structurally very similar to the active site of the hydroxylase enzyme component of reduced methane monooxygenase (MMOHred). Solution characterization of these complexes demonstrates that they undergo intramolecular carboxylate rearrangements, or carboxylate shifts, a dynamic feature relevant to the reactivity of the diiron centers in bacterial multicomponent monooxygenases. PMID:26418547

  6. 19F NMR Study of Ligand Dynamics in Carboxylate-Bridged Diiron(II) Complexes Supported by a Macrocyclic Ligand

    Science.gov (United States)

    Minier, Mikael A.; Lippard, Stephen J.

    2015-01-01

    A series of asymmetrically carboxylate-bridged diiron(II) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe2(PIM)(Ar4F-PhCO2)2] (10), [Fe2(F2PIM)(ArTolCO2)2] (11), and [Fe2(F2PIM)(Ar4F-PhCO2)2] (12), were prepared and characterized by X-ray crystallography, Mössbauer spectroscopy, and VT 19F NMR spectroscopy. These complexes are part of a rare family of syn-N diiron(II) complexes, [Fe2(X2PIM)(RCO2)2], that are structurally very similar to the active site of the hydroxylase enzyme component of reduced methane monooxygenase (MMOHred). Solution characterization of these complexes demonstrates that they undergo intramolecular carboxylate rearrangements, or carboxylate shifts, a dynamic feature relevant to the reactivity of the diiron centers in bacterial multicomponent monooxygenases. PMID:26418547

  7. A facile and novel approach towards carboxylic acid functionalization of multiwalled carbon nanotubes and efficient water dispersion

    KAUST Repository

    Rehman, Ata Ur

    2013-10-01

    A convenient, cheap and mild covalent functionalization route for multiwalled carbon nanotubes (MWCNTs) have been developed for the first time. The MWCNTs were treated with wet chemical oxidants (NaNO2/HCl, HNO3/H2O2) in order to modify MWCNTs with carboxyl groups. Surface functionality groups and morphology of MWCNTs were analyzed by FTIR, TGA, SEM and TEM. The results consistently confirmed the formation of carboxyl functionalities on MWCNTs, while the structure of MWCNTs has remained relatively intact. Functionalized MWCNTs showed good dispersion in aqueous media than untreated MWCNTs. Results show that NaNO2/HCl treatment is best suited for the chemical functionalization, giving optimum surface carboxyl groups and minimum length shortening of MWCNTs. © 2013 Elsevier B.V.

  8. Influence of cyclic dimer formation on the phase behavior of carboxylic acids. II. Cross-associating systems.

    Science.gov (United States)

    Janeček, Jiří; Paricaud, Patrice

    2013-08-15

    The doubly bonded dimer association scheme (DBD) proposed by Sear and Jackson is extended to mixtures exhibiting both self- and cross-associations. The PC-SAFT equation of state is combined with the new DBD association contribution to describe the vapor-liquid equilibria of binary mixtures of carboxylic acids + associating compounds (water, alcohols, and carboxylic acids). The effect of doubly bonded dimers on the phase behavior in such systems is less important than in mixtures of carboxylic acids with nonassociating compounds, due to the cross-associations that compete with the formation of DBDs. Nevertheless, a clear improvement in the description of vapor-liquid coexistence curves is achieved over the classical 2B association model, particularly for the dew point curves.

  9. Biomimetic Decarboxylation of Carboxylic Acids with PhI(OAc)2 Catalyzed by Manganese Porphyrin [Mn(TPP)OAcl

    Institute of Scientific and Technical Information of China (English)

    GHOLAM REZA Karimipour; ROXANA Ahmadpour

    2008-01-01

    Manganese(Ⅲ) meso-tetraphenylporphyrin acetate [Mn(TPP)OAc] served as an effective catalyst for the oxidative decarboxylation of carboxylic acids with (diacetoxyiodo)benzene [Phl(OAc)2] in CH2C12-H2O(95:5,volume ratio),The aryl substituted acetic acids are more reactive than the less electron rich linear carboxylic acids in the presence of catalyst Mn(TPP)OAc,In the former case,the formation of carbonyl products was complete within just a few minutes with >97% selectivities,and no further oxidation of the produced aldehydes was achieved under these catalytic conditions,This method provides a benign procedure owing to the utilization of low toxic(diacetoxyiodo)benzene,biologically relevant manganese porphyrins,and carboxylic acids.

  10. Anti-cancer evaluation of carboxamides of furano-sesquiterpene carboxylic acids from the soft coral Sinularia kavarattiensis.

    Science.gov (United States)

    Rajaram, Singanaboina; Ramulu, Udugu; Ramesh, Dasari; Srikanth, Dudem; Bhattacharya, Papri; Prabhakar, Peddikotla; Kalivendi, Shasi V; Babu, Katragadda Suresh; Venkateswarlu, Yenamandra; Navath, Suryakiran

    2013-12-01

    The chemical investigation of soft coral Sinularia kavarattiensis is described. It yielded furano-sesquiterpene carboxylic acids 1 and 2 and their methyl esters 3 and 4. Semi-synthesis of furano-sesquiterpene carboxylic acid 1 gave amide derivatives 5-12. Structures of all the compounds were established by IR, NMR and mass spectral analysis. Interestingly all compounds are selectively potent on leukemia cell line. All these compounds were screened for cytotoxic activity against five human cancer cell lines (leukemia, prostate, lung, breast and cervix). Among these compounds 9 and 10 showed promising activity against leukemia and prostate cancer cell lines. PMID:24144848

  11. Benzylidene Acetal Protecting Group as Carboxylic Acid Surrogate: Synthesis of Functionalized Uronic Acids and Sugar Amino Acids.

    Science.gov (United States)

    Banerjee, Amit; Senthilkumar, Soundararasu; Baskaran, Sundarababu

    2016-01-18

    Direct oxidation of the 4,6-O-benzylidene acetal protecting group to C-6 carboxylic acid has been developed that provides an easy access to a wide range of biologically important and synthetically challenging uronic acid and sugar amino acid derivatives in good yields. The RuCl3 -NaIO4 -mediated oxidative cleavage method eliminates protection and deprotection steps and the reaction takes place under mild conditions. The dual role of the benzylidene acetal, as a protecting group and source of carboxylic acid, was exploited in the efficient synthesis of six-carbon sialic acid analogues and disaccharides bearing uronic acids, including glycosaminoglycan analogues. PMID:26572799

  12. Iron-Catalyzed, Highly Regioselective Synthesis of alpha-Aryl Carboxylic Acids from Styrene Derivatives and CO2

    OpenAIRE

    Greenhalgh, Mark D.; Thomas, Stephen P.

    2012-01-01

    The iron-catalyzed hydrocarboxylation of aryl alkenes has been developed using a highly active bench-stable iron(II) precatalyst to give alpha-aryl carboxylic acids in excellent yields and with near-perfect regioselectivity. Using just 1 mol % FeCl2, bis(imino)pyridine 6 (1 mol %), CO2 (atmospheric pressure), and a hydride source (EtMgBr, 1.2 equiv), a range of sterically and electronically differentiated aryl alkenes were transformed to the corresponding alpha-aryl carboxylic acids (up to 96...

  13. Synthesis and Transformations of di-endo-3-Aminobicyclo-[2.2.2]oct-5-ene-2-carboxylic Acid Derivatives

    Directory of Open Access Journals (Sweden)

    Márta Palkó

    2011-09-01

    Full Text Available all-endo-3-amino-5-hydroxybicyclo[2.2.2]octane-2-carboxylic acid (13 and all-endo-5-amino-6-(hydroxymethylbicyclo[2.2.2]octan-2-ol (10 were prepared via dihydro-1,3-oxazine or g-lactone intermediates by the stereoselective functionalization of an N-protected derivative of endo-3-aminobicyclo[2.2.2]oct-5-ene-2-carboxylic acid (2. Ring closure of b-amino ester 4 resulted in tricyclic pyrimidinones 15 and 16. The structures, stereochemistry and relative configurations of the synthesized compounds were determined by IR and NMR.

  14. Gas-Phase Partial Oxidation of Lignin to Carboxylic Acids over Vanadium Pyrophosphate and Aluminum-Vanadium-Molybdenum.

    Science.gov (United States)

    Lotfi, Samira; Boffito, Daria C; Patience, Gregory S

    2015-10-26

    Lignin is a complex polymer that is a potential feedstock for aromatic compounds and carboxylic acids by cleaving the β-O-4 and 5-5' linkages. In this work, a syringe pump atomizes an alkaline solution of lignin into a catalytic fluidized bed operating above 600 K. The vanadium heterogeneous catalysts convert all the lignin into carboxylic acids (up to 25 % selectivity), coke, carbon oxides, and hydrogen. Aluminum-vanadium-molybdenum mostly produced lactic acid (together with formic acid, acrylic acid, and maleic anhydride), whereas the vanadium pyrophosphate catalyst produced more maleic anhydride. PMID:26361086

  15. Iodine-Catalyzed Decarboxylative Amidation of β,γ-Unsaturated Carboxylic Acids with Chloramine Salts Leading to Allylic Amides.

    Science.gov (United States)

    Kiyokawa, Kensuke; Kojima, Takumi; Hishikawa, Yusuke; Minakata, Satoshi

    2015-10-26

    The iodine-catalyzed decarboxylative amidation of β,γ-unsaturated carboxylic acids with chloramine salts is described. This method enables the regioselective synthesis of allylic amides from various types of β,γ-unsaturated carboxylic acids containing substituents at the α- and β-positions. In the reaction, N-iodo-N-chloroamides, generated by the reaction of a chloramine salt with I2 , function as a key active species. The reaction provides an attractive alternative to existing methods for the synthesis of useful secondary allylic amine derivatives. PMID:26493878

  16. Catalytic conversion of carboxylic acids in bio-oil for liquid hydrocarbons production

    International Nuclear Information System (INIS)

    Bio-oil must be upgraded to be suitable for use as a high-grade transport fuel. Crude bio-oil has a high content of carboxylic acids which can cause corrosion, and the high oxygen content of these acids also reduces the oil’s heating value. In this paper, acetic acid and propanoic acid were chosen as the model carboxylic acids in bio-oil. Their behavior in the production of liquid hydrocarbons during a catalytic conversion process was investigated in a micro-fixed bed reactor. The liquid organic phase from this catalytic conversion process mainly consisted of liquid hydrocarbons and phenol derivatives. Under the condition of low Liquid Hourly Space Velocity (LHSV), the liquid organic phase from acetic acid cracking had a selectivity of 22% for liquid hydrocarbons and a selectivity of 65% for phenol derivatives. The composition of the organic products changed considerably with the LHSV increasing to 3 h−1. The selectivity for liquid hydrocarbons increased up to 52% while that for phenol derivatives decreased to 32%. Propanoic acid performed much better in producing liquid hydrocarbons than acetic acid. Its selectivity for liquid hydrocarbons was as high as 80% at LHSV = 3 h−1. A mechanism for this catalytic conversion process was proposed according to the analysis of the components in the liquid organic phases. The pathways of the main compounds formation in the liquid organic phases were proposed, and the reason why liquid hydrocarbons were more effectively produced when using propanoic acid rather than acetic acid was also successfully explained. In addition, BET and SEM characterization were used to analyze the catalyst coke deposition. -- Graphical abstract: Display Omitted Highlights: ► High content of carboxylic acids in bio-oil causes its corrosiveness. ► Acetic acid and propanoic acid are two dominant acids in bio-oil. ► Liquid hydrocarbons were produced by cracking of these two dominant acids. ► A mechanism model was proposed to explain the

  17. Catalytic, Conjugate Reduction-Aldol Addition Reaction of β'Oxoal kyl α, β-Unsatu rated Carboxylates%Catalytic, Conjugate Reduction-Aldol Addition Reaction of β'Oxoal kyl α, β-Unsatu rated Carboxylates

    Institute of Scientific and Technical Information of China (English)

    郑爱军; 姜岚; 李争宁

    2012-01-01

    Intramolecular conjugate reduction-aldol addition reactions of β'-oxoalkyl a,fl-unsaturated carboxylates were performed in the presence of copper catalysts generated in situ from copper salts, phosphine ligands and silanes. Moderate to good yields and high diastereoselectivities were obtained in 15 min to 3 h using bis[(2-diphenyl- phosphino)phenyl] ether as the ligand.

  18. Synthesis, structural characterization and antimicrobial activities of diorganotin(IV) complexes with azo-imino carboxylic acid ligand: Crystal structure and topological study of a doubly phenoxide-bridged dimeric dimethyltin(IV) complex appended with free carboxylic acid groups

    Science.gov (United States)

    Roy, Manojit; Roy, Subhadip; Devi, N. Manglembi; Singh, Ch. Brajakishor; Singh, Keisham Surjit

    2016-09-01

    Diorganotin(IV) complexes appended with free carboxylic acids were synthesized by reacting diorganotin(IV) dichlorides [R2SnCl2; R = Me (1), Bu (2) and Ph (3)] with an azo-imino carboxylic acid ligand i.e. 2-{4-hydroxy-3-[(2-hydroxyphenylimino)methyl]phenylazo}benzoic acid in presence of triethylamine. The complexes were characterized by elemental analysis, IR and multinuclear NMR (1H, 13C and 119Sn) spectroscopy. The structure of 1 in solid state has been determined by X-ray crystallography. Crystal structure of 1 reveals that the compound crystallizes in monoclinic space group P21/c and is a dimeric dimethyltin(IV) complex appended with free carboxylic acid groups. In the structure of 1, the Sn(IV) atoms are hexacoordinated and have a distorted octahedral coordination geometry in which two phenoxy oxygen atoms and the azomethine nitrogen atom of the ligand coordinate to each tin atom. One of the phenoxy oxygen atom bridges the two tin centers resulting in a planar Sn2O2 core. Topological analysis is used for the description of molecular packing in 1. Tin NMR spectroscopy study indicates that the complexes have five coordinate geometry around tin atom in solution state. Since the complexes have free carboxylic acids, these compounds could be further used as potential metallo-ligands for the synthesis of other complexes. The synthesized diorganotin(IV) complexes were also screened for their antimicrobial activities and compound 2 showed effective antimicrobial activities.

  19. Polymorphism in Self-Assembled Structures of 9-Anthracene Carboxylic Acid on Ag(111

    Directory of Open Access Journals (Sweden)

    Bo Xu

    2012-06-01

    Full Text Available Surface self-assembly process of 9-anthracene carboxylic acid (AnCA on Ag(111 was investigated using STM. Depending on the molecular surface density, four spontaneously formed and one annealed AnCA ordered phases were observed, namely a straight belt phase, a zigzag double-belt phase, two simpler dimer phases, and a kagome phase. The two high-density belt phases possess large unit cells on the scale length of 10 nm, which are seldom observed in molecular self-assembled structures. This structural diversity stems from a complicated competition of different interactions of AnCA molecules on metal surface, including intermolecular and molecular-substrate interactions, as well as the steric demand from high molecular surface density.

  20. Dysprosium-carboxylate nanomeshes with tunable cavity size and assembly motif through ionic interactions.

    Science.gov (United States)

    Cirera, B; Đorđević, L; Otero, R; Gallego, J M; Bonifazi, D; Miranda, R; Ecija, D

    2016-09-28

    We report the design of dysprosium directed metallo-supramolecular architectures on a pristine Cu(111) surface. By an appropriate selection of the ditopic molecular linkers equipped with terminal carboxylic groups (TPA, PDA and TDA species), we create reticular and mononuclear metal-organic nanomeshes of tunable internodal distance, which are stabilized by eight-fold DyO interactions. A thermal annealing treatment for the reticular Dy:TDA architecture gives rise to an unprecedented quasi-hexagonal nanostructure based on dinuclear Dy clusters, exhibiting a unique six-fold DyO bonding motif. All metallo-supramolecular architectures are stable at room temperature. Our results open new avenues for the engineering of supramolecular architectures on surfaces incorporating f-block elements forming thermally robust nanoarchitectures through ionic bonds. PMID:27560774

  1. Lewis acid promoted ruthenium(II)-catalyzed etherifications by selective hydrogenation of carboxylic acids/esters.

    Science.gov (United States)

    Li, Yuehui; Topf, Christoph; Cui, Xinjiang; Junge, Kathrin; Beller, Matthias

    2015-04-20

    Ethers are of fundamental importance in organic chemistry and they are an integral part of valuable flavors, fragrances, and numerous bioactive compounds. In general, the reduction of esters constitutes the most straightforward preparation of ethers. Unfortunately, this transformation requires large amounts of metal hydrides. Presented herein is a bifunctional catalyst system, consisting of Ru/phosphine complex and aluminum triflate, which allows selective synthesis of ethers by hydrogenation of esters or carboxylic acids. Different lactones were reduced in good yields to the desired products. Even challenging aromatic and aliphatic esters were reduced to the desired products. Notably, the in situ formed catalyst can be reused several times without any significant loss of activity. PMID:25728921

  2. Aldehydes, ketones, and carboxylic acids formed radiolytically in aqueous solutions of cyanides and simple nitriles

    Energy Technology Data Exchange (ETDEWEB)

    Negron-Mendoza, A.; Draganic, Z.D.; Navarro-Gonzalez, R.; Graganic, I.G.

    1983-08-01

    A systematic search for aldehydes, ketones, and carboxylic acids was carried out in aqueous solutions of HCN, NH/sub 4/CN, CH/sub 3/CN, and C/sub 2/H/sub 4/CN, that had received multikilogray doses of /sup 60/Co ..gamma.. radiation. About 30 radiolytic products were identified, among them a large variety of dicarboxylic and tricarboxylic acids. Some of them might be of significant interest in molecular evolution studies of prebiotic processes. They originate in the free-radical-initiated chemical reactions where the additional oligomerization processes are particularly important. Most of the radiolytic products appear in both cyanides and nitriles and point to the importance of reactions involving the carbon-nitrogen triple bond.

  3. Carboxyl-functionalized magnetic microparticle carrier for isolation and identification of DNA in dairy products

    International Nuclear Information System (INIS)

    Magnetite nanoparticles about 14nm in diameter were obtained by chemical coprecipitation of Fe(II) and Fe(III) salts with aqueous ammonia in the presence of poly(ethylene glycol) (PEG). Magnetic poly(glycidyl methacrylate) (PGMA) microspheres about 1μm in diameter were prepared by dispersion polymerization of GMA in aqueous ethanol in the presence of PEG-coated magnetite nanoparticles. The microspheres were hydrolyzed and carboxyl groups introduced by oxidation with KMnO4. The particles reversibly bound bacterial DNA of Bifidobacterium and Lactobacillus genera in the presence of high concentrations of PEG 6000 and sodium chloride from crude cell lysates of various dairy products (butter milk, cheese, yoghurt, probiotic tablets) or from cell lyophilisates. The presence of Bifidobacterium and Lactobacillus DNA in samples was confirmed by PCR amplification

  4. Fluorescence of complexes of Eu( Ⅱ ) with aromatic carboxylic acid-1, 1O-phenanthroline

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The 1, 10-phenanthroline-aromatic carboxylic acid (benzoic acid and o-phthalic acid) binary and ternary complexes of europium were synthesized. The fluorescence and FT-IR spectroscopy, elemental analysis, UV spectroscopic studies on these complexes were also performed. These complexes can emit strong red fluorescence of Eu( m ) excited by UV light. At the same excited wavelength, the fluorescence spectra of the complexes were also studied. The results indi cated that the fluorescence intensities of ternary complexes are stronger than that of binary complexes. The reason is that phenanthroline has higher electron density and higher orbit scope in the conjugated system and consequently an easier ener gy transfer to the europium ion, which makes the fluorescence intensity of ternary complexes be stronger than that of bi nary complexes.

  5. Multiple functionalization of multi-walled carbon nanotubes with carboxyl and amino groups

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Zhiyuan [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Yang, Zhanhong, E-mail: zhongnan320@gmail.com [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Key Laboratory of Resource Chemistry of Nonferrous Metals, Ministry of Education, Central South University, Changsha 410083 (China); Hu, Youwang; Li, Jianping [College of Mechanical and Electrical Engineering, Central South University, Changsha 410083 (China); Fan, Xinming [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

    2013-07-01

    In this paper, carboxyl and amino groups have been introduced onto the surface of the multi-walled carbon nanotubes (MWCNTs) by the mixed acid treatment and the diazonium reaction, respectively. The presence of multifunctionality groups on the MWCNTs has been characterized by Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric (TGA) analysis, Raman spectra, scanning electron microscopy (SEM) and energy dispersive X-ray spectrum (EDS). The multifunctionalized carbon nanotubes were further utilized to react with acetyl chloride and ethylenediamine (EDA). The formation of the amide bond in the grafting reaction has been confirmed by FT-IR spectroscopy. The result indicates that the further grafting is successful. The multifunctionalized MWCNTs can be a new versatile platform for many interesting applications.

  6. Oxidized amylose with high carboxyl content: A promising solubilizer and carrier of linalool for antimicrobial activity.

    Science.gov (United States)

    Zhou, Ying; Ye, Youxin; Zhang, Wenwen; Li, Songling; Chen, Jing; Wang, Shiting; Li, Defu; Mu, Changdao

    2016-12-10

    The oxidized amyloses with different carboxyl content were prepared to include linalool for antimicrobial activity in aqueous environment. The results show that linalool can be effectively reserved from volatilization through encapsulation into amylose and oxidized amyloses. The inclusion ability of oxidized amyloses towards linalool is decreasing with the increase of oxidation level due to the depolymerization of amylose. However, the solubilization effect of oxidized amyloses to linalool is enhanced efficiently owning to the high water solubility of oxidized amyloses. It is interesting that the inclusion complexes have good antimicrobial activity in aqueous environment. Linalool solubilized by oxidized amyloses presents better antimicrobial performance than that solubilized by amylose, mainly resulting from that amylose-linalool inclusion complex would aggregate and retrograde fast in aqueous solution, which is disadvantageous for the release of linalool. The study suggests that oxidized amylose is a promising solubilizer and carrier of linalool for antimicrobial activity in aqueous environment.

  7. 2-[3-Cyano-4-(2-methylpropoxyphenyl]-4-methylthiazole-5-carboxylic acid pyridine solvate

    Directory of Open Access Journals (Sweden)

    Xiong Zhu

    2009-11-01

    Full Text Available In the title compound, C16H16N2O3S·C5H5N, the benzene and thiazole rings of the Febuxostat [2-(3-cyano-4-isobutyloxyphenyl-4-methyl-5-thiazolecarboxylic acid] molecule are almost coplanar [dihedral angle = 2.4 (1°]. The carboxyl group is coplanar with the thiazole ring [O—C—C—C and O—C—C—S torsion angles of −0.7 (4 and 0.6 (3°, respectively]. The pyridine molecule of crystallization is linked to the Febuxostat molecule through an O—H...N hydrogen bond. A weak π–π stacking interaction is observed between the benzene ring of the Febuxostat molecule and pyridine molecule, with a centroid–centroid distance of 3.7530 (18 Å.

  8. Synthesis and Structural Characterization of 1- and 2-Substituted Indazoles: Ester and Carboxylic Acid Derivatives

    Directory of Open Access Journals (Sweden)

    Isabel Bento

    2006-11-01

    Full Text Available A series of indazoles substituted at the N-1 and N-2 positions with ester-containing side chains -(CH2nCO2R of different lengths (n = 0-6, 9, 10 are described.Nucleophilic substitution reactions on halo esters (X(CH2nCO2R by 1H-indazole inalkaline solution lead to mixtures of N-1 and N-2 isomers, in which the N-1 isomerpredominates. Basic hydrolysis of the ester derivatives allowed the synthesis of thecorresponding indazole carboxylic acids. All compounds were fully characterised bymultinuclear NMR and IR spectroscopies, MS spectrometry and elemental analysis; theNMR spectroscopic data were used for structural assignment of the N-1 and N-2 isomers.The molecular structure of indazol-2-yl-acetic acid (5b was determined by X-raydiffraction, which shows a supramolecular architecture involving O2-H...N1intermolecular hydrogen bonds.

  9. Red-emitting alkaline-earth rare-earth pentaoxometallates powders prepared by metal carboxylates solution

    Indian Academy of Sciences (India)

    Kyu-Seog Hwang; Sung-Dae Kim; Seung Hwangbo; Jin-Tae Kim

    2013-06-01

    Moisture-insensitive metal carboxylates that are mostly liquids at room temperature have been first applied to the preparation of strontium europium aluminate (Sr2EuAlO5) powders for red-emitting phosphor under near ultraviolet radiation. Strontium naphthenate, aluminium-2-ethylhexanoate and europium-2-ethylhexanoate were dissolved with toluene to prepare starting solution. Precursor pyrolyzed at 500 °C for 240 min was finally annealed at 900–1200 °C for 240 min in Ar. X-ray diffraction analysis, field emission–scanning electron microscope and fluorescent spectrophotometer were used to evaluate structural and optical properties. For the 1000 °C-annealed powders with regular shape and narrow size distribution confirmed by FE–SEM observation, strong red emission at 615nm under the excitation of 395nm maximum was reached, then the higher annealed samples at above 1100 °C gave the lower emission intensities.

  10. Dichloridobis(4-pyridylmethyl 1H-pyrrole-2-carboxylate-κNzinc

    Directory of Open Access Journals (Sweden)

    Guilong Zhang

    2012-03-01

    Full Text Available In the title molecule, [ZnCl2(C11H10N2O22], the ZnII ion, situated on a twofold axis, is in a distorted tetrahedral coordination environment formed by two chloride anions and two pyridine N atoms of the two organic ligands. In the pyrrole-2-carboxylate unit, the pyrrole N—H group and the carbonyl group point approximately in the same direction. The dihedral angle between the two pyridine rings is 54.8 (3°. The complex molecules are connected into chains extending along [101] by N—H...Cl hydrogen bonds. The chains are further assembled into (-101 layers by C—H...O and C—H...Cl interactions.

  11. Crowned spiropyran fluoroionophores with a carboxyl moiety for the selective detection of lithium ions.

    Science.gov (United States)

    Stubing, D B; Heng, S; Abell, A D

    2016-04-12

    The absorbance and fluorescence spectra of carboxylated spiropyrans containing methyl-1-aza-12-crown-4, methyl-1-aza-15-crown-5, methyl-1-aza-18-crown-6 moieties are compared. Characteristic changes in spectra after addition of the alkali metal salts of Li(+), Na(+), K(+) and Cs(+) were observed. Chromism induced by the binding of the metal cations was observed as an increase in absorbance and fluorescence. Of these metal cations, the Li(+) ion produced the largest change in all three spiropyran systems. Reversible photoswitching of the spiropyran-metal complexes was observed on irradiation with alternating 352 nm UV and white light. This results in reversible fluorescence based sensing of lithium ions with potential for use in a biological sensor device. PMID:27001932

  12. Catalyst-free multicomponent synthesis of novel adamantyl-containing tetrahydropyrimidine carboxylates.

    Science.gov (United States)

    Kalita, Utpalparna; Kaping, Shunan; Vishwakarma, Jai Narain

    2016-08-01

    [Formula: see text]-Enaminoesters were generated in situ by the reaction of aliphatic or aromatic primary amines to electron-deficient alkynes, dimethyl acetylenedicarboxylate, and methyl propiolate. [Formula: see text]-Enaminoesters thus formed were reacted with 1-adamantanamine and formaldehyde in methanol to give novel molecular hybrids: dimethyl 3-((3s,5s,7s)-adamantan-1-yl)-1-(alkyl/aralkyl/aryl)-1,2,3,4-tetrahydropyrimidine-5,6-dicarboxylates (5a-j) and methyl 3-((3s,5s,7s)-adamantan-1-yl)-1-(alkyl/aralkyl/aryl)-1,2,3,4-tetrahydropyrimidine-5-carboxylates (9a-j). The structures of the molecular hybrids have been established based on the spectral and analytical data. Structural confirmation of the products was done by X-ray crystallography of 5d as a representative product of the series. PMID:26797716

  13. Synthesis,structure and physical properties of the one-dimensional chain complex of tetrathiafulvalene carboxylate

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A new Co(Ⅱ) coordination polymer bearing TTF carboxylate group, [{Co2(trioTTF)2(H2O)6}·5H2O]n (1) (trioTTF=2-(5,6,8,9,11,12,14,15-octahydro-[1,3]dithiolo[4,5-h][1,4,13,7,10]trioxadithiacyclopentadecin-2-ylidene)-1,3-dithiole-4,5-dicarboxylate), has been prepared and characterized. In the structure of 1, shorter intermolecular S····S contacts (3.565 △) are found between the trioTTF groups from neighboring chains. The electric conductivity of 1 is poor due to the bulky crown-ether group, but it exhibits ferromagnetic interaction at low temperature.

  14. Probing the orthosteric binding site of GABAA receptors with heterocyclic GABA carboxylic acid bioisosteres

    DEFF Research Database (Denmark)

    Petersen, Jette G; Bergmann, Rikke; Krogsgaard-Larsen, Povl;

    2013-01-01

    the orthosteric binding site. The physicochemical properties of the heterocyclic moieties making them suitable for bioisosteric replacement of the carboxylic acid in the molecule of GABA are discussed. A variety of synthetic strategies for synthesis of the heterocyclic scaffolds are available. Likewise, methods...... for introduction of substituents into specific positions of the heterocyclic scaffolds facilitate the investigation of different regions in the orthosteric binding pocket in close vicinity of the core scaffolds of muscimol/GABA. The development of structural models, from pharmacophore models to receptor homology...... models, has provided more insight into the molecular basis for binding. Similar binding modes are proposed for the heterocyclic GABA analogues covered in this review by use of ligand-receptor docking into the receptor homology model and the presented structure-activity relationships. A network...

  15. Electrochemiluminescence Study of Europium (III Complex with Coumarin3-Carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Stefan Lis

    2008-01-01

    Full Text Available The europium (III complex of coumarin-3-carboxylic acid (C3CA has been prepared and characterized on the basis of elemental analysis, IR, and emission (photoluminescence and electrochemiluminescence spectroscopy. The synthesised complex having a formula Eu(C3CA2(NO3(H2O2 was photophysically characterized in solution and in the solid state. Electrochemiluminescence, ECL, of the system containing the Eu(III/C3CA complex was studied using an oxide-covered aluminium electrode. The goal of these studies was to show the possibility of the use of electrochemical excitation of the Eu(III ion in aqueous solution for emission generation. The generated ECL emission was very weak, and therefore its measurements and spectral analysis were carried out with the use of cut-off filters method. The studies proved a predominate role of the ligand-to-metal energy transfer (LMET in the generated ECL.

  16. Carboxyl-functionalized magnetic microparticle carrier for isolation and identification of DNA in dairy products

    Science.gov (United States)

    Horák, Daniel; Rittich, Bohuslav; Španová, Alena

    2007-04-01

    Magnetite nanoparticles about 14 nm in diameter were obtained by chemical coprecipitation of Fe(II) and Fe(III) salts with aqueous ammonia in the presence of poly(ethylene glycol) (PEG). Magnetic poly(glycidyl methacrylate) (PGMA) microspheres about 1 μm in diameter were prepared by dispersion polymerization of GMA in aqueous ethanol in the presence of PEG-coated magnetite nanoparticles. The microspheres were hydrolyzed and carboxyl groups introduced by oxidation with KMnO4. The particles reversibly bound bacterial DNA of Bifidobacterium and Lactobacillus genera in the presence of high concentrations of PEG 6000 and sodium chloride from crude cell lysates of various dairy products (butter milk, cheese, yoghurt, probiotic tablets) or from cell lyophilisates. The presence of Bifidobacterium and Lactobacillus DNA in samples was confirmed by PCR amplification.

  17. Absorption of carbon dioxide in aqueous solutions of imidazolium ionic liquids with carboxylate anions

    Energy Technology Data Exchange (ETDEWEB)

    Baj, Stefan; Krawczyk, Tomasz; Dabrowska, Aleksandra; Siewniak, Agnieszka [Silesian University of Technology, Gliwice (Poland); Sobolewski, Aleksander [Institute for Chemical Processing of Coal, Zabrze (Poland)

    2015-11-15

    The solubility of carbon dioxide at atmospheric pressure in aqueous mixtures of 1,3-alkyl substituted imidazolium ionic liquids (ILs) containing carboxylic anions was studied. The ILs showed increased solubility of CO{sub 2} with decreasing water concentration. The relationship between the CO{sub 2} concentration in solution and the mole fraction of water in the ILs describes a sigmoidal curve. The regression constants of a logistic function were used to quantitatively assess the absorbent capacity and the effect of water on CO{sub 2} absorption. ILs containing the most basic anions, such as pivalate, propionate and acetate, had the best properties. It was observed that the impact of water on absorption primarily depended on the cation structure. The best absorption performance was observed for 1,3-dibutylimidazolium pivalate and 1-butyl-3-methyl imidazolium acetate.

  18. Electrocatalytic carboxylation of chloroacetonitrile at a silver cathode for the synthesis of cyanoacetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Scialdone, Onofrio [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy)], E-mail: scialdone@dicpm.unipa.it; Galia, Alessandro; Filardo, Giuseppe [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy); Isse, Abdirisak Ahmed [Dipartimento di Scienze Chimiche, Universita di Padova, Via Marzolo 1, 35131 Padova (Italy)], E-mail: Abdirisak.ahmedisse@unipd.it; Gennaro, Armando [Dipartimento di Scienze Chimiche, Universita di Padova, Via Marzolo 1, 35131 Padova (Italy)

    2008-12-30

    The electrocatalytic carboxylation of chloroacetonitrile to cyanoacetic acid performed at silver cathodes was investigated both theoretically and experimentally. Silver exhibits powerful electrocatalytic activities towards the reduction of chloroacetonitrile. In CO{sub 2}-saturated CH{sub 3}CN, reduction of NCCH{sub 2}Cl occurs at potentials that are about 0.7 V more positive than those observed at glassy carbon and gives cyanoacetic acid in good yields. Theoretical considerations on the effect of operative parameters on the performances of the process were confirmed by electrocarboxylation experiments performed in undivided cells equipped with sacrificial anodes both in a bench-scale electrochemical batch reactor and in a continuous batch recirculation reaction system equipped with a parallel plate electrochemical cell. Selectivities and Faradic efficiencies higher than 80% were obtained by working under anhydrous conditions both under amperostatic and potentiostatic alimentation at proper values of either current density or applied potential.

  19. Structure-activity relationship of an ozonide carboxylic acid (OZ78) against Fasciola hepatica.

    Science.gov (United States)

    Zhao, Qingjie; Vargas, Mireille; Dong, Yuxiang; Zhou, Lin; Wang, Xiaofang; Sriraghavan, Kamaraj; Keiser, Jennifer; Vennerstrom, Jonathan L

    2010-05-27

    In this paper, we describe the SAR of ozonide carboxylic acid OZ78 (1) as the first part of our search for a trematocidal synthetic peroxide drug development candidate. We found that relatively small structural changes to 1 resulted most commonly in loss of activity against Fasciola hepatica in vivo. A spiroadamantane substructure and acidic functional group (or ester prodrug) were required for activity. Of 26 new compounds administered at single 100 mg/kg oral doses to F. hepatica infected rats, 8 had statistically significant worm burden reductions, 7 were partially curative, and 1 (acylsulfonamide 6) was completely curative and comparable to 1 in flukicidal efficacy. This study also showed that the activity of 1 is peroxide-bond-dependent, suggesting that its flukicidal efficacy depends upon hemoglobin digestion in F. hepatica. PMID:20423101

  20. Electrochemical Reduction and Carboxylation of Ethyl Cinnamate in MeCN

    Institute of Scientific and Technical Information of China (English)

    WANG Huan; DU Yan-Fang; LIN Mei-Yu; ZHANG Kai; LU Jia-Xing

    2008-01-01

    The electrochemical reduction and carboxylation of ethyl cinnamate have been carded out in an undivided cell equipped with a Mg sacrificial anode using MeCN as solvent.Direct electroreduction led to the formation of the hydrodimers and saturated ester.And electrocarboxylation was carried out in the presence of CO2.The global yield and the ratio of mono- to dicarboxylic acids were strongly affected by various factors:electrode material,electrolysis potential,the substrate concentration and temperature.The high yield (78%) was obtained under an optimized reaction condition (cathode:Ni;electrolysis potential:-1.7V;substrate concentration:0.1 mol·L-1;and temperature:-10℃).

  1. Conjugates of 1'-Aminoferrocene-1-carboxylic Acid and Proline: Synthesis, Conformational Analysis and Biological Evaluation

    Directory of Open Access Journals (Sweden)

    Monika Kovačević

    2014-08-01

    Full Text Available Our previous studies showed that alteration of dipeptides Y-Fca-Ala-OMe (III into Y-Ala-Fca-OMe (IV (Y = Ac, Boc; Fca = 1'-aminoferrocene-1-carboxylic acid significantly influenced their conformational space. The novel bioconjugates Y-Fca-Pro-OMe (1, Y = Ac; 2, Y = Boc and Y-Pro-Fca-OMe (3, Y = Boc; 4, Y = Ac have been prepared in order to investigate the influence of proline, a well-known turn-inducer, on the conformational properties of small organometallic peptides with an exchanged constituent amino acid sequences. For this purpose, peptides 1–4 were subjected to detailed spectroscopic analysis (IR, NMR, CD spectroscopy in solution. The conformation of peptide 3 in the solid state was determined. Furthermore, the ability of the prepared conjugates to inhibit the growth of estrogen receptor-responsive MCF-7 mammary carcinoma cells and HeLa cervical carcinoma cells was tested.

  2. Isolation and Molecular Characterization of 1-Aminocyclopropane-1-carboxylic Acid Synthase Genes in Hevea brasiliensis

    Directory of Open Access Journals (Sweden)

    Jia-Hong Zhu

    2015-02-01

    Full Text Available Ethylene is an important factor that stimulates Hevea brasiliensis to produce natural rubber. 1-Aminocyclopropane-1-carboxylic acid synthase (ACS is a rate-limiting enzyme in ethylene biosynthesis. However, knowledge of the ACS gene family of H. brasiliensis is limited. In this study, nine ACS-like genes were identified in H. brasiliensis. Sequence and phylogenetic analysis results confirmed that seven isozymes (HbACS1–7 of these nine ACS-like genes were similar to ACS isozymes with ACS activity in other plants. Expression analysis results showed that seven ACS genes were differentially expressed in roots, barks, flowers, and leaves of H. brasiliensis. However, no or low ACS gene expression was detected in the latex of H. brasiliensis. Moreover, seven genes were differentially up-regulated by ethylene treatment. These results provided relevant information to help determine the functions of the ACS gene in H. brasiliensis, particularly the functions in regulating ethylene stimulation of latex production.

  3. Solid-Phase Synthesis of Amine/Carboxyl Substituted Prolines and Proline Homologues: Scope and Limitations.

    Science.gov (United States)

    Zhou, Ziniu; Scott, William L; O'Donnell, Martin J

    2016-03-15

    A solid-phase procedure is used to synthesize racemic peptidomimetics based on the fundamental peptide unit. The peptidomimetics are constructed around proline or proline homologues variably substituted at the amine and carbonyl sites. The procedure expands the diversity of substituted peptidomimetic molecules available to the Distributed Drug Discovery (D3) project. Using a BAL-based solid-phase synthetic sequence the proline or proline homologue subunit is both constructed and incorporated into the peptidomimetic by an α-alkylation, hydrolysis and intramolecular cyclization sequence. Further transformations on solid-phase provide access to a variety of piperazine derivatives representing a class of molecules known to exhibit central nervous system activity. The procedure works well with proline cores, but with larger six- and seven-membered ring homologues the nature of the carboxylic acid acylating the cyclic amine can lead to side reactions and result in poor overall yields.

  4. Carboxyl-functionalized magnetic microparticle carrier for isolation and identification of DNA in dairy products

    Energy Technology Data Exchange (ETDEWEB)

    Horak, Daniel [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovskeho Sq. 2, 162 06 Prague 6 (Czech Republic)]. E-mail: horak@imc.cas.cz; Rittich, Bohuslav [Masaryk University Brno, Tvrdeho 14, 602 00 Brno (Czech Republic)]. E-mail: rittich@sci.muni.cz; Spanova, Alena [Masaryk University Brno, Tvrdeho 14, 602 00 Brno (Czech Republic)]. E-mail: spanova@sci.muni.cz

    2007-04-15

    Magnetite nanoparticles about 14nm in diameter were obtained by chemical coprecipitation of Fe(II) and Fe(III) salts with aqueous ammonia in the presence of poly(ethylene glycol) (PEG). Magnetic poly(glycidyl methacrylate) (PGMA) microspheres about 1{mu}m in diameter were prepared by dispersion polymerization of GMA in aqueous ethanol in the presence of PEG-coated magnetite nanoparticles. The microspheres were hydrolyzed and carboxyl groups introduced by oxidation with KMnO{sub 4}. The particles reversibly bound bacterial DNA of Bifidobacterium and Lactobacillus genera in the presence of high concentrations of PEG 6000 and sodium chloride from crude cell lysates of various dairy products (butter milk, cheese, yoghurt, probiotic tablets) or from cell lyophilisates. The presence of Bifidobacterium and Lactobacillus DNA in samples was confirmed by PCR amplification.

  5. Gloves against mineral oils and mechanical hazards: composites of carboxylated acrylonitrile–butadiene rubber latex

    Science.gov (United States)

    Krzemińska, Sylwia; Rzymski, Władysław M.; Malesa, Monika; Borkowska, Urszula; Oleksy, Mariusz

    2016-01-01

    Resistance to permeation of noxious chemical substances should be accompanied by resistance to mechanical factors because the glove material may be torn, cut or punctured in the workplace. This study reports on glove materials, protecting against mineral oils and mechanical hazards, made of carboxylated acrylonitrile–butadiene rubber (XNBR) latex. The obtained materials were characterized by a very high resistance of the produced materials to oil permeation (breakthrough time > 480 min). The mechanical properties, and especially tear resistance, of the studied materials were improved after the addition of modified bentonite (nanofiller) to the XNBR latex mixture. The nanocomposite meets the requirements in terms of parameters characterizing tear, abrasion, cut and puncture resistance. Therefore, the developed material may be used for the production of multifunctional protective gloves. PMID:26757889

  6. Effect of pH and nitrogen source in carboxylation by seedlings of wheat and maize

    International Nuclear Information System (INIS)

    Carboxylation has been studied in leaves homogenate, expressed as RuBP-carboxylase activity, using as one of the substrates NaH14CO3, and giving the acitivity value as nanomols of 14CO2 incorporated by mg.. of protein per minute in the determined conditions. The variable is the pH of the culture media. Cultures has been studied with pH values between 3.5 and 6.2. Three different nitrogen sources has been used, carefully calculating the composition of each medium in order that all of them have same nitrogen content:1) Nitrate medium, 2) Ammonium sulfate medium and 3) Ammonium nitrate medium. The results are presented graphically with a discussion about them. It is shown that the effect of pH is less pronounced in maize that in wheat, with NO3 nitrogen source that with NH4+, and in plants 28 days age than in plants 7 days age. (author)

  7. Crystals of the carboxyl-terminal functional unit from Octopus dofleini hemocyanin.

    Science.gov (United States)

    Cuff, M E; Hendrickson, W A; Lamy, J; Lamy, J N; Miller, K I; van Holde, K E

    1990-05-01

    The carboxyl-terminal oxygen-binding unit of the polypeptide from Octopus dofleini hemocyanin has been crystallized in a form suitable for three-dimensional X-ray analysis. This proteolytic fragment has a molecular weight of 47 kDa and reversibly binds O2 while exhibiting a slight Bohr effect. Two types of crystals have been grown. Type I crystals, currently under analysis, belong to the orthorhombic space group P2(1)2(1)2(1) and have unit cell dimensions of 92.6 A x 167.4 A x 59.2 A. A composition of two protein molecules per asymmetric unit and 50% solvent content is consistent with a self-rotation function that identifies a non-crystallographic 2-fold axis of symmetry relating these molecules. Diffraction extending beyond 1.9 A Bragg spacings can be detected with synchrotron X-radiation. PMID:2338711

  8. Enriched surface acidity for surfactant-free suspensions of carboxylated carbon nanotubes purified by centrifugation

    Directory of Open Access Journals (Sweden)

    Elizabeth I. Braun

    2016-06-01

    Full Text Available It is well known that surfactant-suspended carbon nanotube (CNT samples can be purified by centrifugation to decrease agglomerates and increase individually-dispersed CNTs. However, centrifugation is not always part of protocols to prepare CNT samples used in biomedical applications. Herein, using carboxylated multi-walled CNTs (cMWCNTs suspended in water without a surfactant, we developed a Boehm titrimetric method for the analysis of centrifuged cMWCNT suspensions and used it to show that the surface acidity of oxidized carbon materials in aqueous cMWCNT suspensions was enriched by ∼40% by a single low-speed centrifugation step. This significant difference in surface acidity between un-centrifuged and centrifuged cMWCNT suspensions has not been previously appreciated and is important because the degree of surface acidity is known to affect the interactions of cMWCNTs with biological systems.

  9. Occurrence and fate of oseltamivir carboxylate (Tamiflu) and amantadine in sewage treatment plants.

    Science.gov (United States)

    Ghosh, Gopal Chandra; Nakada, Norihide; Yamashita, Naoyuki; Tanaka, Hiroaki

    2010-09-01

    We investigated the occurrence and fate of the two antiviral drugs oseltamivir carboxylate (OC)-the active metabolite of Tamiflu-and amantadine (AMT) at three sewage treatment plants (STPs) during the 2008-2009 and 2009-2010 influenza seasons in Japan. Both compounds were detected in all samples analyzed. The concentrations in raw influents at the STPs ranged from 140 to 460 ng L(-1) OC and from 184 to 538 ng L(-1) AMT. Primary treatment gave no substantial removal of the drugs (OC, 2-9%; AMT, 7-17%). Biological nutrient-removal-based secondary treatment (anoxic-oxic-anoxic-oxic and anaerobic-anoxic-oxic) removed 20-37% of OC, whereas extended-aeration-based conventional activated sludge treatment removed ozonation removed >90%. Ozonation after secondary treatment in STPs will be necessary during an influenza pandemic to reduce the risks associated with the widespread use of antiviral drugs. PMID:20692015

  10. Analysis of aliphatic carboxylic acids in anaerobic digestion process waters by ion-exclusion chromatography

    Institute of Scientific and Technical Information of China (English)

    Kazuaki ITO; Kazuhiko TANAKA; Jun SAKAMOTO; Kazuya NAGAOKA; Yohichi TAKAYAMA; Takashi KANAHORI; Hiroshi SUNAHARA; Tsuneo HAYASHI; Shinji SATO; Takeshi HIROKAWA

    2012-01-01

    The analysis of seven aliphatic carboxylic acids ( formic,acetic,propionic,iso-butyric,n-butyric,iso-valeric and n-valeric acid) in anaerobic digestion process waters for biogas production was examined by ion-exclusion chromatography with dilute acidic eluents (benzoic acid,perfluorobutyric acid (PFBA) and sulfuric acid) and non-suppressed conductivity/ultraviolet (UV) detection.The columns used were a styrene/divinylbenzene-based strongly acidic cation-exchange resin column ( TSKgel SCX) and a polymethacrylate-based weakly acidic cation-exchange resin column ( TSKgel Super IC-A/C ).Good separation was performed on the TSKgel SCX in shorter retention times.For the TSKgel Super IC-A/C,peak shape of the acids was sharp and symmetrical in spite of longer retention times.In addition,the mutual separation of the acids was good except for iso- and n-butyric acids.The better separation and good detection was achieved by using the two columns (TSKgel SCX and TSKgel Super IC-A/C connected in series),lower concentrations of PFBA and sulfuric acid as eluents,non-suppressed conductivity detection and UV detection at 210 nm.This analysis was applied to anaerobic digestion process waters.The chromatograms with conductivity detection were relatively simpler compared with those of UV detection.The use of two columns with different selectivities for the aliphatic carboxylic acids and the two detection modes was effective for the determination and identification of the analytes in anaerobic digestion process waters containing complex matrices.

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

    Science.gov (United States)

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

    2016-08-01

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

  12. Evaluation of toxic effects of several carboxylic acids on bacterial growth by toxicodynamic modelling

    Directory of Open Access Journals (Sweden)

    Vázquez José

    2011-11-01

    Full Text Available Abstract Background Effects of organic acids on microbial fermentation are commonly tested in investigations about metabolic behaviour of bacteria. However, they typically provide only descriptive information without modelling the influence of acid concentrations on bacterial kinetics. Results We developed and applied a mathematical model (secondary model to capture the toxicological effects of those chemicals on kinetic parameters that define the growth of bacteria in batch cultures. Thus, dose-response kinetics were performed with different bacteria (Leuconostoc mesenteroides, Carnobacterium pisicola, Escherichia coli, Bacillus subtilis and Listonella anguillarum exposed at increasing concentrations of individual carboxylic acids (formic, acetic, propionic, butyric and lactic. In all bioassays the acids affected the maximum bacterial load (Xm and the maximum growth rate (vm but only in specific cases the lag phase (λ was modified. Significance of the parameters was always high and in all fermentations the toxicodynamic equation was statistically consistent and had good predictability. The differences between D and L-lactic acid effects were significant for the growth of E. coli, L. mesenteroides and C. piscicola. In addition, a global parameter (EC50,τ was used to compare toxic effects and provided a realistic characterization of antimicrobial agents using a single value. Conclusions The effect of several organic acids on the growth of different bacteria was accurately studied and perfectly characterized by a bivariate equation which combines the basis of dose-response theory with microbial growth kinetics (secondary model. The toxicity of carboxylic acids was lower with the increase of the molecular weight of these chemicals.

  13. Metallaphotoredox-catalysed sp(3)-sp(3) cross-coupling of carboxylic acids with alkyl halides.

    Science.gov (United States)

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

    2016-08-18

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp(3)-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp(2)-hybridized species, the development of methods for sp(3)-sp(3) bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp(3)-sp(3) bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp(3)-sp(3) coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp(3)-sp(3) bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox

  14. Biological roles and therapeutic potential of hydroxy-carboxylic acid receptors

    Directory of Open Access Journals (Sweden)

    Kashan eAhmed

    2011-10-01

    Full Text Available In the recent past, deorphanization studies have described intermediates of energy metabolism to activate G protein-coupled receptors (GPCRs and to thereby regulate metabolic functions. GPR81, GPR109A and GPR109B, formerly known as the nicotinic acid receptor family, are encoded by clustered genes and share a high degree of sequence homology. Recently, hydroxy-carboxylic acids were identified as endogenous ligands of GPR81, GPR109A and GPR109B, and therefore these receptors have been placed into a novel receptor family of hydroxy-carboxylic acid (HCA receptors. The HCA1 receptor (GPR81 is activated by the glycolytic metabolite 2-hydroxy-propionic acid (lactate, the HCA2 receptor is activated by the ketone body 3-hydroxy-butyric acid and the HCA3 receptor (GPR109B is a receptor for the β-oxidation intermediate 3-hydroxy-octanoic acid. While HCA1 and HCA2 receptors are present in most mammalian species, the HCA3 receptor is exclusively found in humans and higher primates. HCA receptors are expressed in adipose tissue and mediate anti-lipolytic effects in adipocytes through Gi-type G-protein-dependent inhibition of adenylyl cyclase. HCA2 and HCA3 inhibit lipolysis during conditions of increased β-oxidation such as prolonged fasting, whereas HCA1 mediates the anti-lipolytic effects of insulin in the fed state. As HCA2 is a receptor for the established anti-dyslipidemic drug nicotinic acid, HCA1 and HCA3 also represent promising drug targets and several synthetic ligands for HCA receptors have been developed. In this article, we will summarize the deorphanization and pharmacological characterization of HCA receptors. Moreover, we will discuss recent progress in elucidating the physiological and pathophysiological role to further evaluate the therapeutic potential of the HCA receptor family for the treatment of metabolic disease.

  15. Δ(1-pyrroline-5-carboxylate/glutamate biogenesis is required for fungal virulence and sporulation.

    Directory of Open Access Journals (Sweden)

    Ziting Yao

    Full Text Available Proline dehydrogenase (Prodh and Δ(1-pyrroline-5-carboxylate dehydrogenase (P5Cdh are two key enzymes in the cellular biogenesis of glutamate. Recombinant Prodh and P5Cdh proteins of the chestnut blight fungus Cryphonectria parasitica were investigated and showed activity in in vitro assays. Additionally, the C. parasitica Prodh and P5Cdh genes were able to complement the Saccharomyces cerevisiae put1 and put2 null mutants, respectively, to allow these proline auxotrophic yeast mutants to grow on media with proline as the sole source of nitrogen. Deletion of the Prodh gene in C. parasitica resulted in hypovirulence and a lower level of sporulation, whereas deletion of P5Cdh resulted in hypovirulence though no effect on sporulation; both Δprodh and Δp5cdh mutants were unable to grow on minimal medium with proline as the sole nitrogen source. In a wild-type strain, the intracellular level of proline and the activity of Prodh and P5Cdh increased after supplementation of exogenous proline, though the intracellular Δ(1-pyrroline-5-carboxylate (P5C content remained unchanged. Prodh and P5Cdh were both transcriptionally down-regulated in cells infected with hypovirus. The disruption of other genes with products involved in the conversion of arginine to ornithine, ornithine and glutamate to P5C, and P5C to proline in the cytosol did not appear to affect virulence; however, asexual sporulation was reduced in the Δpro1 and Δpro2 mutants. Taken together, our results showed that Prodh, P5Cdh and related mitochondrial functions are essential for virulence and that proline/glutamate pathway components may represent down-stream targets of hypovirus regulation in C. parasitica.

  16. Stability study of ZnO nanoparticles in aqueous solutions of carboxylate anions

    Energy Technology Data Exchange (ETDEWEB)

    Godymchuk, Anna, E-mail: godymchuk@tpu.ru; Karepina, Elizaveta; Yunda, Elena; Lyamina, Galina [National Research Tomsk Polytechnic University (Russian Federation); Kosova, Natalia [National Research Tomsk State University (Russian Federation); Kuznetsov, Denis [National University of Science and Technology “MISiS” (Russian Federation)

    2015-03-15

    The paper is devoted to the use of carboxylic acids and salts for the elaboration of stable suspensions of ZnO engineered nanoparticles (40 and 200 nm) in physiological media at pH 6–8. It was shown that the aggregation degree of ZnO-200 particles increases with the growth of carboxylic anion activity, e.g., at pH 7 in the row «Acetate{sup −}–Citrate{sup 3−}–Oxalate{sup 2−}» the average size of ZnO-200 particles in suspensions amounts to «169–523–770» nm, zeta potential–«35.9–−19.9–+5.42 mV», respectively. The aggregation degree of ZnO-40 particles increases in the row «Citrate{sup 3−}–Acetate{sup −}–Oxalate{sup 2−}», at pH 7, the average size of ZnO-40 particles in suspension amounts to «50–121–430» nm, zeta potential–«−28.3–−14.5–+2.3» mV, respectively. pH-impact was found to be size-dependent: there was a significantly less effect of pH on adsorption, dispersion, and electrokinetic properties of ZnO-40 particles when compared to ZnO-200 particles. The main reason for the difference between micro- and nanosized particles behavior is a change of the ratio of acidic, basic, and neutral Bronsted centers for particles of nanosized scale.

  17. Oxidized Cellulose with Different Carboxyl Content: Structure and Properties before and after Beating

    Science.gov (United States)

    Vendula, Hejlová; Miloslav, Milichovský

    Our recent studies concentrated in investigating influence of beating oxidized cellulose, with different carboxyl content, on changing their basic properties (degree of polymerization, WRV - water resistant value and X-ray diffraction). Cellulose samples of oxidized cellulose were beated by toroidal beating machine. Cellulose consists of both amorphous and crystalline regions. Cellulose consists of linear chains of poly[ß-1,4-D- anhydroglucopyranose] (C6nH10n + 2O5n + 1 (n = degree of polymerization of glucose)), which crystallize through hydrogen bonding between the chains and has cellobiose as repeat unit. Oxidized cellulose is preparing by oxidation of cellulose in the C6 position of the glucopyranose units to carboxylic group (-COOH) and polyanhydroglukuronic acid (PAGA) is arised. An other option is oxidation with sodium hypochlorite with catalytic amounts of sodium bromide and 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) under various conditions. Beating and refining or mechanical treatment of fibers in water is an important step in using pulps for papermaking. It is an energy intensive process. The purpose of the treatment is to modify fiber properties to obtain the most desirable paper machine runnability and product properties. End of beating pulps was characterized by position, when all beated pulps under mixture passed through of riddle (about sizes mesh of 50). During beating of samples about different ratio of oxidation it was found, that samples with higher contents of COOH groups in starting pulp are characterized by a significantly lower specific beating energy consumption needed to achieving the same sizes of particles. X-ray analyse shows that for non-beated oxidized cellulose was perceptible high share amorphous contents compared with beated oxidized cellulose.

  18. The effect of aliphatic carboxylic acids on olfaction-based host-seeking of the malaria mosquito Anopheles gambiae sensu stricto

    NARCIS (Netherlands)

    Smallegange, R.C.; Qiu, Y.T.; Bukovinszkine-Kiss, G.; Loon, van J.J.A.; Takken, W.

    2009-01-01

    The role of aliphatic carboxylic acids in host-seeking response of the malaria mosquito Anopheles gambiae sensu stricto was examined both in a dual-choice olfactometer and with indoor traps. A basic attractive blend of ammonia + lactic acid served as internal standard odor. Single carboxylic acids w

  19. LIQUID-CHROMATOGRAPHIC ANALYSIS OF CARBOXYLIC-ACIDS USING N-(4-AMINOBUTYL)-N-ETHYLISOLUMINOL AS CHEMILUMINESCENT LABEL - DETERMINATION OF IBUPROFEN IN SALIVA

    NARCIS (Netherlands)

    STEIJGER, OM; LINGEMAN, H; BRINKMAN, UAT; HOLTHUIS, JJM; SMILDE, AK; DOORNBOS, DA

    1993-01-01

    N-(4-Aminobutyl)-N-ethylisoluminol was used for labelling of carboxylic acids. The derivatization reaction was carried out with 1-hydroxybenzotriazole as pre-activator of the carboxylic acid function and N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide as the coupling reagent. Optimum conditions for t

  20. Carboxylated single-walled carbon nanotubes induce an inflammatory response in human primary monocytes through oxidative stress and NF-{kappa}B activation

    Energy Technology Data Exchange (ETDEWEB)

    Ye Shefang, E-mail: yeshefang@xmu.edu.cn; Zhang Honggang; Wang Yifang; Jiao Fei; Lin Cuilin; Zhang Qiqing, E-mail: zhangqiq@xmu.edu.cn [Xiamen University, Department of Biomaterials, Research Center of Biomedical Engineering, Key Laboratory of Biomedical Engineering of Fujian Province, College of Materials (China)

    2011-09-15

    A mechanistic understanding of interactions between carbon nanotubes (CNTs) and living systems has become imperative owing to the growing nanomedicine applications and the mounting societal concerns on nanosafety. The addition of different chemical groups leads to a significant change in the properties of CNTs, and the resulting functionalized CNTs are generating great interest in many biological applications, such as biosensors and transporters. This study aimed to assess the toxicity exhibited by carboxylic acid functionalized single-walled CNTs (SWCNTs) (with a diameter of 1-2 nm and mean length of 500 nm) and to elucidate possible molecular mechanisms underlying the biological effects of carboxylated SWCNTs in human primary monocytes. The results demonstrated that carboxylated SWCNTs were cytotoxic, triggering apoptosis and G{sub 2}/M phase arrest in human primary monocytes. Flow cytometric and confocal microscopic analysis indicated that internalized carboxylated SWCNTs were mainly accumulated in the cytoplasm. Exposure of human primary monocytes to carboxylated SWCNTs led to interleukin-8 (IL-8) and interleukin-6 (IL-6) expression, reactive oxygen species (ROS) production, and nuclear factor-kappa B (NF-{kappa}B) activation in human primary monocytes. Pretreatment of human primary monocytes with antioxidants or NF-{kappa}B-specific inhibitor before exposure to carboxylated SWCNTs significantly abolished carboxylated SWCNTs-induced IL-8 and IL-6 expression. These results provide novel insights into the carboxylated SWCNTs-mediated chemokine induction and inflammatory responses in vitro.

  1. Selenium speciation in urine by ion-pairing chromatography with perfluorinated carboxylic acids and ICP-MS detection

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Bendahl, L.; Sidenius, U.;

    2002-01-01

    in methanol. Two different perfluorinated carboxylic acids, heptafluorobutanoic acid (HFBA) and nonafluoropentanoic acid (NFPA), were used as ion-pairing agents in the separation. The selectivities of the ion-pairing agents were different. The separation was performed on a microbore column, which...

  2. The binding of 3'-N-piperidine-4-carboxyl-3'-deoxy-ara-uridine to ribonuclease A in the crystal.

    Science.gov (United States)

    Leonidas, Demetres D; Maiti, Tushar Kanti; Samanta, Anirban; Dasgupta, Swagata; Pathak, Tanmaya; Zographos, Spyros E; Oikonomakos, Nikos G

    2006-09-01

    The binding of a moderate inhibitor, 3'-N-piperidine-4-carboxyl-3'-deoxy-ara-uridine, to ribonuclease A has been studied by X-ray crystallography at 1.7A resolution. Two inhibitor molecules are bound in the central RNA binding cavity of RNase A exploiting interactions with residues from peripheral binding sites rather than from the active site of the enzyme. The uracyl moiety of the first inhibitor molecule occupies the purine-preferring site of RNase A, while the rest of the molecule projects to the solvent. The second inhibitor molecule binds with the carboxyl group at the pyrimidine recognition site and the uridine moiety exploits interactions with RNase A residues Lys66, His119 and Asp121. Comparative structural analysis of the 3'-N-piperidine-4-carboxyl-3'-deoxy-ara-uridine complex with other RNase A-ligand complexes provides a structural explanation of its potency. The crystal structure of the RNase A-3'-N-piperidine-4-carboxyl-3'-deoxy-ara-uridine complex provides evidence of a novel ligand-binding pattern in RNase A for 3'-N-aminonucleosides that was not anticipated by modelling studies, while it also suggests ways to improve the efficiency and selectivity of such compounds to develop pharmaceuticals against pathologies associated with RNase A homologues. PMID:16730994

  3. Octyl- and Nonylphenol Ethoxylates and Carboxylates in Wastewater and Sediments by Isotope Dilution Liquid Chromatography/Tandem Mass Spectrometry

    Science.gov (United States)

    This work presents an LC-MS-MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using...

  4. DETERMINATION OF CARBOXYLIC ACIDS BY ION-EXCLUSION CHROMATOGRAPHY WITH NON-SUPPRESSED CONDUCTIVITY AND OPTICAL DETECTORS

    Science.gov (United States)

    Determination of carboxylic acids using non-suppressed conductivity and UV detections is described. The background conductance of 1-octanesulfonic acid, hexane sulfonic acid and sulfuric acid at varying concentrations was determined. Using 0.2 mM 1-octanesulfonic acid as a mobile...

  5. Selective preparation of terminal alkenes from aliphatic carboxylic acids by a palladium-catalysed decarbonylation-eliminiation reaction

    NARCIS (Netherlands)

    Notre, le J.E.L.; Scott, E.L.; Franssen, M.C.R.; Sanders, J.P.M.

    2010-01-01

    Trialkylamines were used as additives in the decarbonylation–elimination reaction catalysed by the combination of palladium(II) chloride and DPE-Phos. Aliphatic carboxylic acids were transformed at relatively low temperature into terminal alkenes in high yield and high selectivity, without the need

  6. Characterization of 1-Aminocyclopropane-1-Carboxylate (ACC) Deaminase-Containing Pseudomonas spp. in the Rhizosphere of Salt-Stressed Canola

    NARCIS (Netherlands)

    Akhgar, A.; Arzanlou, M.; Bakker, Peter; Hamidpour, M.

    2014-01-01

    When exposed to biotic or abiotic stress conditions, plants produce ethylene from its immediate precursor 1-aminocyclopropane-1- carboxylate (ACC), leading to retarded root growth and senescence. Many plant growth-promoting rhizobacteria contain the enzyme ACC deaminase and this enzyme can cleave AC

  7. Characterisation and application of new carboxylic acid-functionalised ruthenium complexes as dye-sensitisers for solar cells

    DEFF Research Database (Denmark)

    Duprez, Virginie; Biancardo, Matteo; Krebs, Frederik C

    2007-01-01

    A series of ruthenium complexes with and without TiO2, anchoring carboxylic acid groups have been synthesised and characterised using nuclear magnetic resonance (NMR), UV-vis and luminescence. These complexes were adsorbed on thin films of the wide band-gap semiconductor anatase and were tested...

  8. Design, Synthesis and Anti-HIV Integrase Evaluation of 4-Oxo-4H-quinolizine-3-carboxylic Acid Derivatives

    Directory of Open Access Journals (Sweden)

    Li-Ming Hu

    2009-02-01

    Full Text Available 4-Oxo-4H-quinolizine-3-carboxylic acid derivatives bearing sulfamido, carboxylamido, benzimidazole and benzothiazole substituents have been designed and synthesized. The structures of these new compounds were confirmed by 1H-NMR, 13C- NMR, IR and ESI (or HRMS spectra. Compounds were screened for possible HIV integrase inhibitory activity.

  9. 7-(3-Chlorophenylamino-1-cyclopropyl-6-fluoro-8-nitro-4-oxo-1,4-dihydroquinoline-3-carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Ghassan F. Shattat

    2010-03-01

    Full Text Available 7-(3-Chlorophenylamino-1-cyclopropyl-6-fluoro-8-nitro-4-oxo-1,4-dihydro-quinoline-3-carboxylic acid (2 was prepared and fully characterized by NMR, IR, and MS. Compound 2 exhibited good antibacterial activity against gram-positive standard and resistant strains.

  10. Carboxylate-Assisted C(sp3)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes

    Science.gov (United States)

    2015-01-01

    The mechanism of C–H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C–H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation–deprotonation mechanism with ΔG⧧298K = 22.2 ± 0.1 kcal·mol–1 for the parent N-adamantyl-N′-mesityl complex. An experimentally determined ΔS⧧ = −5.2 ± 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp3)–H activation. Experimental results, including measurement of a large primary kinetic isotope effect (kH/kD = 8.1 ± 1.7), agree closely with a computed six-membered carboxylate-assisted C–H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment. PMID:24731019

  11. Anodic coupling of carboxylic acids to electron-rich double bonds: A surprising non-Kolbe pathway to lactones

    Directory of Open Access Journals (Sweden)

    Robert J. Perkins

    2013-08-01

    Full Text Available Carboxylic acids have been electro-oxidatively coupled to electron-rich olefins to form lactones. Kolbe decarboxylation does not appear to be a significant competing pathway. Experimental results indicate that oxidation occurs at the olefin and that the reaction proceeds through a radical cation intermediate.

  12. Chiral dirhodium(II) carboxylates and carboxamidates as effective chemzymes in asymmetric synthesis of three-membered carbocycles.

    Science.gov (United States)

    Adly, Frady G; Ghanem, Ashraf

    2014-11-01

    In this review the recent advances in the utilization of two of the most important classes of dirhodium(II) paddlewheel complexes, dirhodium(II) carboxylates and carboxamidates, as chemzymes in inter- and intramolecular asymmetric cyclopropanation, as well as cyclopropenation reactions are discussed.

  13. Synthesis, Characterization and catalytic activity of triorganotin(IV) carboxylates for the production of biodiesel from rocket seed oil

    International Nuclear Information System (INIS)

    Organotin(IV) carboxylates have a wide range of industrial applications such as antifouling paints, PVC stabilization, ion carries in electrochemical membranes and homogeneous catalysts. The catalytic application of organotin carboxylates are in the field of silicone curing, polyurethane formation and esterification. Only a limited literature is available regarding the use of organotin carboxylates in the transesterification of vegetable oil to produce biodiesel . The present study deals with the synthesis of some new triorganotin(IV) carboxylates for their subsequent use as catalyst for transesterification of rocket seed oil to produce biodiesel. The three new triorganotin(IV) i.e. (Me/sub 3/SnL) (1),(Bu/sub 3/Snl) (2) and (Ph/sub 3/SnL) (3), were synthesized by refluxing sodium salt of ligand (NaL), where L=O/sub 2/C(CH/sub 3/)C=CHC/sub 6/H/sub 4/F with trimethyl, tributyl and triphenyl tin(IV) chlorides, respectively for 10 hrs. The synthesized compounds were characterized by instrumental techniques like FT-IR and NMR (1H, 13C). The catalytic activity of these compounds was assessed for transesterification of triglycerides in rocket seed oil to produce biodiesel. All the tested compounds showed good catalytic activity in the order 1> 2 > 3. (author)

  14. Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes

    KAUST Repository

    Li, Yang

    2014-11-07

    © 2014 AIP Publishing LLC. The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green\\'s function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

  15. Synthesis of 2,2'-Dipyrryl Ketones from Pyrrole-2-carboxylic Acids with Trifluoroacetic Anhydride

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Se Hee; Lim, Jin Woo; Yu, Jin; Kim, Jae Nyoung [Chonnam National Univ., Gwangju (Korea, Republic of)

    2013-09-15

    An efficient synthesis of 2,2'-dipyrryl ketones has been carried out from pyrrole-2-carboxylic acids using trifluoroacetic anhydride (TFAA). Simultaneous generation of both mixed anhydride and 2-unsubstituted pyrrole, via facile decarboxylation with in-situ generated TFA, made their cross reaction (intermolecular Friedel-Crafts acylation) possible and efficient.

  16. Occurrence of carboxylic acids in different steps of two drinking-water treatment plants using different disinfectants.

    Science.gov (United States)

    Jurado-Sánchez, Beatriz; Ballesteros, Evaristo; Gallego, Mercedes

    2014-03-15

    The occurrence of 35 aliphatic and aromatic carboxylic acids within two full scale drinking-water treatment plants was evaluated for the first time in this research. At the intake of each plant (raw water), the occurrence of carboxylic acids varied according to the quality of the water source although in both cases 13 acids were detected at average concentrations of 6.9 and 4.7 μg/L (in winter). In the following steps in each treatment plant, the concentration patterns of these compounds differed depending on the type of disinfectant applied. Thus, after disinfection by chloramination, the levels of the acids remained almost constant (average concentration, 6.3 μg/L) and four new acids were formed (butyric, 2-methylbutyric, 3-hydroxybenzoic and 2-nitrobenzoic) at low levels (1.1-5 μg/L). When ozonation/chlorination was used, the total concentration of the carboxylic acids in the raw water sample (4.7 μg/L) increased up to 6 times (average concentration, 26.3 μg/L) after disinfection and 6 new acids (mainly aromatic) were produced at high levels (3.5-100 μg/L). Seasonal variations of the carboxylic acids under study showed that in both plants, maximum levels of all the analytes were reached in the coldest months (autumn and winter), aromatic acids only being found in those seasons.

  17. Copper-Catalyzed N-Arylation of Amides Using (S-N-Methylpyrrolidine-2-carboxylate as the Ligand

    Directory of Open Access Journals (Sweden)

    Dong-Sheng Ma

    2010-03-01

    Full Text Available (S-N-methylpyrrolidine-2-carboxylate, a derivative of natural L-proline, was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides with aryl halides under mild conditions. A variety of N-arylamides were synthesized in good to high yields.

  18. Erbium trifluoromethanesulfonate-catalyzed Friedel–Crafts acylation using aromatic carboxylic acids as acylating agents under monomode-microwave irradiation

    DEFF Research Database (Denmark)

    Tran, Phuong Hoang; Hansen, Poul Erik; Nguyen, Hai Truong;

    2015-01-01

    Erbium trifluoromethanesulfonate is found to be a good catalyst for the Friedel–Crafts acylation of arenes containing electron-donating substituents using aromatic carboxylic acids as the acylating agents under microwave irradiation. An effective, rapid and waste-free method allows the preparation...... of a wide range of aryl ketones in good yields and in short reaction times with minimum amounts of waste...

  19. Alkaline battery containing a separator of a cross-linked copolymer of vinyl alcohol and unsaturated carboxylic acid

    Science.gov (United States)

    Hsu, L. C.; Philipp, W. H.; Sheibley, D. W.; Gonzalez-Sanabria, O. D. (Inventor)

    1985-01-01

    A battery separator for an alkaline battery is described. The separator comprises a cross linked copolymer of vinyl alcohol units and unsaturated carboxylic acid units. The cross linked copolymer is insoluble in water, has excellent zincate diffusion and oxygen gas barrier properties and a low electrical resistivity. Cross linking with a polyaldehyde cross linking agent is preferred.

  20. Synthesis of new series of 4, 5-dihydroisoxazole-5-carboxylate derivatives for the study of their liquid crystalline properties

    Indian Academy of Sciences (India)

    SUMANA Y KOTIAN; NARAYANA U KUDVA N; K M LOKANATHA RAI; K BYRAPPA

    2016-07-01

    A new series of 4,5-dihydroisoxazole-5-carboxylate derivatives were synthesized via [3+2] cycloaddition reaction between ethyl acrylate and nitrile oxide generated in situ in presence of Chloramine-T. The synthesized derivatives were characterized by Mass, IR and NMR Spectroscopy and their mesomorphic behavior were studied using DSC and Polarising Optical Microscopy.

  1. Synthesis of Fischer indole derivatives using carboxyl-functionalized ionic liquid as an efficient and recyclable catalyst

    Institute of Scientific and Technical Information of China (English)

    Feng Ping Yi; Hai Yang Sun; Xian Hua Pan; Yuan Xu; Ji Zong Li

    2009-01-01

    Fischer indole cyclization of phenylhydrazine and various ketones using carboxyl-functionalized ionic liquid, 1-carboxymethyl-3-methylimidazolium tetrafluoroborate (abbreviated as [cmmim][BF4]) as catalyst was successfully performed. The yields of thetarget compounds were 80-92%, the purities were 96-98%. The catalyst could be rocovered and reused for at least six times without significant loss in activity.

  2. Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes

    Science.gov (United States)

    Li, Yang; Tu, Xingchen; Wang, Minglang; Wang, Hao; Sanvito, Stefano; Hou, Shimin

    2014-11-01

    The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

  3. Methyl 6-Methyl-1-(4-methylphenyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Haiping Wang

    2012-04-01

    Full Text Available Methyl 6-methyl-1-(4-methylphenyl-2-oxo-4-phenyl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylate has been synthesized via the modified Biginelli reaction from benzaldehyde, p-tolylurea, and methyl acetoacetate, promoted with microwave irradiation and catalyzed by TsOH under solvent-free conditions in high yield.

  4. Contribution of the gamma-carboxyl group of Glu-43(beta) to the alkaline Bohr effect of hemoglobin A.

    Science.gov (United States)

    Rao, M J; Acharya, A S

    1992-08-18

    Glu-43(beta) of hemoglobin A exhibits a high degree of chemical reactivity around neutral pH for amidation with nucleophiles in the presence of carbodiimide. Such a reactivity is unusual for the side-chain carboxyl groups of proteins. In addition, the reactivity of Glu-43(beta) is also sensitive to the ligation state of the protein [Rao, M. J., & Acharya, A. S. (1991) J. Protein Chem. 10, 129-138]. The influence of deoxygenation of hemoglobin A on the chemical reactivity of the gamma-carboxyl group of Glu-43(beta) has now been investigated as a function of pH (from 5.5 to 7.5). The chemical reactivity of Glu-43(beta) for amidation increases upon deoxygenation only when the modification reaction is carried out above pH 6.0. The pH-chemical reactivity profile of the amidation of hemoglobin A in the deoxy conformation reflects an apparent pKa of 7.0 for the gamma-carboxyl group of Glu-43(beta). This pKa is considerably higher than the pKa of 6.35 for the oxy conformation. The deoxy conformational transition mediated increase in the pKa of the gamma-carboxyl group of Glu-43(beta) implicates this carboxyl group as an alkaline Bohr group. The amidated derivative of hemoglobin A with 2 mol of glycine ethyl ester covalently bound to the protein was isolated by CM-cellulose chromatography.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1354984

  5. Aromatic carboxylate effect on dimensionality of three bis(benzimidazole)-based cobalt(II) coordination polymers: Syntheses, structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li; Tian, Ai-Xiang; Wang, Xiu-Li, E-mail: wangxiuli@bhu.edu.cn

    2013-09-15

    Three new metal-organic coordination polymers [Co(4-bbc){sub 2}(bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H{sub 2}O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H{sub 2}pdc=3,5-pyridinedicarboxylic acid, 1,4-H{sub 2}ndc=1,4-naphthalenedicarboxylic acid and bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) were hydrothermally synthesized and structurally characterized. Polymer 1 is a 1D chain formed by the bbbm ligands and Co{sup II} ions. Polymer 2 exhibits a 2D network with a (3·4·5)(3{sup 2}·4·5·6{sup 2}·7{sup 4}) topology. Polymer 3 possesses a 3D three-fold interpenetrating framework. The versatile structures of title polymers indicate that the aromatic carboxylates have an important influence on the dimensionality of 1–3. Moreover, the thermal stability, electrochemical and luminescent properties of 1–3 were investigated. - graphical abstract: Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were hydrothermally synthesized and structurally characterized. The aromatic carboxylates play a key role in the dimensionality of three polymers. The electrochemical and luminescent properties of three polymers were investigated. Display Omitted - Highlights: • Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were obtained. • The aromatic carboxylates have an important influence on the dimensionality of three polymers. • The electrochemical and luminescent properties of three polymers were investigated.

  6. Integrating syngas fermentation with the carboxylate platform and yeast fermentation to reduce medium cost and improve biofuel productivity.

    Science.gov (United States)

    Richter, Hanno; Loftus, Sarah E; Angenent, Largus T

    2013-01-01

    To ensure economic implementation of syngas fermentation as a fuel-producing platform, engineers and scientists must both lower operating costs and increase product value. A considerable part of the operating costs is spent to procure chemicals for fermentation medium that can sustain sufficient growth of carboxydotrophic bacteria to convert synthesis gas (syngas: carbon monoxide, hydrogen, and carbon dioxide) into products such as ethanol. Recently, we have observed that wildtype carboxydotrophic bacteria (including Clostridium ljungdahlii) can produce alcohols with a longer carbon chain than ethanol via syngas fermentation when supplied with the corresponding carboxylic acid precursors, resulting in possibilities of increasing product value. Here, we evaluated a proof-of-concept system to couple syngas fermentation with the carboxylate platform to both lower medium costs and increase product value. Our carboxylate platform concept consists of an open culture, anaerobic fermentor that is fed with corn beer from conventional yeast fermentation in the corn kernel-to-ethanol industry. The mixed-culture anaerobic fermentor produces a mixture ofcarboxylic acids at dilute concentrations within the carboxylate platform effluent (CPE). Besides providing carboxylic acid precursors, this effluent may represent an inexpensive growth medium. An elemental analysis demonstrated that the CPE lacked certain essential trace metals, but contained ammonium, phosphate, sodium, chloride, potassium, magnesium, calcium, and sulphate at required concentrations. CPE medium with the addition of a trace metal solution supported growth and alcohol production of C. ljungdahlii at similar or better levels compared with an optimized synthetic medium (modified ATCC 1754 medium). Other expensive supplements, such as yeast extract or macro minerals (ammonium, phosphate), were not required. Finally, n-butyric acid and n-caproic acid within the CPE were converted into their corresponding medium

  7. Photo- and thermochromic and adsorption properties of porous coordination polymers based on bipyridinium carboxylate ligands.

    Science.gov (United States)

    Toma, Oksana; Mercier, Nicolas; Allain, Magali; Kassiba, Abdel Adi; Bellat, Jean-Pierre; Weber, Guy; Bezverkhyy, Igor

    2015-09-21

    The zwitterionic bipyridinium carboxylate ligand 1-(4-carboxyphenyl)-4,4'-bipyridinium (hpc1) in the presence of 1,4-benzenedicarboxylate anions (BDC(2-)) and Zn(2+) ions affords three porous coordination polymers (PCPs): [Zn5(hpc1)2(BDC)4(HCO2)2]·2DMF·EtOH·H2O (1), [Zn3(hpc1)(BDC)2(HCO2)(OH)(H2O)]·DMF·EtOH·H2O (2), and [Zn10(hpc1)4(BDC)7(HCO2)2(OH)4(EtOH)2]·3DMF·3H2O (3), with the formate anions resulting from the in situ decomposition of dimethylformamide (DMF) solvent molecules. 1 and 3 are photo- and thermochromic, turning dark green as a result of the formation of bipyridinium radicals, as shown by electron paramagnetic resonance measurements. Particularly, crystals of 3 are very photosensitive, giving an eye-detectable color change upon exposure to the light of the microscope in air within 1-2 min. A very nice and interesting feature is the regular discoloration of crystals from the "edge" to the "core" upon exposition to O2 (reoxidation of organic radicals) due to the diffusion of O2 inside the pores, with this discoloration being slower in an oxygen-poor atmosphere. The formation of organic radicals is explained by an electron transfer from the oxygen atoms of the carboxylate groups to pyridinium cycles. In the structure of 3', [Zn10(hpc1)4(BDC)7(OH)6(H2O)2], resulting from the heating of sample 3 (desolvation and loss of CO molecules due to the decomposition of formate anions), no suitable donor-acceptor interaction is present, and as a consequence, this compound does not exhibit any chromic properties. The presence of permanent porosity in desolvated 1, 2, and 3' is confirmed by methanol adsorption at 25 °C with the adsorbed amount reaching 5 wt % for 1, 10 wt % for 3', and 13 wt % for 2. The incomplete desorption of methanol at 25 °C under vacuum points to strong host-guest interactions. PMID:26370743

  8. Carboxylated nanodiamonds inhibit γ-irradiation damage of human red blood cells

    Science.gov (United States)

    Santacruz-Gomez, K.; Silva-Campa, E.; Melendrez-Amavizca, R.; Teran Arce, F.; Mata-Haro, V.; Landon, P. B.; Zhang, C.; Pedroza-Montero, M.; Lal, R.

    2016-03-01

    Nanodiamonds when carboxylated (cNDs) act as reducing agents and hence could limit oxidative damage in biological systems. Gamma (γ)-irradiation of whole blood or its components is required in immunocompetent patients to prevent transfusion-associated graft versus host disease (TA-GVHD). However, γ-irradiation of blood also deoxygenates red blood cells (RBCs) and induces oxidative damage, including abnormalities in cellular membranes and hemolysis. Using atomic force microscopy (AFM) and Raman spectroscopy, we examined the effect of cNDs on γ-irradiation mediated deoxygenation and morphological damage of RBCs. γ-Radiation induced several morphological phenotypes, including stomatocytes, codocytes and echinocytes. While stomatocytes and codocytes are reversibly damaged RBCs, echinocytes are irreversibly damaged. AFM images show significantly fewer echinocytes among cND-treated γ-irradiated RBCs. The Raman spectra of γ-irradiated RBCs had more oxygenated hemoglobin patterns when cND-treated, resembling those of normal, non-irradiated RBCs, compared to the non-cND-treated RBCs. cND inhibited hemoglobin deoxygenation and morphological damage, possibly by neutralizing the free radicals generated during γ-irradiation. Thus cNDs have the therapeutic potential to preserve the quality of stored blood following γ-irradiation.Nanodiamonds when carboxylated (cNDs) act as reducing agents and hence could limit oxidative damage in biological systems. Gamma (γ)-irradiation of whole blood or its components is required in immunocompetent patients to prevent transfusion-associated graft versus host disease (TA-GVHD). However, γ-irradiation of blood also deoxygenates red blood cells (RBCs) and induces oxidative damage, including abnormalities in cellular membranes and hemolysis. Using atomic force microscopy (AFM) and Raman spectroscopy, we examined the effect of cNDs on γ-irradiation mediated deoxygenation and morphological damage of RBCs. γ-Radiation induced several

  9. Alpha-bungarotoxin binding to target cell in a developing visual system by carboxylated nanodiamond

    International Nuclear Information System (INIS)

    Biological molecules conjugating with nanoparticles are valuable for applications including bio-imaging, bio-detection, and bio-sensing. Nanometer-sized diamond particles have excellent electronic and chemical properties for bio-conjugation. In this study, we manipulated the carboxyl group produced on the surface of nanodiamond (carboxylated nanodiamond, cND) for conjugating with alpha-bungarotoxin (α-BTX), a neurotoxin derived from Bungarus multicinctus with specific blockade of alpha7-nicotinic acetylcholine receptor (α7-nAChR). The electrostatic binding of cND-α-BTX was mediated by the negative charge of the cND and the positive charge of the α-BTX in physiological pH conditions. Sodium dodecyl sulfate-polyacrylamide gel analysis and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI/TOF-MS) spectra displayed that α-BTX proteins were conjugated with cND particles via non-covalent bindings. The green fluorescence of the cND particles combining with the red fluorescence of tetramethylrhodamine-labeled α-BTX presented a yellow color at the same location, which indicated that α-BTX proteins were conjugated with cND particles. Xenopus laevis's oocytes expressed the human α7-nAChR proteins by microinjection with α7-nAChR mRNA. The cND-α-BTX complexes were bound to α7-nAChR locating on the cell membrane of oocytes and human lung A549 cancer cells analyzed by laser scanning confocal microscopy. The choline-evoked α7-nAChR-mediated inward currents of the oocytes were blocked by cND-α-BTX complexes in a concentration-dependent manner using two-electrode voltage-clamp recording. Furthermore, the fluorescence intensity of cND-α-BTX binding on A549 cells could be quantified by flow cytometry. These results indicate that cND-conjugated α-BTX still preserves its biological activity in blocking the function of α7-nAChR, and provide a visual system showing the binding of α-BTX to α7-nAChR

  10. Conjugation of Methotrexate-Amino Derivatives to Macromolecules through Carboxylate Moieties Is Superior Over Conventional Linkage to Amino Residues: Chemical, Cell-Free and In Vitro Characterizations

    Science.gov (United States)

    Cooper, Itzik; Fridkin, Mati; Shechter, Yoram

    2016-01-01

    In this study, we examined the possibility of introducing methotrexate (MTX) to the carboxylate rather than to the ε-amino side chains of proteins. We found that MTX—amino compounds covalently linked to the carboxylate moieties of macromolecules, undergo unusual peptide-bond cleavage, with the release of the MTX amino derivatives from the conjugates. This event takes place at an accelerated rate under acidic conditions, and at a slower rate at physiological pH values. The glutamate portion of MTX is responsible for this behavior, with little or no contribution of the p-aminobenzoate-pteridine ring that is linked to the α-amino side chain of the glutamate. Carboxylate-linked Fmoc-Glu-γ-CONH-(CH2)6-NH2 undergoes hydrolysis in a nearly indistinguishable fashion. A free α carboxylate moiety is essential for this effect. Carboxylate linked Fmoc-glutamic-amide-γ-CONH-(CH2)6-NH2 undergoes no hydrolysis under acidic conditions. Based on these findings, we engineered a cysteine specific MTX containing reagent. Its linkage to bovine serum albumin (BSA) yielded a conjugate with profound antiproliferative efficacy in a MTX-sensitive glioma cell line. In conclusion, carboxylate linked MTX-amino derivatives in particular, and carboxylate linked R-α-GLU-γ amino compounds in general are equipped with‘built-in chemical machinery’ that releases them under mild acidic conditions. PMID:27403959

  11. 2-substituted thiazolidine-4(R)-carboxylic acids as prodrugs of L-cysteine. Protection of mice against acetaminophen hepatotoxicity

    Energy Technology Data Exchange (ETDEWEB)

    Nagasawa, H.T.; Goon, D.J.; Muldoon, W.P.; Zera, R.T.

    1984-05-01

    A number of 2-alkyl- and 2-aryl-substituted thiazolidine-4(R)-carboxylic acids were evaluated for their protective effect against hepatotoxic deaths produced in mice by LD/sub 90/ doses of acetaminophen. 2(RS)-Methyl-, 2(RS)-n-propyl-, and 2(RS)-n- pentylthiazolidine -4(R)-carboxylic acids (compounds 1b,d,e, respectively) were nearly equipotent in their protective effect based on the number of surviving animals at 48 h as well as by histological criteria. 2(RS)-Ethyl-, 2(RS)-phenyl-, and 2(RS)-(4-pyridyl)thiazolidine-4(R)-carboxylic acids (compounds 1c,f,g) were less protective. The enantiomer of 1b, viz., 2(RS)- methylthiazolidine -4(S)-carboxylic acid (2b), was totally ineffective in this regard. Thiazolidine-4(R)-carboxylic acid (1a), but not its enantiomer, 2a, was a good substrate for a solubilized preparation of rat liver mitochondrial proline oxidase (K/sub m/ 1.1 x 10(-4) M; V/sub max/ . 5.4 mumol min-1 (mg of protein)-1). Compound 1b was not a substrate for proline oxidase but dissociated to L-cysteine in this system. At physiological pH and temperature, the hydrogens on the methyl group of 1b underwent deuterium exchange with solvent D/sub 2/O (k1 . 2.5 X 10(-5) s), suggesting that opening of the thiazolidine ring must have taken place. Indeed, 1b labeled with /sup 14/C in the 2 and methyl positions was rapidly metabolized by the rat to produce /sup 14/CO/sub 2/, 80% of the dose being excreted in this form in the expired air after 24 h. It is suggested that these 2-substituted thiazolidine-4(R)-carboxylic acids are prodrugs of L-cysteine that liberate this sulfhydryl amino acid in vivo by nonenzymatic ring opening, followed by solvolysis.

  12. Studies on the physico-mechanical and thermal characteristics of blends of DGEBA epoxy, 3,4 epoxy cyclohexylmethyl, 3',4'-epoxycylohexane carboxylate and carboxyl terminated butadiene co-acrylonitrile (CTBN)

    International Nuclear Information System (INIS)

    Toughening of blend of diglycidyl ether of bisphenol-A (DGEBA) and 3,4 epoxy cyclohexylmethyl, 3',4'-epoxycylohexane carboxylate, i.e. cycloaliphatic epoxy resin (CAE) with varying weight ratios (0-25 wt%) of carboxyl terminated butadiene acrylonitrile (CTBN) copolymer have been investigated. Fourier transform infrared (FTIR) spectroscopic analysis established that the interaction between oxirane groups of DGEBA, CAE and CTBN were responsible for characteristics peak shifts in the blends compared to their counterparts. Physico-mechanical properties of the prepared samples, e.g. tensile, flexural and impact strengths showed an optimum concentration of CTBN (15 wt%) into epoxy matrix, which offered maximum toughening. Thermal stability of the prepared samples was analyzed by dynamic thermogravimetric runs. Cross-sections of the cured samples which failed during impact testing have been critically studied through scanning electron microscopic (SEM) analysis to gain insight into the phase morphology

  13. Studies on the physico-mechanical and thermal characteristics of blends of DGEBA epoxy, 3,4 epoxy cyclohexylmethyl, 3',4'-epoxycylohexane carboxylate and carboxyl terminated butadiene co-acrylonitrile (CTBN)

    Energy Technology Data Exchange (ETDEWEB)

    Tripathi, Garima [Department of Plastic Technology, H. B. Technological Institute, Kanpur 208002 (India); Srivastava, Deepak [Department of Plastic Technology, H. B. Technological Institute, Kanpur 208002 (India)], E-mail: deepak_sri92@rediffmail.com

    2008-11-25

    Toughening of blend of diglycidyl ether of bisphenol-A (DGEBA) and 3,4 epoxy cyclohexylmethyl, 3',4'-epoxycylohexane carboxylate, i.e. cycloaliphatic epoxy resin (CAE) with varying weight ratios (0-25 wt%) of carboxyl terminated butadiene acrylonitrile (CTBN) copolymer have been investigated. Fourier transform infrared (FTIR) spectroscopic analysis established that the interaction between oxirane groups of DGEBA, CAE and CTBN were responsible for characteristics peak shifts in the blends compared to their counterparts. Physico-mechanical properties of the prepared samples, e.g. tensile, flexural and impact strengths showed an optimum concentration of CTBN (15 wt%) into epoxy matrix, which offered maximum toughening. Thermal stability of the prepared samples was analyzed by dynamic thermogravimetric runs. Cross-sections of the cured samples which failed during impact testing have been critically studied through scanning electron microscopic (SEM) analysis to gain insight into the phase morphology.

  14. Synthesis and Intramolecular Azo Coupling of 4-Diazopyrrole-2-carboxylates: Selective Approach to Benzo and Hetero [c]-Fused 6H-Pyrrolo[3,4-c]pyridazine-5-carboxylates.

    Science.gov (United States)

    Galenko, Ekaterina E; Galenko, Alexey V; Khlebnikov, Alexander F; Novikov, Mikhail S; Shakirova, Julia R

    2016-09-16

    A high yield synthesis of fluorescent benzo, thieno, and furo [c]-fused methyl 7-aryl-6H-pyrrolo[3,4-c]pyridazine-5-carboxylates, including unprecedented heterocyclic skeletons, was performed by the transformation of methyl 4-aminopyrrole-2-carboxylate into the corresponding diazo compound, followed by intramolecular azo coupling under acid conditions onto a nucleophilic aryl or hetaryl group in the 3-position. Azo coupling is completely regioselective and, according to DFT calculations, a kinetically controlled reaction. N-Methylation of 1,3-disubstituted 2H-pyrrolo[3,4-c]cinnolines occurs selectively at N5 under kinetic control, leading exclusively to 5-methyl-5H-pyrrolo[3,4-c]cinnoline derivatives. PMID:27548333

  15. [11C]Carbon Monoxide in Palladium- / Selenium-Promoted Carbonylation Reactions : Synthesis of 11C-Imides, Hydrazides, Amides, Carboxylic Acids, Carboxylic Esters, Carbothioates, Ketones and Carbamoyl Compounds

    OpenAIRE

    Karimi, Farhad

    2002-01-01

    [11C]Carbon monoxide in low concentrations has been used in palladium- or seleniummediated carbonylation reactions such as the synthesis of 11C-imides, hydrazides, amides, carboxylic acids, esters, carbothioates, ketones and carbamoyl compounds. In these reactions aryl iodides have been used in most cases. However, less reactive aryl triflate, chloride and bromides were activated using tetrabutylammonium iodide. The reactivities of nucleophiles may have influence on the radiochemical yield of...

  16. Application of the Organic Photosensitizers Bearing Two Carboxylic Acid Groups to Dye-Sensitized Solar Cells

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xue-Hua; YAO Yi-Shan; LI Chao; WANG Wei-Bo; CHENG Xue-Xin; WANG Xue-Song; ZHANG Bao-Wen

    2008-01-01

    Three electron donor-n bridge-electron acceptor(D-π-A)organic dyes bearing two carboxylic acid groups were applied to dye-sensitized solar cells(DSSC)as sensitizers,in Which one triphenylamine or modified triphenylamine and two rhodanine-3-acetic acid fragments act as D and A.respectively.It was found that the introduction of t-butyl or methoxy group in the triphenylamine subunit could lead to more efficient photoinduced intramolecular charge transfer,thus improving the overall photoelectric conversion efficiency of the resultant DSSC.Under global AM 1.5 solar irradiation(73 mW·cm-2),the dye molecule based on methoxy-substituted triphenylamine achieved the best photovoltaic performance:a short circuit photocurrent density(Jsc)of 12.63 mA·cm-2,an open circuit voltage(Voc)of 0.55 V,a fill factor(FF)of 0.62,corresponding to an overall efficiency(η)of 5.9%.

  17. A new fluorinated urethane dimethacrylate with carboxylic groups for use in dental adhesive compositions.

    Science.gov (United States)

    Buruiana, Tinca; Melinte, Violeta; Aldea, Horia; Pelin, Irina M; Buruiana, Emil C

    2016-05-01

    A urethane macromer containing hexafluoroisopropylidene, poly(ethylene oxide) and carboxylic moieties (UF-DMA) was synthesized and used in proportions varying between 15 and 35 wt.% (F1-F3) in dental adhesive formulations besides BisGMA, triethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate. The FTIR and (1)H ((13)C) NMR spectra confirmed the chemical structure of the UF-DMA. The experimental adhesives were characterized with regard to the degree of conversion, water sorption/solubility, contact angle, diffusion coefficient, Vickers hardness, and morphology of the crosslinked networks and compared with the specimens containing 10 wt.% hydroxyapatite (HAP) or calcium phosphate (CaP). The conversion degree (after 180 s of irradiation with visible light) ranged from 59.5% (F1) to 74.8% (F3), whereas the water sorption was between 23.15 μg mm(-3) (F1) and 40.52 μg mm(-3) (F3). Upon the addition of HAP or CaP this parameter attained values of 37.82-49.14 μg mm(-3) (F1-F3-HAP) and 34.58-45.56 μg mm(-3), respectively. Also, the formation of resin tags through the infiltration of a dental composition (F3) was visualized by SEM analysis. The results suggest that UF-DMA taken as co-monomer in dental adhesives of acrylic type may provide improved properties in the moist environment of the mouth. PMID:26952402

  18. Carboxylic ester hydrolase and amylase in ischemic pancreatitis in the guinea pig.

    Science.gov (United States)

    Blind, P J; Bläckberg, L; Lundström, E B; Emdin, S O; Hernell, O

    1996-05-01

    The observation that an elevated level of pancreatic carboxylic ester hydrolase (CEH) in serum is a more sensitive and specific marker of acute pancreatitis than is elevated serum amylase activity prompted us to explore whether these findings could be confirmed in an experimental model and, if so, to find the explanation behind this difference. We therefore developed a model for ischemic pancreatitis in the guinea pig and a sandwich enzyme-linked immunosorbent assay for determination of CEH in this species. There was a strong correlation between duration of ischemia and severity of pancreatic inflammation and between severity of inflammation and serum CEH level. In contrast, serum amylase was elevated only in animals with the most severe grade of inflammation. Amylase was, however, increased in urine in animals with mild inflammation, but the level did not increase with severity of inflammation. Only one of 31 animals had detectable CEH in urine. In animals with intermediate serum CEH levels the serum and biliary concentrations correlated, indicating that CEH may be cleared by the liver. Amylase was detectable in bile only in animals with high serum levels. The results confirm our observations made in previous clinical studies. A likely explanation for differences in serum levels of CEH and amylase is clearance from the circulation at different rates and, at least partly, via different routes, e.g., the liver and kidney, respectively.

  19. Clozapine-carboxylic acid plasticized co-amorphous dispersions: Preparation, characterization and solution stability evaluation

    Directory of Open Access Journals (Sweden)

    Ali Ahmed Mahmoud Abdelhaleem

    2015-06-01

    Full Text Available This study addressed the possibility of forming of co-amorphous systems between clozapine (CZ and various carboxylic acid plasticizers (CAPs. The aim was to improve the solubility and oral bioavailability of clozapine. Co-amorphous dispersions were prepared using modified solvent evaporation methodology at drug/plasticizer stoichiometric ratios of 1:1, 1:1.5 and 1:2. Solid state characterization was performed using differential scanning calorimetry, X-ray diffraction and infra red spectroscopy. Highly soluble homogeneous co-amorphous dispersions were formed between clozapine and CAPs via hydrogen bonding. The co-amorphous dispersions formed with tartaric acid (1:2 showed the highest dissolution percentage (> 95 % in 20 minutes compared to pure crystalline CZ (56 %. Highly stable solutions were obtained from co-amorphous CZ-citric and CZ-tartaric acid at 1:1.5 molar ratio. The prepared dispersions suggest the possibility of peroral or sublingual administration of highly soluble clozapine at a reduced dose with the great chance to bypass the first pass metabolism.

  20. Enhanced Hydrothermal Stability and Catalytic Performance of HKUST-1 by Incorporating Carboxyl-Functionalized Attapulgite.

    Science.gov (United States)

    Yuan, Bo; Yin, Xiao-Qian; Liu, Xiao-Qin; Li, Xing-Yang; Sun, Lin-Bing

    2016-06-29

    Much attention has been paid to metal-organic frameworks (MOFs) due to their large surface areas, tunable functionality, and diverse structure. Nevertheless, most reported MOFs show poor hydrothermal stability, which seriously hinders their applications. Here a strategy is adopted to tailor the properties of MOFs by means of incorporating carboxyl-functionalized natural clay attapulgite (ATP) into HKUST-1, a well-known MOF. A new type of hybrid material was thus fabricated from the hybridization of HKUST-1 and ATP. Our results indicated that the hydrothermal stability of the MOFs as well as the catalytic performance was apparently improved. The frameworks of HKUST-1 were severely destroyed after hydrothermal treatment (hot water vapor, 60 °C), while that of the hybrid materials was maintained. For the hybrid materials containing 8.4 wt % of ATP, the surface area reached 1302 m(2)·g(-1) and was even higher than that of pristine HKUST-1 (1245 m(2)·g(-1)). In the ring-opening of styrene oxide, the conversion reached 98.9% at only 20 min under catalysis from the hybrid material, which was obviously higher than that over pristine HKUST-1 (80.9%). Moreover, the hybrid materials showed excellent reusability and the catalytic activity was recoverable without loss after six cycles. Our materials provide promising candidates for heterogeneous catalysis owing to the good catalytic activity and reusability. PMID:27268731

  1. The antimicrobial effects and metabolomic footprinting of carboxyl-capped bismuth nanoparticles against Helicobacter pylori.

    Science.gov (United States)

    Nazari, P; Dowlatabadi-Bazaz, R; Mofid, M R; Pourmand, M R; Daryani, N E; Faramarzi, M A; Sepehrizadeh, Z; Shahverdi, A R

    2014-01-01

    Organic salts of bismuth are currently used as antimicrobial agents against Helicobacter pylori. This study evaluated the antibacterial effect of elemental bismuth nanoparticles (Bi NPs) using a serial agar dilution method for the first time against different clinical isolates and a standard strain of H. pylori. The Bi NPs were biologically prepared and purified by a recently described method and subjected to further characterization by infrared spectroscopy and anti-H. pylori evaluation. Infrared spectroscopy results showed the presence of carboxyl functional groups on the surface of biogenic Bi NPs. These biogenic nanoparticles showed good antibacterial activity against all tested H. pylori strains. The resulting MICs varied between 60 and 100 μg/ml for clinical isolates of H. pylori and H. pylori (ATCC 26695). The antibacterial effect of bismuth ions was also tested against all test strains. The antimicrobial effect of Bi ions was lower than antimicrobial effect of bismuth in the form of elemental NPs. The effect of Bi NPs on metabolomic footprinting of H. pylori was further evaluated by (1)H NMR spectroscopy. Exposure of H. pylori to an inhibitory concentration of Bi NPs (100 μg/ml) led to release of some metabolites such as acetate, formic acid, glutamate, valine, glycine, and uracil from bacteria into their supernatant. These findings confirm that these nanoparticles interfere with Krebs cycle, nucleotide, and amino acid metabolism and shows anti-H. pylori activity.

  2. Carboxylated nanodiamond and re-oxygenation process of gamma irradiated red blood cells

    Energy Technology Data Exchange (ETDEWEB)

    Acosta-Elias, M. [Doctorado en Nanotecnologia, Universidad de Sonora (Mexico); Sarabia-Sainz, A.; Silva-Campa, E.; Angulo-Molina, A.; Soto-Puebla, D.; Barboza-Flores, M.; Melendrez, R.; Alvarez-Garcia, S.; Pedroza-Montero, M. [Departamento de Investigacion en Fisica, Universidad de Sonora, Hermosillo (Mexico); Pedroso-Santana, S. [Doctorado en Ciencias (Fisica), Universidad de Sonora, Hermosillo (Mexico); Santacruz-Gomez, K.; Castaneda, B. [Departamento de Fisica, Universidad de Sonora, Hermosillo (Mexico)

    2015-11-15

    Nanodiamonds (NDs) possess exceptional physical, chemical, and biological properties, which make them suitable for potential biomedical applications. They are biocompatible and their usefulness as effective Raman/fluorescence probes for labeling as well as for drug delivery has been demonstrated. Related to their biocompatibility, the interaction between NDs and red blood cells (RBCs) is of great interest. In this work, the influence of carboxylated NDs (cNDs) in the re-oxygenation capability of both γ-irradiated and stored RBCs was studied. The standard 25 Gy γ dose recommended to prevent transfusion associated graft-versus-host disease was used. A 5-day maximum storage time was used to evaluate the ''storage lesion''. The hemoglobin (Hb) oxygenation state was assessed by Raman microspectroscopy and the morphologic changes on cells were tracked by optical imaging. Our results show that irradiated RBCs have a better re-oxygenation capability and morphological recovery when they are in presence of cNDs. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Surface grafting of carboxylic groups onto thermoplastic polyurethanes to reduce cell adhesion

    Energy Technology Data Exchange (ETDEWEB)

    Alves, P., E-mail: palves@eq.uc.pt [CIEPQPF, Departamento de Engenharia Química, Universidade de Coimbra, Polo II, Pinhal de Marrocos, 3030-790 Coimbra (Portugal); Ferreira, P. [CIEPQPF, Departamento de Engenharia Química, Universidade de Coimbra, Polo II, Pinhal de Marrocos, 3030-790 Coimbra (Portugal); Kaiser, Jean-Pierre [EMPA, St. Gallen, Lerchenfeldstrasse 5, CH-9014 St. Gallen (Switzerland); Salk, Natalie [Mikrofertigung – Micro Engineering, Fraunhofer IFAM, Wiener Strasse 12, D-288359 Bremen (Germany); Bruinink, Arie [EMPA, St. Gallen, Lerchenfeldstrasse 5, CH-9014 St. Gallen (Switzerland); Sousa, Hermínio C. de; Gil, M.H. [CIEPQPF, Departamento de Engenharia Química, Universidade de Coimbra, Polo II, Pinhal de Marrocos, 3030-790 Coimbra (Portugal)

    2013-10-15

    The interaction of polymers with other materials is an important issue, being their surface properties clearly crucial. For some important polymer applications, their surfaces have to be modified. Surface modification aims to tailor the surface characteristics of a material for a specific application without affecting its bulk properties. Materials can be surface modified by using biological, chemical or physical methods. The aim of this work was to improve the reactivity of the thermoplastic polyurethane (TPU) material (Elastollan{sup ®}) surface and to make its surface cell repellent by grafting carboxylic groups onto its surface. Two TPU materials were studied: a polyether-based TPU and a polyester-based TPU. The grafting efficiency was evaluated by contact angle measurements and by analytical determination of the COOH groups. Scanning electron microscopy (SEM) of the membranes surface was performed as well as cell adhesion tests. It was proved that the surfaces of the TPUs membranes were successfully modified and that cell adhesion was remarkably reduced.

  4. Production and Characterization of Activated Carbon from Oil-Palm Shell for Carboxylic Acid Adsorption

    Directory of Open Access Journals (Sweden)

    Hector Ruiz

    2015-06-01

    Full Text Available In this study, the recovery of volatile carboxylic acids (VCA by adsorption onto activated carbon adsorbent (CA was explored. The CA was synthesized from palm-oil kernel shells using H3PO4 at 10 and 60% w/w as activating agent. The samples produced in this manner were labeled as CA10A, CA60A respectively. Also KOH was used as activating agent at 10 and 60% w/w. In this case, the produced samples were labeled as CA10B, CA60B respectively. After activation, the surface of all four CA samples was extensively characterized both physically and chemically. The obtained CA adsorption behavior for VCA was assessed by submerging samples of CA in solutions at a fixed initial VCA concentration. Because some of the acids were adsorbed on the CA surface, the VCA concentration in solution was reduced. Carbon CA60B exhibited the greatest adsorption capacity, reaching 1300 mg of adsorbed acids/g carbon. Five adsorption isotherms models were fitted to experimental data. The Langmuir-Freundlich model described best the adsorption phenomena. Desorption behavior was assessed by placing CA after adsorption in water and was not high, which forces to reconsider either de desorption mechanism proposed in this study and/or the use CA as synthesized here for VCA recovery.

  5. The Ameliorative Effects of L-2-Oxothiazolidine-4-Carboxylate on Acetaminophen-Induced Hepatotoxicity in Mice

    Directory of Open Access Journals (Sweden)

    Jun Ho Shin

    2013-03-01

    Full Text Available The aim of the study was to investigate the ameliorative effects and the mechanism of action of L-2-oxothiazolidine-4-carboxylate (OTC on acetaminophen (APAP-induced hepatotoxicity in mice. Mice were randomly divided into six groups: normal control group, APAP only treated group, APAP + 25 mg/kg OTC, APAP + 50 mg/kg OTC, APAP + 100 mg/kg OTC, and APAP + 100 mg/kg N-acetylcysteine (NAC as a reference control group. OTC treatment significantly reduced serum alanine aminotransferase and aspartate aminotransferase levels in a dose dependent manner. OTC treatment was markedly increased glutathione (GSH production and glutathione peroxidase (GSH-px activity in a dose dependent manner. The contents of malondialdehyde and 4-hydroxynonenal in liver tissues were significantly decreased by administration of OTC and the inhibitory effect of OTC was similar to that of NAC. Moreover, OTC treatment on APAP-induced hepatotoxicity significantly reduced the formation of nitrotyrosin and terminal deoxynucleotidyl transferase dUTP nick end labeling positive areas of liver tissues in a dose dependent manner. Furthermore, the activity of caspase-3 in liver tissues was reduced by administration of OTC in a dose dependent manner. The ameliorative effects of OTC on APAP-induced liver damage in mice was similar to that of NAC. These results suggest that OTC has ameliorative effects on APAP-induced hepatotoxicity in mice through anti-oxidative stress and anti-apoptotic processes.

  6. Oxidation of ethoxylated fatty alcohols to alkylpolyglycol carboxylic acids using noble metals as catalysts

    Directory of Open Access Journals (Sweden)

    Sagredos, Angelos

    2009-09-01

    Full Text Available The conversion of ethoxylated fatty alcohols to the corresponding carboxylic acids through dehydrogenation/ oxidation using noble-metal catalysts has been studied. Ethoxylated primary aliphatic alcohols, ethoxylated random secondary aliphatic alcohols and ethoxylated alkylphenols have been converted to the corresponding acids in the presence of a base. The noble metal catalysts Palladium and Platinum were used without significant degradation of the ethoxyl chain in yields that exceeded 90%. On the other hand, the catalysts Rhodium and Ruthenium gave yields of about 80% and 60% respectively.La conversión de alcoholes grasos etoxilados a los correspondientes ácidos carboxílicos por deshidrogenación/ oxidación con metales nobles como catalizador ha sido estudiada. Alcoholes primarios alifáticos etoxilados, alcoholes alifáticos secundarios etoxilados al azar y alquilfenoles etoxilados han sido convertidos a los correspondientes ácidos en presencia de base. Los catalizadores paladio y platino fueron usados sin degradación significativa de las cadenas etoxiladas con un rendimiento que excedió del 90%. Por otra parte catalizadores de rodio y rutenio produjeron rendimientos del 80 y 60%, respectivamente.

  7. Jasmonic acid carboxyl methyltransferase regulates development and herbivory-induced defense response in rice.

    Science.gov (United States)

    Qi, Jinfeng; Li, Jiancai; Han, Xiu; Li, Ran; Wu, Jianqiang; Yu, Haixin; Hu, Lingfei; Xiao, Yutao; Lu, Jing; Lou, Yonggen

    2016-06-01

    Jasmonic acid (JA) and related metabolites play a key role in plant defense and growth. JA carboxyl methyltransferase (JMT) may be involved in plant defense and development by methylating JA to methyl jasmonate (MeJA) and thus influencing the concentrations of JA and related metabolites. However, no JMT gene has been well characterized in monocotyledon defense and development at the molecular level. After we cloned a rice JMT gene, OsJMT1, whose encoding protein was localized in the cytosol, we found that the recombinant OsJMT1 protein catalyzed JA to MeJA. OsJMT1 is up-regulated in response to infestation with the brown planthopper (BPH; Nilaparvata lugens). Plants in which OsJMT1 had been overexpressed (oe-JMT plants) showed reduced height and yield. These oe-JMT plants also exhibited increased MeJA levels but reduced levels of herbivore-induced JA and jasmonoyl-isoleucine (JA-Ile). The oe-JMT plants were more attractive to BPH female adults but showed increased resistance to BPH nymphs, probably owing to the different responses of BPH female adults and nymphs to the changes in levels of H2 O2 and MeJA in oe-JMT plants. These results indicate that OsJMT1, by altering levels of JA and related metabolites, plays a role in regulating plant development and herbivore-induced defense responses in rice. PMID:26466818

  8. Carboxylated ficolls: preparation, characterization, and electrophoretic behavior of model charged nanospheres.

    Science.gov (United States)

    Guo, Xuhong; Kirton, Gavin F; Dubin, Paul L

    2006-10-26

    Carboxylated ficolls were prepared as model spherical colloids of variable charge and size, with radii ranging from 3.0 to 19.3 nm. Capillary electrophoresis (CE), electrophoretic light scattering (ELS), and potentiometric titration were used to determine mobilities as a function of pH, degree of ionization alpha, and surface potential psi(0). Measured mobilities typically display a plateau at high pH, corresponding to high alpha and psi(0), confirming the general nature of this effect for charged spheres, seen also for charged dendrimers and charged latex particles. This result is examined in the context of a discontinuity in mobility predicted by the Wiersema, O'Brien, and White (WOW) theory and a more recent primitive model electrophoresis (PME) theory, in which bound counterions are considered either as point charges or as hard spheres. While no mobility maximum can be determined as expected by these two theories, our data seem more to support Belloni's theoretical expectations on charged polymers and spheres. Here we explain the mobility plateaus in terms of counterions accumulated close to the surface (surface potential-determining ions) or within the shear plane (mobility-determining ions).

  9. Secondary structural analysis of the carboxyl-terminal domain from different connexin isoforms.

    Science.gov (United States)

    Spagnol, Gaëlle; Al-Mugotir, Mona; Kopanic, Jennifer L; Zach, Sydney; Li, Hanjun; Trease, Andrew J; Stauch, Kelly L; Grosely, Rosslyn; Cervantes, Matthew; Sorgen, Paul L

    2016-03-01

    The connexin carboxyl-terminal (CxCT) domain plays a role in the trafficking, localization, and turnover of gap junction channels, as well as the level of gap junction intercellular communication via numerous post-translational modifications and protein-protein interactions. As a key player in the regulation of gap junctions, the CT presents itself as a target for manipulation intended to modify function. Specific to intrinsically disordered proteins, identifying residues whose secondary structure can be manipulated will be critical toward unlocking the therapeutic potential of the CxCT domain. To accomplish this goal, we used biophysical methods to characterize CxCT domains attached to their fourth transmembrane domain (TM4). Circular dichroism and nuclear magnetic resonance were complementary in demonstrating the connexin isoforms that form the greatest amount of α-helical structure in their CT domain (Cx45 > Cx43 > Cx32 > Cx50 > Cx37 ≈ Cx40 ≈ Cx26). Studies compared the influence of 2,2,2-trifluoroethanol, pH, phosphorylation, and mutations (Cx32, X-linked Charcot-Marie Tooth disease; Cx26, hearing loss) on the TM4-CxCT structure. While pH modestly influences the CT structure, a major structural change was associated with phosphomimetic substitutions. Since most connexin CT domains are phosphorylated throughout their life cycle, studies of phospho-TM4-CxCT isoforms will be critical toward understanding the role that structure plays in regulating gap junction function. PMID:26542351

  10. Differential expression of two genes for 1-aminocyclopropane-1-carboxylate synthase in tomato fruits

    Energy Technology Data Exchange (ETDEWEB)

    Olson, D.C.; White, J.A.; Edelman, L.; Kende, H. (Michigan State Univ., East Lansing (United States)); Harkins, R.N. (Berlex Biosciences, Alameda, CA (United States))

    1991-06-15

    1-Aminocyclopropane-1-carboxylate synthase is the regulated enzyme in the biosynthetic pathway of the plant hormone ethylene. A full-length cDNA encoding this enzyme has been cloned from tomato fruits. The authors report here the complete nucleotide and derived amino acid sequences of a cDNA encoding a second isoform of ACC synthase from tomato fruits. The cDNAs coding for both isoforms contain highly conserved regions that are surrounded by regions of low homology, especially at the 5{prime} and 3{prime} ends. Gene-specific probes were constructed to examine the expression of transcripts encoding the two ACC synthase isoforms under two conditions of enhanced ethylene formation--namely, during fruit ripening and in response to mechanical stress (wounding). The level of mRNA encoding both isoforms, ACC synthase 1 and 2, increased during ripening. In contrast, wounding caused an increase in only the level of mRNA coding for ACC synthase 1. Blot analysis of genomic DNA digested with restriction enzymes confirmed that ACC synthase 1 and 2 are encoded by different genes.

  11. Effect of A Long Chain Carboxylate Acid on Sodium Dodecyl Sulfate Micelle Structure: A SANS Study

    Science.gov (United States)

    Patriati, Arum; Giri Rachman Putra, Edy; Seok Seong, Baek

    2010-01-01

    The effect of a different hydrocarbon chain length of carboxylate acid, i.e. dodecanoic acid, CH3(CH)10COOH or lauric acid and hexadecanoic acid, CH3(CH2)14COOH or palmitic acid as a co-surfactant in the 0.3 M sodium dedecyl sulfate, SDS micellar solution has been studied using small angle neutron scattering (SANS). The present of lauric acid has induced the SDS structural micelles. The ellipsoid micelles structures changed significantly in length (major axis) from 22.6 Å to 37.1 Å at a fixed minor axis of 16.7 Å in the present of 0.005 M to 0.1 M lauric acid. Nevertheless, this effect did not occur in the present of palmitic acid with the same concentration range. The present of palmitic acid molecules performed insignificant effect on the SDS micelles growth where the major axis of the micelle was elongated from 22.9 Å to 25.3 Å only. It showed that the appropriate hydrocarbon chain length between surfactant and co-surfactant molecules emerged as one of the determining factors in forming a mixed micelles structure.

  12. Porous, rigid metal(III)-carboxylate metal-organic frameworks for the delivery of nitric oxide

    Science.gov (United States)

    Eubank, Jarrod F.; Wheatley, Paul S.; Lebars, Gaëlle; McKinlay, Alistair C.; Leclerc, Hervé; Horcajada, Patricia; Daturi, Marco; Vimont, Alexandre; Morris, Russell E.; Serre, Christian

    2014-12-01

    The room temperature sorption properties of the biological gas nitric oxide (NO) have been investigated on the highly porous and rigid iron or chromium carboxylate based metal-organic frameworks Material Institut Lavoisier (MIL)-100(Fe or Cr) and MIL-127(Fe). In all cases, a significant amount of NO is chemisorbed at 298 K with a loading capacity that depends both on the nature of the metal cation, the structure and the presence of additional iron(II) Lewis acid sites. In a second step, the release of NO triggered by wet nitrogen gas has been studied by chemiluminescence and indicates that only a partial release of NO occurs as well as a prolonged delivery at the biological level. Finally, an in situ infrared spectroscopy study confirms not only the coordination of NO over the Lewis acid sites and the stronger binding of NO on the additional iron(II) sites, providing further insights over the partial release of NO only in the presence of water at room temperature.

  13. Mechanical and thermal properties of crab chitin reinforced carboxylated SBR composites

    Directory of Open Access Journals (Sweden)

    C. Santulli

    2012-05-01

    Full Text Available The addition of small amounts (up to 9 wt% of chitin microsized particles, originating from shellfish waste, to carboxylated styrene-butadiene rubber (XSBR matrix (as received and annealed to 100°C has been studied. In particular, this study concentrated on their mechanical (creep investigation by nanoindentation and dynamical-mechanical analysis, thermal (differential scanning calorimetry and thermogravimetry and swelling behaviour (toluene absorption and was completed by morphological characterisation by scanning electron microscopy and atomic force microscopy. The results show that annealing has a limited effect on materials properties, effects which are further reduced by the addition of growing amounts of crab chitin. It should be noted that the limited filler content used in the study does not substantially modify the linear creep behaviour of XSBR for sufficiently long loading times. The thermal stability of the system does also appear to be preserved even with the maximum chitin content added, while it serves sufficiently as an effective barrier against aromatic solvent absorption.

  14. A novel ubiquitin carboxyl terminal hydrolase is involved in toad oocyte maturation

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    p28, a 28kD protein from toad (Bufo bufo gargarizans) oocytes, was identified by using p13suc1-agaroseaffinity chromatography. Sequence homology analysis of the full-length cDNA of p28 (Gene Bank accessionnumber: AF 314091) indicated that it encodes a protein containing 224 amino-acids with about 55% iden-tities and more than 70% positives to human, rat or mouse UCH-L1, and contains homological functionaldomains of UCH family. Anti-p28 monoclonal antibody, on injecting into the oocytes, could inhibit theprogesterone-induced resumption of meiotic division in a dose-dependent manner. The recombinant proteinp28 showed similar SDS/PAGE behaviors to the native one, and promoted ubiquitin ethyl ester hydrolysis,a classical catalytic reaction for ubiquitin carboxyl terminai hydrolases (UCHs). The results in this paperreveal that a novel protein, p28, exists in the toad oocytes, is a UCH L1 homolog, was engaged in theprocess of progesterone-induced oocyte maturation possibly through an involvement in protein turnover anddegradation.

  15. Structure of eight molecular salts assembled from noncovalent bonding between carboxylic acids, imidazole, and benzimidazole

    Science.gov (United States)

    Jin, Shouwen; Zhang, Huan; Liu, Hui; Wen, Xianhong; Li, Minghui; Wang, Daqi

    2015-09-01

    Eight organic salts of imidazole/benzimidazole have been prepared with carboxylic acids as 2-methyl-2-phenoxypropanoic acid, α-ketoglutaric acid, 5-nitrosalicylic acid, isophthalic acid, 4-nitro-phthalic acid, and 3,5-dinitrosalicylic acid. The eight crystalline forms reported are proton-transfer compounds of which the crystals and compounds were characterized by X-ray diffraction analysis, IR, mp, and elemental analysis. These structures adopted hetero supramolecular synthons, with the most common R22(7) motif observed at salts 2, 3, 5, 6 and 8. Analysis of the crystal packing of 1-8 suggests that there are extensive strong Nsbnd H⋯O, and Osbnd H⋯O hydrogen bonds (charge assisted or neutral) between acid and imidazolyl components in all of the salts. Except the classical hydrogen bonding interactions, the secondary propagating interactions also play important roles in structure extension. This variety, coupled with the varying geometries and number of acidic groups of the acids utilized, has led to the creation of eight supramolecular arrays with 1D-3D structure. The role of weak and strong noncovalent interactions in the crystal packing is analyzed. The results presented herein indicate that the strength and directionality of the Nsbnd H⋯O, and Osbnd H⋯O hydrogen bonds between acids and imidazole/benzimidazole are sufficient to bring about the formation of organic salts.

  16. A physiologically based pharmacokinetic model for quinoxaline-2-carboxylic acid in rats, extrapolation to pigs.

    Science.gov (United States)

    Yang, X; Zhou, Y-F; Yu, Y; Zhao, D-H; Shi, W; Fang, B-H; Liu, Y-H

    2015-02-01

    A multi-compartment physiologically based pharmacokinetic (PBPK) model to describe the disposition of cyadox (CYX) and its metabolite quinoxaline-2-carboxylic acid (QCA) after a single oral administration was developed in rats (200 mg/kg b.w. of CYX). Considering interspecies differences in physiology and physiochemistry, the model efficiency was validated by pharmacokinetic data set in swine. The model included six compartments that were blood, muscle, liver, kidney, adipose, and a combined compartment for the rest of tissues. The model was parameterized using rat plasma and tissue concentration data that were generated from this study. Model simulations were achieved using a commercially available software program (ACSLXL ibero version 3.0.2.1). Results supported the validity of the model with simulated tissue concentrations within the range of the observations. The correlation coefficients of the predicted and experimentally determined values for plasma, liver, kidney, adipose, and muscles in rats were 0.98, 0.98, 0.98, 0.99, and 0.95, respectively. The rat model parameters were then extrapolated to pigs to estimate QCA disposition in tissues and validated by tissue concentration of QCA in swine. The correlation coefficients between the predicted and observed values were over 0.90. This model could provide a foundation for developing more reliable pig models once more data are available.

  17. Structure–anticancer activity relationships among 4-azolidinone-3-carboxylic acids derivatives

    Directory of Open Access Journals (Sweden)

    Lesyk R. B.

    2010-04-01

    Full Text Available The aim of present research was investigation of anticancer activity of 4-azolidinone-3-carboxylic acids derivatives, and studies of structure–activity relationships (SAR aspects. Methods. Organic synthesis; spectral methods; anticancer screening was performed according to the US NCI protocol (Developmental Therapeutic Program. Results. The data of new 4-thiazolidinone-3-alkanecarboxylic acids derivatives in vitro anticancer activity were described. The most active compounds which belong to 5-arylidene-2,4- thia(imidazolidinone-3-alkanecarboxylic acids; 5-aryl(heterylidenerhodanine-3-succinic acids derivatives were selected. Determination of some SAR aspects which allowed to determine directions in lead- compounds structure optimization, as well as desirable molecular fragments for design of potential anticancer agents based on 4-azolidinone scaffold were performed. 5-Arylidenehydantoin-3-acetic acids amides were identified as a new class of significant selective antileukemic agents. Possible pharmacophore scaffold of 5-ylidenerhodanine-3-succinic acids derivatives was suggested. Conclusions. The series of active compounds with high anticancer activity and/or selectivity levels were selected. Some SAR aspects were determined and structure design directions were proposed.

  18. Effective removal of cationic dyes using carboxylate-functionalized cellulose nanocrystals.

    Science.gov (United States)

    Qiao, Han; Zhou, Yanmei; Yu, Fang; Wang, Enze; Min, Yinghao; Huang, Qi; Pang, Lanfang; Ma, Tongsen

    2015-12-01

    A novel carboxylate-functionalized adsorbent (CNM) based on cellulose nanocrystals (CNCs) was prepared and adsorptive removal of multiple cationic dyes (crystal violet, methylene blue, malachite green and basic fuchsin) were investigated. The maximum cationic dyes uptakes ranged from 30.0 to 348.9mgg(-1) following the order of: CNM>CNCs>raw cellulose. Furthermore, the removal of crystal violet by CNM was investigated representatively where kinetics, thermodynamics and isotherm analysis were employed to explain in-depth information associated with the adsorption process. The adsorption kinetics fitted well to the pseudo-second-order model and thermodynamic analysis revealed that the adsorption process was spontaneous and exothermic. Meanwhile, isothermal study demonstrated a monolayer adsorption behavior following the Langmuir model with a calculated maximum absorption capacity of 243.9mgg(-1), which is higher than those of many other reported adsorbents. These findings prefigure the promising potentials of CNM as a versatile adsorbent for the efficient removal of cationic dyes from wastewater. PMID:26298027

  19. Jasmonic acid carboxyl methyltransferase regulates development and herbivory-induced defense response in rice

    Institute of Scientific and Technical Information of China (English)

    Jinfeng Qi; Yonggen Lou; Jiancai Li; Xiu Han; Ran Li; Jianqiang Wu; Haixin Yu; Lingfei Hu; Yutao Xiao; Jing Lu

    2016-01-01

    Jasmonic acid (JA) and related metabolites play a key role in plant defense and growth. JA carboxyl methyltransferase (JMT) may be involved in plant defense and development by methylating JA to methyl jasmonate (MeJA) and thus influencing the concentrations of JA and related metabolites. However, no JMT gene has been well characterized in monocotyledon defense and development at the molecular level. After we cloned a rice JMT gene, OsJMT1, whose encoding protein was localized in the cytosol, we found that the recombinant OsJMT1 protein catalyzed JA to MeJA. OsJMT1 is up-regulated in response to infestation with the brown planthopper (BPH; Nilaparvata lugens). Plants in which OsJMT1 had been overexpressed (oe-JMT plants) showed reduced height and yield. These oe-JMT plants also exhibited increased MeJA levels but reduced levels of herbivore-induced JA and jasmonoyl-isoleucine (JA-Ile). The oe-JMT plants were more attractive to BPH female adults but showed increased resistance to BPH nymphs, probably owing to the different responses of BPH female adults and nymphs to the changes in levels of H2O2 and MeJA in oe-JMT plants. These results indicate that OsJMT1, by altering levels of JA and related metabolites, plays a role in regulating plant development and herbivore-induced defense responses in rice.

  20. Purification of homologous protein carboxyl methyltransferase isozymes from human and bovine erythrocytes

    International Nuclear Information System (INIS)

    The authors have purified the two major isozymes of the L-isoaspartyl/D-aspartyl protein methyltransferase from both human and bovine erythrocytes. These four enzymes all have polypeptide molecular weights of approximately 26,500 and appear to be monomers in solution. Each of these enzymes cross-reacts with antibodies directed against protein carboxyl methyltransferase I from bovine brain. Their structures also appear to be similar when analyzed by dodecyl sulfate gel electrophoresis for the large fragments produced by digestion with Staphylococcus aureus protease V8 or when analyzed by high-performance liquid chromatography (HPLC) for tryptic peptides. The structural relatedness of these enzymes was confirmed by sequence analysis of a total of 433 residues in 32 tryptic fragments of the human erythrocyte isozymes I and II and of the bovine erythrocyte isozyme II. They found sequence identity or probable identity in 111 out of 112 residues when they compared the human isozymes I and II and identities in 127 out of 134 residues when the human and bovine isozymes II were compared. These results suggest that the erythrocyte isozymes from both organisms may have nearly identical structures and confirm the similarities in the function of these methyltransferases that have been previously demonstrated

  1. Purification and characterization of pyrroline-5-carboxylate dehydrogenase from rat liver mitochondrial matrix

    International Nuclear Information System (INIS)

    Pyrroline-5-carboxylate (P5C) dehydrogenase catalyzes the second step of the irreversible two-step oxidation of proline to glutamate or the oxidative second step of the two-step conversion of ornithine to glutamate in mitochondria. Activity was assayed by monitoring directly the conversion of (3H) L-P5C to (3H) L-glutamate. Using this assay, the authors find P5C dehydrogenase most prevalent in liver in rat, with kidney having 71%, heart 51%, and and spleen 15% of the specific activity of liver. Starting with a subcellular fraction enriched for mitochondria, they have isolated a protein fraction enriched in this activity. The soluble protein fraction of the mitochondrial isolate was subjected to (NH4)2SO4 precipitation and successive chromatography on DE 52 anion exchange and Brown 10 dye ligand affinity resins. This procedure yielded a fraction purified more than 500-fold over whole liver homogenate. HPLC and 5'-AMP agarose fractionation experiments now in progress to achieve further purification show promise. Physical studies show a M/sub r/ of 105,000 upon sucrose density gradient centrifugation and 94,000 on molecular sieve HPLC for the activity. Flat bed gel isoelectric focusing of the protein indicates a pI of 5.7. The purified protein exhibits an apparent K/sub m/ of 0.1 mM for L-P5C

  2. The antimicrobial effects and metabolomic footprinting of carboxyl-capped bismuth nanoparticles against Helicobacter pylori.

    Science.gov (United States)

    Nazari, P; Dowlatabadi-Bazaz, R; Mofid, M R; Pourmand, M R; Daryani, N E; Faramarzi, M A; Sepehrizadeh, Z; Shahverdi, A R

    2014-01-01

    Organic salts of bismuth are currently used as antimicrobial agents against Helicobacter pylori. This study evaluated the antibacterial effect of elemental bismuth nanoparticles (Bi NPs) using a serial agar dilution method for the first time against different clinical isolates and a standard strain of H. pylori. The Bi NPs were biologically prepared and purified by a recently described method and subjected to further characterization by infrared spectroscopy and anti-H. pylori evaluation. Infrared spectroscopy results showed the presence of carboxyl functional groups on the surface of biogenic Bi NPs. These biogenic nanoparticles showed good antibacterial activity against all tested H. pylori strains. The resulting MICs varied between 60 and 100 μg/ml for clinical isolates of H. pylori and H. pylori (ATCC 26695). The antibacterial effect of bismuth ions was also tested against all test strains. The antimicrobial effect of Bi ions was lower than antimicrobial effect of bismuth in the form of elemental NPs. The effect of Bi NPs on metabolomic footprinting of H. pylori was further evaluated by (1)H NMR spectroscopy. Exposure of H. pylori to an inhibitory concentration of Bi NPs (100 μg/ml) led to release of some metabolites such as acetate, formic acid, glutamate, valine, glycine, and uracil from bacteria into their supernatant. These findings confirm that these nanoparticles interfere with Krebs cycle, nucleotide, and amino acid metabolism and shows anti-H. pylori activity. PMID:24104691

  3. The cysteine releasing pattern of some antioxidant thiazolidine-4-carboxylic acids.

    Science.gov (United States)

    Önen Bayram, F Esra; Sipahi, Hande; Acar, Ebru Türköz; Kahveci Ulugöl, Reyhan; Buran, Kerem; Akgün, Hülya

    2016-05-23

    Oxidative stress that corresponds to a significant increase in free radical concentration in cells can cause considerable damage to crucial biological macromolecules if not prevented by cellular defense mechanisms. The low-molecular-weight thiol glutathione (GSH) constitutes one of the main intracellular antioxidants. It is synthesized via cysteine, an amino acid found only in limited amounts in cells because of its neurotoxicity. Thus, to ensure an efficient GSH synthesis in case of an oxidative stress, cysteine should be provided extracellularly. Yet, given its nucleophilic properties and its rapid conversion into cystine, its corresponding disulfide, cysteine presents some toxicity and therefore is usually supplemented in a prodrug approach. Here, some thiazolidine-4-carboxylic acids were synthesized and evaluated for their antioxidant properties via the DDPH and CUPRAC assays. Then, the cysteine releasing capacity of the obtained compounds was investigated in aqueous and organic medium in order to correlate the relevant antioxidant properties of the molecules with their cysteine releasing pattern. As a result, the structures' antioxidative properties were not only attributed to cysteine release but also to the thiazolidine cycle itself. PMID:27017266

  4. The pentose phosphate pathway and pyruvate carboxylation after neonatal hypoxic-ischemic brain injury.

    Science.gov (United States)

    Brekke, Eva M F; Morken, Tora S; Widerøe, Marius; Håberg, Asta K; Brubakk, Ann-Mari; Sonnewald, Ursula

    2014-04-01

    The neonatal brain is vulnerable to oxidative stress, and the pentose phosphate pathway (PPP) may be of particular importance to limit the injury. Furthermore, in the neonatal brain, neurons depend on de novo synthesis of neurotransmitters via pyruvate carboxylase (PC) in astrocytes to increase neurotransmitter pools. In the adult brain, PPP activity increases in response to various injuries while pyruvate carboxylation is reduced after ischemia. However, little is known about the response of these pathways after neonatal hypoxia-ischemia (HI). To this end, 7-day-old rats were subjected to unilateral carotid artery ligation followed by hypoxia. Animals were injected with [1,2-(13)C]glucose during the recovery phase and extracts of cerebral hemispheres ipsi- and contralateral to the operation were analyzed using (1)H- and (13)C-NMR (nuclear magnetic resonance) spectroscopy and high-performance liquid chromatography (HPLC). After HI, glucose levels were increased and there was evidence of mitochondrial hypometabolism in both hemispheres. Moreover, metabolism via PPP was reduced bilaterally. Ipsilateral glucose metabolism via PC was reduced, but PC activity was relatively preserved compared with glucose metabolism via pyruvate dehydrogenase. The observed reduction in PPP activity after HI may contribute to the increased susceptibility of the neonatal brain to oxidative stress.

  5. Carboxyl modified magnetic nanoparticles coated open tubular column for capillary electrochromatographic separation of biomolecules.

    Science.gov (United States)

    Wang, Wentao; Xiao, Xing; Chen, Jia; Jia, Li

    2015-09-11

    Carboxyl modified magnetic nanoparticles (Fe3O4-COOH MNPs) coated open tubular (OT) columns were prepared for capillary electrochromatography. The Fe3O4-COOH MNPs coatings were constructed on the surface of positively charged poly(diallydimethylammonium chloride) (PDDA) modified capillaries through electrostatic self-assembly approach. The as-prepared PDDA@Fe3O4-COOH MNPs coated OT columns were characterized by scanning electron microscopy and electroosmotic flow measurement. The electrochromatographic characterization of the OT columns was evaluated by separation of amino acids, dipeptides and proteins. The influences of background solution pH, concentration, and organic modifier content on separation were investigated. The separation of these analytes was primarily based on the electrophoretic mechanism in combination with chromatographic mechanism. The Fe3O4-COOH MNPs coatings improved the separation resolution of these analytes due to their large surface area. Three variants of bovine serum albumin, two variants of β-lactoglobulin and nine glycoisoforms of ovalbumin were successfully separated. The relative standard deviations of migration times of analytes representing run-to-run, day-to-day and column-to-column were less than 4.3%. Furthermore, the feasibility of the PDDA@Fe3O4-COOH MNPs coated OT column was verified by successful separation of acidic proteins in egg white. PMID:26265004

  6. The physical and degradation properties of starch-graft-acrylonitrile/carboxylated nitrile butadiene rubber latex films.

    Science.gov (United States)

    Misman, M A; Azura, A R; Hamid, Z A A

    2015-09-01

    Starch-graft-acrylonitrile (ANS) is compounded with carboxylated nitrile butadiene rubber (XNBR) latex. The control XNBR and the ANS/XNBR latex films were prepared through a coagulant dipping process. The films were subjected to ageing and soil burial procedures. For the biodegradation experiment, the surface of the film was assessed after the 2nd, 4th and 8th week of soil burial. The ANS, XNBR, and ANS/XNBR colloidal stability were determined with a Malvern Zetasizer. For the dipped latex films, the mechanical, morphological and thermal properties were analyzed. The addition of ANS into the XNBR latex increased the stability of the colloidal dispersions, decreased the latex film tensile strength, but increased the elongation at break due to the bipolar interaction of the ANS and XNBR particles. The ANS/XNBR latex films aged faster than the control films while the morphological analysis showed the existence of a starch crystal region and the formation of microbial colonies on the surfaces of the films. Based on the TGA-DTA curves, a higher ΔT was observed for the ANS/XNBR latex films signifying high thermal energy needed for the film to thermally degrade. PMID:26005134

  7. Anti-Inflammatory and Antinociceptive Activities of Anthraquinone-2-Carboxylic Acid.

    Science.gov (United States)

    Park, Jae Gwang; Kim, Seung Cheol; Kim, Yun Hwan; Yang, Woo Seok; Kim, Yong; Hong, Sungyoul; Kim, Kyung-Hee; Yoo, Byong Chul; Kim, Shi Hyung; Kim, Jong-Hoon; Cho, Jae Youl

    2016-01-01

    Anthraquinone compounds are one of the abundant polyphenols found in fruits, vegetables, and herbs. However, the in vivo anti-inflammatory activity and molecular mechanisms of anthraquinones have not been fully elucidated. We investigated the activity of anthraquinones using acute inflammatory and nociceptive experimental conditions. Anthraquinone-2-carboxylic acid (9,10-dihydro-9,10-dioxo-2-anthracenecarboxylic acid, AQCA), one of the major anthraquinones identified from Brazilian taheebo, ameliorated various inflammatory and algesic symptoms in EtOH/HCl- and acetylsalicylic acid- (ASA-) induced gastritis, arachidonic acid-induced edema, and acetic acid-induced abdominal writhing without displaying toxic profiles in body and organ weight, gastric irritation, or serum parameters. In addition, AQCA suppressed the expression of inflammatory genes such as cyclooxygenase- (COX-) 2 in stomach tissues and lipopolysaccharide- (LPS-) treated RAW264.7 cells. According to reporter gene assay and immunoblotting analyses, AQCA inhibited activation of the nuclear factor- (NF-) κB and activator protein- (AP-) 1 pathways by suppression of upstream signaling involving interleukin-1 receptor-associated kinase 4 (IRAK1), p38, Src, and spleen tyrosine kinase (Syk). Our data strongly suggest that anthraquinones such as AQCA act as potent anti-inflammatory and antinociceptive components in vivo, thus contributing to the immune regulatory role of fruits and herbs. PMID:27057092

  8. Binary and ternary complexation of NpO{sub 2}{sup +} with carboxylate and aminocarboxylate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Thakur, Punam [Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry; Van Luik, Abraham E. [Department of Energy, Carlsbad Field Office, NM (United States)

    2014-11-01

    The complex formation of NpO{sub 2}{sup +} with carboxylates: oxalic acid (Ox), malonic acid (Mal) succinic acid (Suc); glutaric acid (Glu), methylmalonic acid (Memal), oxydiacetic acid (ODA), TDA (thiodiacetic acid) and citric acid (Cit) and aminocarboxylates: iminodiacetic acid (IDA), methyliminodiacetic acid (MIDA), nitrilotriacetic acid (NTA), 2-hydroxyethylethylenediamine triacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) was studied by solvent extraction in 6.60 m NaClO{sub 4} at 25 C. The formation of only the 1: 1 NpO{sub 2}{sup +} complex was observed with the ligands under investigation. The complexation of NpO{sub 2}{sup +} with Ox, IDA, ODA and TDA was also measured at variable temperatures ranging from 25-60 C in 6.60 m NaClO{sub 4}. Results show that the complexation of NpO{sub 2}{sup +} with these ligands increases with increasing temperature. The enthalpy and entropy of complexation of NpO{sub 2}{sup +} were calculated from the temperature dependence of the stability constants using the Van't Hoff equation. Additionally, the formation of an aqueous ternary complex of the form NpO{sub 2}(X)(L) (X = EDTA or HEDTA; L = Ox or ODA) was identified for NpO{sub 2}{sup +} at 25 C. Stabilities of these complexes are measured and discussed in term of their structures and basicities.

  9. Nature of olefins and carboxyl groups in an Australian brown coal resin

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, M.A.; Collin, P.J.; Vassallo, A.M.; Russell, N.J.

    1984-01-01

    The chemical structure of the resin from an Australian soft brown coal (Yallourn) has been investigated by cross-polarization nuclear magnetic resonance spectroscopy with magic angle spinning (/sup 13/C CP MAS NMR). Some additional solution /sup 1/H and /sup 13/C data were also obtained. Solid-state experiments were performed with and without a delay period before data acquisition. The resulting free induction decays were Fourier transformed with respect to acquisition time and delay period to produce two-dimensional solid-state spectra. Assignments made from the spectra clearly demonstrate that the gross chemical structure of the Yallourn resin is best described as a polymerized diterpenoid with one axial carboxylic group and two double bonds. One double bond is trisubstituted, the other is monosubstituted. After consideration of various mechanisms for polymerization of diterpenoid units during biogenesis and coalification, it was concluded that polymerization occurs at the C/sub 15/ carbon atoms in the diterpenoids without cyclization of the methylene units at C/sub 8/. 26 references.

  10. Radioimmunoassay for anileridine, meperidine, and other N-substituted phenylpiperidine carboxylic acid esters

    Energy Technology Data Exchange (ETDEWEB)

    Van Vunakis, H.; Freeman, D.S.; Gjika, H.B.

    1975-10-01

    Antibodies that bind an /sup 125/I-tyramyl derivative of N-succinylanileridine have been produced in animals immunized with N-succinylanileridine-hemocyanin conjugate. Several congeners and metabolites have been tested as competitors of this antigen-antibody reaction. The concentrations (in picomoles) required for 50 percent inhibition have been found to be: anileridine (0.2), meperidine (3.5), piminodine (3.8), diphenoxylate (20.5), normeperidine (20.0), meperidine acid (45,000) and anileridine acid (3,400). Although ester hydrolysis results in changes in inhibiting capacities on the order of 10/sup 4/, major structural changes in the substituent on the nitrogen of the piperidine ring are not readily recognized by the antibody. This radioimmunoassay can be used to study a variety of N-substituted phenylpiperidine carboxylic acid esters by relating the results to the standard curve obtained for the drug under investigation. For all practical purposes, alphaprodine, morphine and methadone do not interfere with the assay.

  11. Radioimmunoassay for anileridine, meperidine, and other N-substituted phenylpiperidine carboxylic acid esters

    International Nuclear Information System (INIS)

    Antibodies that bind an 125I-tyramyl derivative of N-succinylanileridine have been produced in animals immunized with N-succinylanileridine-hemocyanin conjugate. Several congeners and metabolites have been tested as competitors of this antigen-antibody reaction. The concentrations (in picomoles) required for 50 percent inhibition have been found to be: anileridine (0.2), meperidine (3.5), piminodine (3.8), diphenoxylate (20.5), normeperidine (20.0), meperidine acid (45,000) and anileridine acid (3,400). Although ester hydrolysis results in changes in inhibiting capacities on the order of 104, major structural changes in the substituent on the nitrogen of the piperidine ring are not readily recognized by the antibody. This radioimmunoassay can be used to study a variety of N-substituted phenylpiperidine carboxylic acid esters by relating the results to the standard curve obtained for the drug under investigation. For all practical purposes, alphaprodine, morphine and methadone do not interfere with the assay

  12. Biosynthesis of Bacterial Cellulose/Carboxylic Multi-Walled Carbon Nanotubes for Enzymatic Biofuel Cell Application

    Directory of Open Access Journals (Sweden)

    Pengfei Lv

    2016-03-01

    Full Text Available Novel nanocomposites comprised of bacterial cellulose (BC with carboxylic multi-walled carbon nanotubes (c-MWCNTs incorporated into the BC matrix were prepared through a simple method of biosynthesis. The biocathode and bioanode for the enzyme biological fuel cell (EBFC were prepared using BC/c-MWCNTs composite injected by laccase (Lac and glucose oxidase (GOD with the aid of glutaraldehyde (GA crosslinking. Biosynthesis of BC/c-MWCNTs composite was characterized by digital photos, scanning electron microscope (SEM, and Fourier Transform Infrared (FTIR. The experimental results indicated the successful incorporation of c-MWCNTs into the BC. The electrochemical and biofuel performance were evaluated by cyclic voltammetry (CV and linear sweep voltammetry (LSV. The power density and current density of EBFCs were recorded at 32.98 µW/cm3 and 0.29 mA/cm3, respectively. Additionally, the EBFCs also showed acceptable stability. Preliminary tests on double cells indicated that renewable BC have great potential in the application field of EBFCs.

  13. Study of kinetics of degradation of cyclohexane carboxylic acid by acclimated activated sludge.

    Science.gov (United States)

    Wang, Chunhua; Shi, Shuian; Chen, Hongyan

    2016-01-01

    Activated sludge contains complex microorganisms, which are highly effective biodegrading agents. In this study, the kinetics of biodegradation of cyclohexane carboxylic acid (CHCA) by an acclimated aerobic activated sludge were investigated. The results showed that after 180 days of acclimation, the activated sludge could steadily degrade >90% of the CHCA in 120 h. The degradation of CHCA by the acclimated activated sludge could be modeled using a first-order kinetics equation. The equations for the degradation kinetics for different initial CHCA concentrations were also obtained. The kinetics constant, kd, decreased with an increase in the CHCA concentration, indicating that, at high concentrations, CHCA had an inhibiting effect on the microorganisms in the activated sludge. The effects of pH on the degradation kinetics of CHCA were also investigated. The results showed that a pH of 10 afforded the highest degradation rate, indicating that basic conditions significantly promoted the degradation of CHCA. Moreover, it was found that the degradation efficiency for CHCA increased with an increase in temperature and concentration of dissolved oxygen under the experimental conditions.

  14. Carboxylate platform: the MixAlco process part 2: process economics.

    Science.gov (United States)

    Granda, Cesar B; Holtzapple, Mark T; Luce, Gary; Searcy, Katherine; Mamrosh, Darryl L

    2009-05-01

    The MixAlco process employs a mixed culture of acid-forming microorganisms to convert biomass to carboxylate salts, which are concentrated via vapor-compression evaporation and subsequently chemically converted to other chemical and fuel products. To make alcohols, hydrogen is required, which can be supplied from a number of processes, including gasifying biomass, separation from fermentor gases, methane reforming, or electrolysis. Using zeolite catalysts, the alcohols can be oligomerized into hydrocarbons, such as gasoline. A 40-tonne/h plant processing municipal solid waste ($45/tonne tipping fee) and using hydrogen from a pipeline or refinery ($2.00/kg H(2)) can sell alcohols for $1.13/gal or gasoline for $1.75/gal with a 15% return on investment ($0.61/gal of alcohol or $0.99/gal of gasoline for cash costs only). The capital cost is $1.95/annual gallon of mixed alcohols. An 800-tonne/h plant processing high-yield biomass ($60/tonne) and gasifying fermentation residues and waste biomass to hydrogen ($1.42/kg H(2)) can sell alcohols for $1.33/gal or gasoline for $2.04/gal with a 15% return on investment ($1.08/gal of alcohol or $1.68/gal of gasoline for cash costs only). The capital cost for the alcohol and gasification plants at 800 tonne/h is $1.45/annual gallon of mixed alcohols.

  15. Porous, rigid metal(III-carboxylate metal-organic frameworks for the delivery of nitric oxide

    Directory of Open Access Journals (Sweden)

    Jarrod F. Eubank

    2014-12-01

    Full Text Available The room temperature sorption properties of the biological gas nitric oxide (NO have been investigated on the highly porous and rigid iron or chromium carboxylate based metal-organic frameworks Material Institut Lavoisier (MIL-100(Fe or Cr and MIL-127(Fe. In all cases, a significant amount of NO is chemisorbed at 298 K with a loading capacity that depends both on the nature of the metal cation, the structure and the presence of additional iron(II Lewis acid sites. In a second step, the release of NO triggered by wet nitrogen gas has been studied by chemiluminescence and indicates that only a partial release of NO occurs as well as a prolonged delivery at the biological level. Finally, an in situ infrared spectroscopy study confirms not only the coordination of NO over the Lewis acid sites and the stronger binding of NO on the additional iron(II sites, providing further insights over the partial release of NO only in the presence of water at room temperature.

  16. Copper Complexes of Nicotinic-Aromatic Carboxylic Acids as Superoxide Dismutase Mimetics

    Directory of Open Access Journals (Sweden)

    Virapong Prachayasittikul

    2008-12-01

    Full Text Available Nicotinic acid (also known as vitamin B3 is a dietary element essential for physiological and antihyperlipidemic functions. This study reports the synthesis of novel mixed ligand complexes of copper with nicotinic and other select carboxylic acids (phthalic, salicylic and anthranilic acids. The tested copper complexes exhibited superoxide dismutase (SOD mimetic activity and antimicrobial activity against Bacillus subtilis ATCC 6633, with a minimum inhibition concentration of 256 μg/mL. Copper complex of nicotinic-phthalic acids (CuNA/Ph was the most potent with a SOD mimetic activity of IC50 34.42 μM. The SOD activities were observed to correlate well with the theoretical parameters as calculated using density functional theory (DFT at the B3LYP/LANL2DZ level of theory. Interestingly, the SOD activity of the copper complex CuNA/Ph was positively correlated with the electron affinity (EA value. The two quantum chemical parameters, highest occupied molecular orbital (HOMO and lowest unoccupied molecular orbital (LUMO, were shown to be appropriate for understanding the mechanism of the metal complexes as their calculated energies show good correlation with the SOD activity. Moreover, copper complex with the highest SOD activity were shown to possess the lowest HOMO energy. These findings demonstrate a great potential for the development of value-added metallovitamin-based therapeutics.

  17. Synthesis and properties of new luminescent acridinium-9-carboxylic acid derivatives and their application in luminescence immunoassays (LIA).

    Science.gov (United States)

    Kinkel, T; Lübbers, H; Schmidt, E; Molz, P; Skrzipczyk, H J

    1989-07-01

    Two new groups of chemiluminescent acridinium labels have been presented: (a) acridinium-9-thiocarboxylates, (b) acridinium-9-(N-sulphonyl)carboxamides. Both groups show higher light yields and faster emission kinetics compared with the known acridinium carboxylate. Owing to the poor storage stability of the thiocarboxylate tracers they are not suitable for commercial use. Acridinium-9-(N-sulphonyl)carboxamides allow a variation of the structure, their stability after conjugation to antibodies is in most cases clearly better than the stability of thiocarboxylate and carboxylate tracers. Light yields and emission kinetics are also superior and good immunoassays have been developed. Therefore, this new class of chemiluminescent labels seems to be suitable for use in commercial assays. PMID:2801207

  18. Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Bahk, Yeon Kyoung; He, Xu; Gitsis, Emmanouil; Kuo, Yu-Ying [ETH Zurich, Institute of Environmental Engineering (Switzerland); Kim, Nayoung [EMPA, Building Energy Materials and Components (Switzerland); Wang, Jing, E-mail: jing.wang@ifu.baug.ethz.ch [ETH Zurich, Institute of Environmental Engineering (Switzerland)

    2015-10-15

    Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH{sub 3}CO{sub 2}NH{sub 4}) and sodium acetate (CH{sub 3}CO{sub 2}Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example.

  19. /sup 67/Zn and /sup 1/H NMR studies of Zn/sup 2 +/-imidazole and carboxylate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Shimizu, T. (Chemical Research Inst. of Non-Aqueous Solutions, Katahira, Japan); Kudaka, M.; Hatano, M.

    1982-06-15

    /sup 67/Zn NMR studies of naturally abundant Zn/sup 2 +/-imidazole and carboxylate ligands. Complexes are shown. Thus, quadrupolar relaxation changes in /sup 67/Zn NMR caused by adding imidazole ligands are more remarkable than those by carboxylate ligands. The changes caused by adding less bulky imidazole ligands are more prominent than those caused by a bulky imidazole ligand. Changes in Zn/sup 2 +/ quadrupolar relaxation rate caused by adding a cyclic hexapeptide consisting of L-histidine, L-cystein(Acm) and D-leucine are larger than those by a corresponding linear hexapeptide. Those changes in the quadrupolar relaxation rate of /sup 67/Zn NMR among Zn/sup 2 +/ complexes can be reasonably interpreted in terms of the differences of equilibrium constants of those complexes to a first approximation.

  20. RECOVERY OF CARBOXYLIC ACIDS FROM AQUEOUS SOLUTIONS BY LIQUID-LIQUID EXTRACTION WITH A TRIISOOCTYLAMINE DILUENT SYSTEM

    Directory of Open Access Journals (Sweden)

    G. Malmary

    2001-12-01

    Full Text Available Tertiary alkylamines in solution with organic diluents are attractive extractants for the recovery of carboxylic acids from dilute aqueous phases. The aim of this study was to investigate the mechanism for extraction of organic acids from water by a long-chain aliphatic tertiary amine. In order to attain this objective, we studied the liquid-liquid equilibria between the triisooctylamine + 1-octanol + n-heptane system as solvent and an aqueous solution of an individual carboxylic acid such as citric, lactic and malic acids. The experiments showed that the partition coefficient for a particular organic acid depends on the kind of solute, notably when the acid concentration in the aqueous phase is low. A mathematical model, where both chemical association and physical distribution are taken into consideration, is proposed. The model suggests that the various complexes obtained between amine and organic acids contribute to the distribution of the solute between the coexisting phases in equilibrium.

  1. A Novel and Facile Synthesis of 2-(Benzofuran-2-yl)benzo[h]- quinoline-3-carboxylic Acid Derivatives

    Institute of Scientific and Technical Information of China (English)

    高文涛; 姜云; 李阳; 李凤; 闫岩

    2012-01-01

    A simple and concise approach for the synthesis of a series of new heterocyclic systems of 2-(benzofuran-2-yl)- benzo[h]quinoline-3-carboxylic acid derivatives (3a--3g) is described. The synthetic strategy features the one-pot reaction of ethyl 2-(chloromethyl)benzo[h]quinoline-3-carboxylate (2) with various substituted salicylaldehydes as well as 2-hydroxy-l-naphthaldehyde as a key step. The substrate 2 was prepared in good yield by a mild, efficient and direct reaction of 1-naphthylamine (1) with Vilsmeier-Haack reagent. The structures of all the new compounds were identified by spectral data and elemental analysis.

  2. Recovery of carboxylic acids produced during dark fermentation of food waste by adsorption on Amberlite IRA-67 and activated carbon.

    Science.gov (United States)

    Yousuf, Ahasa; Bonk, Fabian; Bastidas-Oyanedel, Juan-Rodrigo; Schmidt, Jens Ejbye

    2016-10-01

    Amberlite IRA-67 and activated carbon were tested as promising candidates for carboxylic acid recovery by adsorption. Dark fermentation was performed without pH control and without addition of external inoculum at 37°C in batch mode. Lactic, acetic and butyric acids, were obtained, after 7days of fermentation. The maximum acid removal, 74%, from the Amberlite IRA-67 and 63% from activated carbon was obtained from clarified fermentation broth using 200gadsorbent/Lbroth at pH 3.3. The pH has significant effect and pH below the carboxylic acids pKa showed to be beneficial for both the adsorbents. The un-controlled pH fermentation creates acidic environment, aiding in adsorption by eliminating use of chemicals for efficient removal. This study proposes simple and easy valorization of waste to valuable chemicals. PMID:26898679

  3. Carboxylic-containing copolymer as template to prepare CdS, ZnS and doped nanoparticles

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    CdS, CdS:Mn, ZnS, ZnS:Mn and ZnS:Tb nanoparticles were preparedby using carboxylic-containing copolymer, polystyrene-maleic anhydride (PSM), as template. Average particle size, 2.5 nm for CdS nanoparticles, is deduced from UV-vis absorption spectra and consistent with the observation of TEM. Characteristic emissions of the doping ions can be observed and the energy transfer from the host to the doping ions is verified. Fourier transform infrared (FTIR) spectra were studied to confirm the bonding effect of the copolymer and the metal ions. PSM hydrolyzed and chelated metal ions by its carboxylic group, and then performed as a protection layer after the formation of nanoparticles.

  4. Detection of a CO and NH3 gas mixture using carboxylic acid-functionalized single-walled carbon nanotubes.

    Science.gov (United States)

    Dong, Ki-Young; Choi, Jinnil; Lee, Yang Doo; Kang, Byung Hyun; Yu, Youn-Yeol; Choi, Hyang Hee; Ju, Byeong-Kwon

    2013-01-01

    Carbon nanotubes (CNT) are extremely sensitive to environmental gases. However, detection of mixture gas is still a challenge. Here, we report that 10 ppm of carbon monoxide (CO) and ammonia (NH3) can be electrically detected using a carboxylic acid-functionalized single-walled carbon nanotubes (C-SWCNT). CO and NH3 gases were mixed carefully with the same concentrations of 10 ppm. Our sensor showed faster response to the CO gas than the NH3 gas. The sensing properties and effect of carboxylic acid group were demonstrated, and C-SWCNT sensors with good repeatability and fast responses over a range of concentrations may be used as a simple and effective detection method of CO and NH3 mixture gas.

  5. Silylesterification of oxidized multi-wall carbon nanotubes by catalyzed dehydrogenative cross-coupling between carboxylic and hydrosilane functions

    Science.gov (United States)

    Seffer, J.-F.; Detriche, S.; Nagy, J. B.; Delhalle, J.; Mekhalif, Z.

    2014-06-01

    Surface modification of oxidized carbon nanotubes (O-CNTs) with silicon based anchoring groups (R-SiR3) is a relatively uncommon approach of the CNTs functionalization. Hydrosilane derivatives constitute an attractive subclass of compounds for silanization reactions on the CNTs surface. In this work, we report on the ZnCl2 catalytically controlled reaction (hydrosilane dehydrogenative cross-coupling, DHCC) of fluorinated hydrosilane probes with the carboxylic functions present on the surface of oxidized multi-wall carbon nanotubes. Carbon nanotubes functionalized with essentially alcohol groups are also used to compare the selectivity of zinc chloride toward carboxylic groups. To assess the efficiency of functionalization, X-ray Photoelectron Spectroscopy is used to determine the qualitative and quantitative composition of the different samples. Solubility tests on the oxidized and silanized MWNTs are also carried out in the framework of the Hansen Solubility Parameters (HSP) theory to apprehend at another scale the effect of DHCC.

  6. Carboxyl functionalization of carbon fibers via aryl diazonium reaction in molten urea to enhance interfacial shear strength

    Science.gov (United States)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Wu, Guangshun; Ma, Lichun; Zhao, Min; Huang, Yudong

    2016-01-01

    Using molten urea as the solvent, carbon fibers were functionalized with carboxylic acid groups via aryl diazonium reaction in 15 min to improve their interfacial bonding with epoxy resin. The surface functionalization was quantified by X-ray photoelectron spectroscopy, which showed that the relative surface coverage of carboxylic acid groups increased from an initial percentage of 3.17-10.41%. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 66%. Meanwhile, the technique did not adopt any pre-oxidation step to produce functional groups prior to grafting and was shown to maintain the tensile strength of the fibers. This methodology provided a rapid, facile and economically viable route to produce covalently functionalized carbon fibers in large quantities with an eco-friendly method.

  7. Design, Synthesis, and Fungicidal Activities of Novel 5-Methyl-1H-1,2,3- trizole-4-carboxyl Amide Analogues.

    Science.gov (United States)

    Wang, Zhen-Jun; Yang, Hui-Hui; Tian, Lei; Zhao, Wei-Guang

    2016-01-01

    Succinate dehydrogenase inhibitors (SDHIs) are fungicides with an amide bond widely used to control plant diseases caused by phytopathogenic fungi. Because of broad spectrum activity of new SDHIs, they have attracted wide attention from the research community. A series of structurally novel SDHIs with a bioactive 1,2,3-triazole moiety were designed and synthesized. Bioactivity screening showed that some of designed N-phenethyl-1,2,3-trizole-4-carboxyl amide analogues exhibited good fungicidal activities toward Sclerotinia sclerotiorum and Botrytis cinerea, while some of Nbenzyl- 1,2,3-trizole-4-carboxyl amide analogues exhibited good fungicidal activities toward Phytophthora capsici and Cercospora arachidicola. EC50 value of compound 5d against Cercospora arachidicola (6.6 µg/mL) was lower than that of chlorothalonil (12.3 µg/mL). PMID:26558376

  8. Phosphazene-promoted metal-free ring-opening polymerization of ethylene oxide initiated by carboxylic acid

    KAUST Repository

    Zhao, Junpeng

    2014-03-11

    The effectiveness of carboxylic acid as initiator for the anionic ring-opening polymerization of ethylene oxide was investigated with a strong phosphazene base (t-BuP4) used as promoter. Kinetic study showed an induction period, i.e., transformation of carboxylic acid to hydroxyl ester, followed by slow chain growth together with simultaneous and fast end-group transesterification, which led to poly(ethylene oxide) (PEO) consisting of monoester (monohydroxyl), diester, and dihydroxyl species. An appropriate t-BuP4/acid ratio was proven to be essential to achieve better control over the polymerization and low dispersity of PEO. This work provides important information and enriches the toolbox for macromolecular and biomolecular engineering with protic initiating sites. © 2014 American Chemical Society.

  9. Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

    International Nuclear Information System (INIS)

    Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH3CO2NH4) and sodium acetate (CH3CO2Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example

  10. Silylesterification of oxidized multi-wall carbon nanotubes by catalyzed dehydrogenative cross-coupling between carboxylic and hydrosilane functions

    Energy Technology Data Exchange (ETDEWEB)

    Seffer, J.-F., E-mail: jean-francois.seffer@unamur.be; Detriche, S.; Nagy, J.B.; Delhalle, J.; Mekhalif, Z.

    2014-06-01

    Surface modification of oxidized carbon nanotubes (O-CNTs) with silicon based anchoring groups (R-SiR{sup ′}{sub 3}) is a relatively uncommon approach of the CNTs functionalization. Hydrosilane derivatives constitute an attractive subclass of compounds for silanization reactions on the CNTs surface. In this work, we report on the ZnCl{sub 2} catalytically controlled reaction (hydrosilane dehydrogenative cross-coupling, DHCC) of fluorinated hydrosilane probes with the carboxylic functions present on the surface of oxidized multi-wall carbon nanotubes. Carbon nanotubes functionalized with essentially alcohol groups are also used to compare the selectivity of zinc chloride toward carboxylic groups. To assess the efficiency of functionalization, X-ray Photoelectron Spectroscopy is used to determine the qualitative and quantitative composition of the different samples. Solubility tests on the oxidized and silanized MWNTs are also carried out in the framework of the Hansen Solubility Parameters (HSP) theory to apprehend at another scale the effect of DHCC.

  11. Morphology and Dynamic Mechanical Properties of Diglycidyl Ether of Bisphenol-A Toughened with Carboxyl-Terminated Butadiene-Acrylonitrile

    Science.gov (United States)

    Hong, S. D.; Chung, S. Y.; Fedors, R. F.; Moacanin, J.; Gupta, A.

    1984-01-01

    The fracture toughness of an incorporation of a carboxyl-terminated butadiene acrylonitrile (CTBN) elastomer in diglycidyl ether bisphenol A (DGEBA) resin was investigated. Measurements of dynamic mechanical properties, scanning electron microscopy and small-angle X-ray scattering were carried out to characterize the state of cure, morphology and particle size and size distribution of the neat resins and their graphite fiber reinforced composites.

  12. Carboxyl-Terminal Truncated HBx Regulates a Distinct MicroRNA Transcription Program in Hepatocellular Carcinoma Development

    OpenAIRE

    Yip, Wing-Kit; Cheng, Alfred Sze-Lok; Zhu, Ranxu; Lung, Raymond Wai-Ming; Tsang, Daisy Pui-Fong; Lau, Suki Shuk-Kei; Chen, Yangchao; Sung, Jonathan Gabriel; Lai, Paul Bo-San; Ng, Enders Kai-On; Yu, Jun; Wong, Nathalie; To, Ka-Fai; Wong, Vincent Wai-Sun; Sung, Joseph Jao-Yiu

    2011-01-01

    Background: The biological pathways and functional properties by which misexpressed microRNAs (miRNAs) contribute to liver carcinogenesis have been intensively investigated. However, little is known about the upstream mechanisms that deregulate miRNA expressions in this process. In hepatocellular carcinoma (HCC), hepatitis B virus (HBV) X protein (HBx), a transcriptional trans-activator, is frequently expressed in truncated form without carboxyl-terminus but its role in miRNA expression and H...

  13. Palmitoylation on the carboxyl terminus tail is required for the selective regulation of dopamine D2 versus D3 receptors.

    Science.gov (United States)

    Zhang, Xiaowei; Le, Hang Thi; Zhang, Xiaohan; Zheng, Mei; Choi, Bo-Gil; Kim, Kyeong-Man

    2016-09-01

    Dopamine D2 receptor (D2R) and D3 receptor (D3R) possess highly conserved amino acid sequences but this study showed that D3R was more extensively palmitoylated than D2R. Based on this finding, the molecular basis of this selective palmitoylation of D3R was determined and the roles of palmitoylation in the regulation of D3R functions were investigated. D3R was palmitoylated on the cysteine residue on its carboxyl terminus tail, the last amino acid residue of D3R, and an exchange of the carboxyl terminus tail between D2R and D3R (D2R-D3C and D3R-D2C) resulted in the switching of the palmitoylation phenotype. When the consensus site for palmitoylation was mutated or the palmitoylation of D3R was inhibited by treatment with 2-bromopalmitate (2BP), a palmitoylation blocker, cell-surface expression, PKC-mediated endocytosis, agonist affinity, and agonist-induced tolerance of D3R were all inhibited. However, these changes were not observed when D3R palmitoylation was inhibited by replacing its carboxyl tail with that of D2R (D3R-D2C) or when the palmitoylation of D2R-D3C was inhibited by treatment with 2BP. Overall, this study shows that D3R is palmitoylated more extensively than D2R even though the carboxyl terminus tails of D2R and D3R are highly homologous, and thus provides a new clue regarding the consensus sequence for palmitoylation. This study also shows that palmitoylation controls various functionalities of D3R only when the receptor is in the intact D3R configuration. PMID:27349735

  14. An easy and direct method for the synthesis of 1,2,4-triazole derivatives through carboxylic acids and hydrazinophthalazine

    OpenAIRE

    Gildardo Rivera; Virgilio Bocanegra-Garcia; Antonio Moreno; Silvia Galiano; Silvia Pérez; Ignacio Aldana; Antonio Monge

    2008-01-01

    We have developed an easy method for the synthesis of thirteen compounds derived from 1,2,4-triazoles through a carboxylic acid and hydrazinophthalazine reaction, with a 75-85% yield mediated by the use of agents such as 1-ethyl-3-(3'-dimethylaminopropyl)-carbodiimide hydrochloride and 1-hydroxybenzotriazole. The operational simplicity of this method and the good yield of products make it valuable for the synthesis of new compounds with pharmacological activity.

  15. An efficient way to coupling amine with derivatives of steric N-Boc-pyrrolidine-2-carboxylic acid

    Institute of Scientific and Technical Information of China (English)

    Feng Zhi Liu; Hao Fang; Wen Fang Xu

    2007-01-01

    An efficient way to coupling amine with the derivatives of steric N-Boc-pyrrolidine-2-carboxylic acid was reported in this paper.We have found that the synthesis of derivatives is problematic with the commonly used DCC/HOBT method. As a substitute, the mixed anhydride method was adopted. A series of 6-(3-nitroguanidino)hexanamidopyrrolidine derivatives were prepared with this method.

  16. Carboxylate-Assisted Iridium-Catalyzed C-H Amination of Arenes with Biologically Relevant Alkyl Azides.

    Science.gov (United States)

    Zhang, Tao; Hu, Xuejiao; Wang, Zhen; Yang, Tiantian; Sun, Hao; Li, Guigen; Lu, Hongjian

    2016-02-24

    An iridium-catalyzed C-H amination of arenes with a wide substrate scope is reported. Benzamides with electron-donating and -withdrawing groups and linear, branched, and cyclic alkyl azides are all applicable. Cesium carboxylate is crucial for both reactivity and regioselectivity of the reactions. Many biologically relevant molecules, such as amino acid, peptide, steroid, sugar, and thymidine derivatives can be introduced to arenes with high yields and 100 % chiral retention. PMID:26712274

  17. An easy and direct method for the synthesis of 1,2,4-triazole derivatives through carboxylic acids and hydrazinophthalazine

    Directory of Open Access Journals (Sweden)

    Gildardo Rivera

    2008-01-01

    Full Text Available We have developed an easy method for the synthesis of thirteen compounds derived from 1,2,4-triazoles through a carboxylic acid and hydrazinophthalazine reaction, with a 75-85% yield mediated by the use of agents such as 1-ethyl-3-(3'-dimethylaminopropyl-carbodiimide hydrochloride and 1-hydroxybenzotriazole. The operational simplicity of this method and the good yield of products make it valuable for the synthesis of new compounds with pharmacological activity.

  18. Precursors of novel Gla-containing conotoxins contain a carboxy-terminal recognition site that directs gamma-carboxylation

    DEFF Research Database (Denmark)

    Brown, Mark A; Begley, Gail S; Czerwiec, Eva;

    2005-01-01

    Vitamin K-dependent gamma-glutamyl carboxylase catalyzes the conversion of glutamyl residues to gamma-carboxyglutamate. Its substrates include vertebrate proteins involved in blood coagulation, bone mineralization, and signal transduction and invertebrate ion channel blockers known as conotoxins....... novel precursor structure for vitamin K-dependent polypeptides. It also provides the first formal evidence to prove that gamma-carboxylation occurs as a post-translational rather than a cotranslational process....

  19. Carboxylic acid reductase is a versatile enzyme for the conversion of fatty acids into fuels and chemical commodities

    OpenAIRE

    Akhtar, M. K.; Turner, N. J.; Jones, P R

    2012-01-01

    Aliphatic hydrocarbons such as fatty alcohols and petroleum-derived alkanes have numerous applications in the chemical industry. In recent years, the renewable synthesis of aliphatic hydrocarbons has been made possible by engineering microbes to overaccumulate fatty acids. However, to generate end products with the desired physicochemical properties (e.g., fatty aldehydes, alkanes, and alcohols), further conversion of the fatty acid is necessary. A carboxylic acid reductase (CAR) from Mycobac...

  20. Synthesis, Chiroptical Behavior, and Sensing of Carboxylic Acid Functionalized.Poly(phenylene ethynylene-alt-bithiophene)s

    OpenAIRE

    Vandeleene, Steven; Verswyvel, Michiel; Verbiest, Thierry; Koeckelberghs, Guy

    2010-01-01

    Several poly(phenylene ethynylene-alt-bithiophene)s with (chiral) nonfunctionalized substituents were synthesized with a variable phenylene ethynylene (PE) spacer length (up to 4 repeating units). The chiroptical behavior was evaluated with UV vis and circular dichroism (CD) spectroscopy, revealing a highly solvent-sensitive aggregate formation. Based on this high sensitivity, both chiral and achiral carboxylic acid functionalized analogues were prepared, of which the length of the spacer con...

  1. Esters of o- and m-carborane-C-carboxylic acids with o- and m-C-carborane alcohols

    International Nuclear Information System (INIS)

    Acid chlorides of o- and m-carborane-C-carboxylic acids reacted with primary o- and m-C-carborane alcohols in anhydrous benzene to form in a high yield (81-86%) previously unknown corresponding o- and m-carborane-containing two- and three-nuclear esters. The composition and structure of the compounds prepared have been characterized by elementary analysis, 1H and 11B NMR, IR and UV spectroscopy, by measuring their molecular weights and melting points

  2. “Fifty Shades” of Black and Red or How Carboxyl Groups Fine Tune Eumelanin and Pheomelanin Properties

    Science.gov (United States)

    Micillo, Raffaella; Panzella, Lucia; Koike, Kenzo; Monfrecola, Giuseppe; Napolitano, Alessandra; d’Ischia, Marco

    2016-01-01

    Recent advances in the chemistry of melanins have begun to disclose a number of important structure-property-function relationships of crucial relevance to the biological role of human pigments, including skin (photo) protection and UV-susceptibility. Even slight variations in the monomer composition of black eumelanins and red pheomelanins have been shown to determine significant differences in light absorption, antioxidant, paramagnetic and redox behavior, particle morphology, surface properties, metal chelation and resistance to photo-oxidative wear-and-tear. These variations are primarily governed by the extent of decarboxylation at critical branching points of the eumelanin and pheomelanin pathways, namely the rearrangement of dopachrome to 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA), and the rearrangement of 5-S-cysteinyldopa o-quinoneimine to 1,4-benzothiazine (BTZ) and its 3-carboxylic acid (BTZCA). In eumelanins, the DHICA-to-DHI ratio markedly affects the overall antioxidant and paramagnetic properties of the resulting pigments. In particular, a higher content in DHICA decreases visible light absorption and paramagnetic response relative to DHI-based melanins, but markedly enhances antioxidant properties. In pheomelanins, likewise, BTZCA-related units, prevalently formed in the presence of zinc ions, appear to confer pronounced visible and ultraviolet A (UVA) absorption features, accounting for light-dependent reactive oxygen species (ROS) production, whereas non-carboxylated benzothiazine intermediates seem to be more effective in inducing ROS production by redox cycling mechanisms in the dark. The possible biological and functional significance of carboxyl retention in the eumelanin and pheomelanin pathways is discussed. PMID:27196900

  3. “Fifty Shades” of Black and Red or How Carboxyl Groups Fine Tune Eumelanin and Pheomelanin Properties

    Directory of Open Access Journals (Sweden)

    Raffaella Micillo

    2016-05-01

    Full Text Available Recent advances in the chemistry of melanins have begun to disclose a number of important structure-property-function relationships of crucial relevance to the biological role of human pigments, including skin (photo protection and UV-susceptibility. Even slight variations in the monomer composition of black eumelanins and red pheomelanins have been shown to determine significant differences in light absorption, antioxidant, paramagnetic and redox behavior, particle morphology, surface properties, metal chelation and resistance to photo-oxidative wear-and-tear. These variations are primarily governed by the extent of decarboxylation at critical branching points of the eumelanin and pheomelanin pathways, namely the rearrangement of dopachrome to 5,6-dihydroxyindole (DHI and 5,6-dihydroxyindole-2-carboxylic acid (DHICA, and the rearrangement of 5-S-cysteinyldopa o-quinoneimine to 1,4-benzothiazine (BTZ and its 3-carboxylic acid (BTZCA. In eumelanins, the DHICA-to-DHI ratio markedly affects the overall antioxidant and paramagnetic properties of the resulting pigments. In particular, a higher content in DHICA decreases visible light absorption and paramagnetic response relative to DHI-based melanins, but markedly enhances antioxidant properties. In pheomelanins, likewise, BTZCA-related units, prevalently formed in the presence of zinc ions, appear to confer pronounced visible and ultraviolet A (UVA absorption features, accounting for light-dependent reactive oxygen species (ROS production, whereas non-carboxylated benzothiazine intermediates seem to be more effective in inducing ROS production by redox cycling mechanisms in the dark. The possible biological and functional significance of carboxyl retention in the eumelanin and pheomelanin pathways is discussed.

  4. Kinetic studies on the carboxylation of 6-amino-penicillanic acid to 8-hydroxy-penillic acid

    DEFF Research Database (Denmark)

    Henriksen, Claus Maxel; Holm, SS; Schipper, D.;

    1997-01-01

    The carboxylation in aqueous solution of 6-amino-penicillanic acid (6-APA) to 8-hydroxy-penillic acid (8-HPA) was studied at 25 degrees C and pH 6.5. During sparging with either a citrate buffer or a chemically defined cultivation medium containing 6-APA with mixtures of carbon dioxide and air (2...... by hydrolysis of beta-lactam ring and eventually further chemical modifications of a citrate-containing penicillin. Copyright (C) 1996 Elsevier Science Ltd...

  5. 二氧化碳作为羧化试剂用于羧酸及其衍生物的合成%Synthesis of Carboxylic Acids and Derivatives Using CO2 as Carboxylative Reagent

    Institute of Scientific and Technical Information of China (English)

    张文珍; 吕小兵

    2012-01-01

    The catalytic transformation of carbon dioxide into high value-added fine chemicals has attracted attention because this will make CO2 into an abundant,inexpensive,and renewable C1 feedstock.More than 20 reactions involving CO2 as a starting material have been developed in recent decades but their successful industrialization is limited.One type of reactions that is technologically viable is to use CO2 as a carboxylative reagent in the production of a wide range of carboxylic acids and derivatives.This review focused on transition metal-catalyzed reactions for the synthesis of various carboxylic acid and derivatives from CO2,by the carboxylation of carbon nucleophiles and C-H bonds and reactions of CO2 with unsaturated organic compounds (especially those with a carbon-carbon multiple bond).This review also included transition metal-free or organocatalytic reactions for the transformation of CO2 into carboxylic acid and derivatives.%二氧化碳是储量丰富、廉价易得且可再生的C1资源,将其催化转化成高附加值精细化学品的研究已经引起了人们的广泛关注.目前,虽然二氧化碳用作初始原料的反应已经工业化的很少,但过去几十年中仍有二十多个具有实际应用前景的二氧化碳参与的新反应被发现,其中以二氧化碳作为羧化试剂合成各种羧酸及其衍生物的反应为突出代表.本文综述了过渡金属催化合成羧酸及其衍生物的二氧化碳与多种碳亲核试剂、碳氢键以及碳碳多重键化合物的反应,并总结了无过渡金属参与或有机小分子催化条件下将二氧化碳转化成羧酸及其衍生物的反应.

  6. Effect of Concentration of Structurally-Different Carboxylic Acids on Growth and Aggregation of Calcium Oxalate in Gel Systems

    Institute of Scientific and Technical Information of China (English)

    DENG,Sui-Ping; OUYANG,Jian-Ming

    2007-01-01

    The effect of concentration of structurally-different carboxylic acids such as ethylene diamine tetraacetic acid (H4edta), citric acid (H3cit), tartaric acid (H2tart), and acetic acid (HOAc) on growth and aggregation of calcium oxalate (CaOxa) in gel systems was comparatively investigated. H2tart and H3cit could change the morphology of calcium oxalate monohydrate (COM) and induce the formation of calcium oxalate dihydrate (COD). H4edta could induce the formation of COD at a lower concentration of 0.33 mmol/L and have the strongest ability to inhibit aggregation of COM. HOAc inhibited COM aggregation only at a higher concentration than 500 mmol/L. With increasing the number of carboxylic groups in an acid or increasing the concentration of carboxylic acid, the capacity of this acid to induce COD formation and to inhibit growth and aggregation of COM crystals increased. That is, this capacity followed the order: H4edta>H3cit>H2tart>>HOAc. The result in this work suggested that the presence of H3cit and H2tart in urine played a role in the natural defense against stone formation.

  7. The effects of solvents and structure on the electronic absorption spectra of the isomeric pyridine carboxylic acid N-oxides

    Directory of Open Access Journals (Sweden)

    Drmanić Saša Ž.

    2013-01-01

    Full Text Available The ultraviolet absorption spectra of the carboxyl group of three isomeric pyridine carboxylic acids N-oxides (picolinic acid N-oxide, nicotinic acid N-oxide and isonicotinic acid N-oxide were determined in fourteen solvents in the wavelength range from 200 to 400 nm. The position of the absorption maxima (λmax of the examined acids showed that the ultraviolet absorption maximum wavelengths of picolinic acid N-oxide are the shortest, and those of isonicotinic acid N-oxide acid are the longest. In order to analyze the solvent effect on the obtained absorption spectra, the ultraviolet absorption frequencies of the electronic transitions in the carboxylic group of the examined acids were correlated using a total solvatochromic equation of the form max = v0 + sπ + aα+ bβ, where υmax is the absorption frequency (1/λmax, p is a measure of the solvent polarity, β represents the scale of solvent hydrogen bond acceptor basicities and α represent the scale of solvent hydrogen bond donor acidities. The correlation of the spectroscopic data was carried out by means of multiple linear regression analysis. The solvent effects on the ultraviolet absorption maximums of the examined acids were discussed.

  8. Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols and Hydroxide Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Santilli, Carola; Makarov, Ilya; Fristrup, Peter;

    2016-01-01

    Primary alcohols have been reacted with hydroxide and the ruthenium complex [RuCl2(IiPr)(p-cymene)] to afford carboxylic acids and dihydrogen. The dehydrogenative reaction is performed in toluene, which allows for a simple isolation of the products by precipitation and extraction. The transformat......Primary alcohols have been reacted with hydroxide and the ruthenium complex [RuCl2(IiPr)(p-cymene)] to afford carboxylic acids and dihydrogen. The dehydrogenative reaction is performed in toluene, which allows for a simple isolation of the products by precipitation and extraction...... reaction is most likely involved in this case. The kinetic isotope effect was determined to be 0.67 using 1-butanol as the substrate. A plausible catalytic cycle was characterized by DFT/B3LYP-D3 and involved coordination of the alcohol to the metal, β-hydride elimination, hydroxide attack...... on the coordinated aldehyde, and a second β-hydride elimination to furnish the carboxylate....

  9. Improving the antidepressant action and the bioavailability of sertraline by co-crystallization with coumarin 3-carboxylate. Structural determination.

    Science.gov (United States)

    Escudero, Graciela E; Laino, Carlos H; Echeverría, Gustavo A; Piro, Oscar E; Martini, Nancy; Rodríguez, Ailén N; Martínez Medina, Juan J; López Tévez, Libertad L; Ferrer, Evelina G; Williams, Patricia A M

    2016-04-01

    To improve the antidepressant action of sertraline a new salt with coumarin-3-carboxylate anion (SerH-CCA) has been synthesized by two different methods and characterized by FTIR spectroscopy and structural determinations by X-ray diffraction methods. The new salt is stabilized by strong intermolecular H-bonds involving the protonated amine group of SerH and the deprotonated carboxylate group of CCA. These findings can be correlated with the interpretation of the infrared spectrum. The salt, sertraline (SerHCl) and the sodium salt of coumarin-3-carboxylate (NaCCA) were orally administered male Wistar rats (10 mg/kg, based on sertraline). Rats were evaluated in separate groups by means of the forced swimming (FST). SerH-CCA produced antidepressant effects in a magnitude that exceeded SerHCl individual effects. None of these treatments affected activity levels by the open field OFT tests. We have also determined that the ion pair also improve the binding to bovine serum albumin (BSA) of the drug but retain its antimicrobial activity. It is reasonable to conclude that the replacement of chloride anion by a large organic anion in sertraline strengthens the pharmacological action of the native drug, binding to BSA with higher activity and retaining the antimicrobial activity of the antidepressant compound.

  10. Anionic sulfonated and carboxylated PPI dendrimers with the EDA core: synthesis and characterization of selective metal complexing agents.

    Science.gov (United States)

    García-Gallego, Sandra; Cangiotti, Michela; Fiorani, Luigi; Fattori, Alberto; Muñoz-Fernández, Ma Ángeles; Gomez, Rafael; Ottaviani, M Francesca; de la Mata, F Javier

    2013-04-28

    Herein we describe the synthesis and characterization of new sulfonated and carboxylated poly(propyleneimino) (PPI) dendrimers with the ethylenediamino (EDA) core, at generations 1, 2 and 3. By means of UV-Vis and EPR spectroscopy, using Cu(2+) as a probe, we concluded that these dendrimers show a specific pattern in the coordination of metal ions. In agreement with the UV-Vis studies, EPR spectra of carboxylated compounds are constituted by 3 different signals which appear and then disappear with increasing copper concentration, corresponding to the saturation of different copper complexation sites. At the lowest copper concentration up to a 1:1 molar ratio between Cu(II) and the dendrimer, the spectrum is characteristic of a CuN2O2 coordination at the core of the dendrimer. The spectrum appearing at higher Cu(II) concentrations indicates a peripheral location of the ions coordinating one nitrogen and 3 oxygen atoms in a square planar geometry in restricted mobility conditions. For the highest concentrations tested, copper ions are confined at the external dendrimer surface with CuO4 coordination. For sulfonate systems, the EPR results are in line with a weaker interaction of Cu(II) with the nitrogen sites and a stronger interaction with the oxygen (SO3(-)) groups with respect to the interactions measured by EPR for carboxylate systems. PMID:23462972

  11. SYNTHESIS AND SPECTRAL-LUMINESCENT PROPERTIES OF CALIX[4]ARENES MODIFIED WITH CARBOXYLIC, PHTHALIMIDE AND AMINOETHOXY-GROUPS, AND THEIR LANTHANIDE-CONTAINING COMPLEXES

    OpenAIRE

    Fadeyev, Y. M.; Snurnikova, O. V.; Lukyanenko, O. P.; Alyeksyeyeva, O. O.; Rusakova, N. V.

    2015-01-01

    p-tert-Butylcalix[4]arene derivatives modified with carboxylic, phthalimide and aminoethoxy-groups on the lower rim as well as their lanthanide (ytterbium and lutetium) complexes were synthesized. Spectral-luminescent properties of obtained compounds were analyzed.

  12. Crystallization and preliminary X-ray analysis of l-azetidine-2-carboxylate hydrolase from Pseudomonas sp. strain A2C

    International Nuclear Information System (INIS)

    l-Azetidine-2-carboxylate hydrolase from Pseudomonas sp. strain A2C was crystallized and diffraction data were collected to a resolution of 1.38 Å. l-Azetidine-2-carboxylate hydrolase from Pseudomonas sp. strain A2C catalyzes a ring-opening reaction that detoxifies l-azetidine-2-carboxylate, an analogue of l-proline. Recombinant l-azetidine-2-carboxylate hydrolase was overexpressed, purified and crystallized using polyethylene glycol and magnesium acetate as precipitants. The needle-shaped crystal belonged to space group P21, with unit-cell parameters a = 35.6, b = 63.6, c = 54.7 Å, β = 105.5°. The crystal diffracted to a resolution of 1.38 Å. The calculated VM value was 2.2 Å3 Da−1, suggesting that the crystal contains one enzyme subunit in the asymmetric unit

  13. Evaluation of a series of prolylamidepyridines as the chiral derivatization reagents for enantioseparation of carboxylic acids by LC-ESI-MS/MS and the application to human saliva.

    Science.gov (United States)

    Kuwabara, Tomohiro; Takayama, Takahiro; Todoroki, Kenichiro; Inoue, Koichi; Min, Jun Zhe; Toyo'oka, Toshimasa

    2014-04-01

    Mass spectrometry has become a popular analytical tool because of its high sensitivity and specificity. The use of a chiral derivatization reagent for the mass spectrometry (MS) detection seems to be efficient for the enantiomeric separation of racemates. However, the number of chiral reagents for the liquid chromatography (LC)-MS/MS analysis is very limited. According to these observations, we are currently in the process of developing novel labeling reagents for chiral molecules in MS/MS analysis. The derivatization reagent that is effective for enhancing not only the electrospray ionization-MS/MS sensitivity but also the reversed-phase LC resolution of carboxylic acid enantiomers should have a highly proton-affinitive moiety and an asymmetric structure near the reactive functional group. Furthermore, the resulting derivative has to provide a characteristic product ion suitable for the selected reaction monitoring. Based upon these considerations, a series of prolylamidepyridines ((S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-2-yl)amide (PCP2), (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-3-yl)amide, and (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-4-yl)amide) was synthesized as ideal labeling reagents for the enantioseparation of chiral carboxylic acids and evaluated in terms of separation efficiency and detection sensitivity by ultra-performance LC (UPLC)-MS/MS. Among the synthesized reagents, PCP2 was the most efficient chiral derivatization reagent for the enantioseparation of carboxylic acid. The Rs values and the detection limits of the derivatives of non-steroidal anti-inflammatory drugs, which were selected as the representative carboxylic acids, were in the range of 2.52-6.07 and 49-260 amol, respectively. The sensitive detection of biological carboxylic acids (detection limits, 32-520 amol) was also carried out by the proposed method using PCP2 and UPLC-MS/MS. The PCP2 was applied to the determination of carboxylic acids in human saliva. Several

  14. Microbiologically produced carboxylic acids used as building blocks in organic synthesis.

    Science.gov (United States)

    Aurich, Andreas; Specht, Robert; Müller, Roland A; Stottmeister, Ulrich; Yovkova, Venelina; Otto, Christina; Holz, Martina; Barth, Gerold; Heretsch, Philipp; Thomas, Franziska A; Sicker, Dieter; Giannis, Athanassios

    2012-01-01

    Oxo- and hydroxy-carboxylic acids are of special interest in organic synthesis. However, their introduction by chemical reactions tends to be troublesome especially with regard to stereoselectivity. We describe herein the biotechnological preparation of selected oxo- and hydroxycarboxylic acids under "green" conditions and their use as promising new building blocks. Thereby, our biotechnological goal was the development of process fundamentals regarding the variable use of renewable raw materials, the development of a multi purpose bioreactor and application of a pilot plant with standard equipment for organic acid production to minimize the technological effort. Furthermore the development of new product isolation procedures, with the aim of direct product recovery, capture of products or single step operation, was necessary. The application of robust and approved microorganisms, also genetically modified, capable of using a wide range of substrates as well as producing a large spectrum of products, was of special importance. Microbiologically produced acids, like 2-oxo-glutaric acid and 2-oxo-D-gluconic acid, are useful educts for the chemical synthesis of hydrophilic triazines, spiro-connected heterocycles, benzotriazines, and pyranoic amino acids. The chiral intermediate of the tricarboxylic acid cycle, (2R,3S)-isocitric acid, is another promising compound. For the first time our process provides large quantities of enantiopure trimethyl (2R,3S)-isocitrate which was used in subsequent chemical transformations to provide new chiral entities for further usage in total synthesis and pharmaceutical research.Oxo- and hydroxy-carboxylic acids are of special interest in organic synthesis. However, their introduction by chemical reactions tends to be troublesome especially with regard to stereoselectivity. We describe herein the biotechnological preparation of selected oxo- and hydroxycarboxylic acids under "green" conditions and their use as promising new building

  15. One-Pot Synthesis of α-Amino Acids through Carboxylation of Ammonium Ylides with CO2 Followed by Alkyl Migration.

    Science.gov (United States)

    Mita, Tsuyoshi; Sugawara, Masumi; Sato, Yoshihiro

    2016-06-17

    A simple, yet powerful protocol for α-amino acid synthesis using carbon dioxide (CO2) was developed. α-Amino silanes could undergo four successive reactions (formation of ammonium salt, carboxylation, esterification, and 2,3- or 1,2-Stevens rearrangement) in the presence of allylic or benzylic halides under a CO2 atmosphere (1 atm). It is noteworthy that carboxylation at the position adjacent to a nitrogen atom proceeded via an ammonium ylide intermediate under mild conditions.

  16. Design of co-crystals/salts of some Nitrogenous bases and some derivatives of thiophene carboxylic acids through a combination of hydrogen and halogen bonds

    OpenAIRE

    Jennifer, Samson Jegan; Muthiah, Packianathan Thomas

    2014-01-01

    Background The utility of N-heterocyclic bases to obtain molecular complexes with carboxylic acids is well studied. Depending on the solid state interaction between the N-heterocyclic base and a carboxylic acid a variety of neutral or ionic synthons are observed. Meanwhile, pyridines and pyrimidines have been frequently chosen in the area of crystal engineering for their multipurpose functionality. HT (hetero trimers) and LHT (linear heterotetramers) are the well known synthons that are forme...

  17. Computational analysis of the CB1 carboxyl-terminus in the receptor-G protein complex.

    Science.gov (United States)

    Shim, Joong-Youn; Khurana, Leepakshi; Kendall, Debra A

    2016-04-01

    Despite the important role of the carboxyl-terminus (Ct) of the activated brain cannabinoid receptor one (CB1) in the regulation of G protein signaling, a structural understanding of interactions with G proteins is lacking. This is largely due to the highly flexible nature of the CB1 Ct that dynamically adapts its conformation to the presence of G proteins. In the present study, we explored how the CB1 Ct can interact with the G protein by building on our prior modeling of the CB1-Gi complex (Shim, Ahn, and Kendall, The Journal of Biological Chemistry 2013;288:32449-32465) to incorporate a complete CB1 Ct (Glu416(Ct)-Leu472(Ct)). Based on the structural constraints from NMR studies, we employed ROSETTA to predict tertiary folds, ZDOCK to predict docking orientation, and molecular dynamics (MD) simulations to obtain two distinct plausible models of CB1 Ct in the CB1-Gi complex. The resulting models were consistent with the NMR-determined helical structure (H9) in the middle region of the CB1 Ct. The CB1 Ct directly interacted with both Gα and Gβ and stabilized the receptor at the Gi interface. The results of site-directed mutagenesis studies of Glu416(Ct), Asp423(Ct), Asp428(Ct), and Arg444(Ct) of CB1 Ct suggested that the CB1 Ct can influence receptor-G protein coupling by stabilizing the receptor at the Gi interface. This research provided, for the first time, models of the CB1 Ct in contact with the G protein. PMID:26994549

  18. Dancing multiplicity states supported by a carboxylated group in dicopper structures bonded to O2

    KAUST Repository

    Poater, Albert

    2013-01-29

    The present study pretends to assign the correct multiplicity state to dinuclear copper complexes when interacting with free molecular oxygen. Recently, the formation of a bridge butterfly μ-η2: η2-peroxo dicopper core structure stabilized by the direct interaction of the counterion, a carboxylate group that allows the double bridge linking both metal-centre atoms, was characterized by crystallography. This system was assigned as a diradical singlet with Ms = 0. However, after new calculations it has turned out to be triplet (Ms = 1) despite the stabilization for this latter multiplicity state is not high. Here, the factors that contribute to make this structure display a multiplicity different with respect to the previously expected diradical singlet are described. In the present theoretical study, the roles of the αSp ligand constraints and the counterion are unravelled. On the other hand, the relative stability between the butterfly μ-η2: η2-peroxo structure and the isomeric bis(μ-oxo) species is also on discussion. Despite the relative stabilities of all these either structural or electronic isomeric species are supposed to depend on the computational method, which is a difficulty to reach a definite conclusion about the nature of the active species, all DFT methods using either pure or not pure DFT functionals here reach the same conclusion, favoring the triplet as the ground state for the butterfly μ-η2: η2-peroxo dicopper core structure, and the bis(μ-oxo) species when removing the benzoate counterion. © Springer-Verlag Berlin Heidelberg 2013.

  19. Effects of transport inhibitors on the cellular uptake of carboxylated polystyrene nanoparticles in different cell lines.

    Directory of Open Access Journals (Sweden)

    Tiago dos Santos

    Full Text Available Nanotechnology is expected to play a vital role in the rapidly developing field of nanomedicine, creating innovative solutions and therapies for currently untreatable diseases, and providing new tools for various biomedical applications, such as drug delivery and gene therapy. In order to optimize the efficacy of nanoparticle (NP delivery to cells, it is necessary to understand the mechanisms by which NPs are internalized by cells, as this will likely determine their ultimate sub-cellular fate and localisation. Here we have used pharmacological inhibitors of some of the major endocytic pathways to investigate nanoparticle uptake mechanisms in a range of representative human cell lines, including HeLa (cervical cancer, A549 (lung carcinoma and 1321N1 (brain astrocytoma. Chlorpromazine and genistein were used to inhibit clathrin and caveolin mediated endocytosis, respectively. Cytochalasin A and nocodazole were used to inhibit, respectively, the polymerisation of actin and microtubule cytoskeleton. Uptake experiments were performed systematically across the different cell lines, using carboxylated polystyrene NPs of 40 nm and 200 nm diameters, as model NPs of sizes comparable to typical endocytic cargoes. The results clearly indicated that, in all cases and cell types, NPs entered cells via active energy dependent processes. NP uptake in HeLa and 1321N1 cells was strongly affected by actin depolymerisation, while A549 cells showed a stronger inhibition of NP uptake (in comparison to the other cell types after microtubule disruption and treatment with genistein. A strong reduction of NP uptake was observed after chlorpromazine treatment only in the case of 1321N1 cells. These outcomes suggested that the same NP might exploit different uptake mechanisms to enter different cell types.

  20. Computational analysis of the CB1 carboxyl-terminus in the receptor-G protein complex.

    Science.gov (United States)

    Shim, Joong-Youn; Khurana, Leepakshi; Kendall, Debra A

    2016-04-01

    Despite the important role of the carboxyl-terminus (Ct) of the activated brain cannabinoid receptor one (CB1) in the regulation of G protein signaling, a structural understanding of interactions with G proteins is lacking. This is largely due to the highly flexible nature of the CB1 Ct that dynamically adapts its conformation to the presence of G proteins. In the present study, we explored how the CB1 Ct can interact with the G protein by building on our prior modeling of the CB1-Gi complex (Shim, Ahn, and Kendall, The Journal of Biological Chemistry 2013;288:32449-32465) to incorporate a complete CB1 Ct (Glu416(Ct)-Leu472(Ct)). Based on the structural constraints from NMR studies, we employed ROSETTA to predict tertiary folds, ZDOCK to predict docking orientation, and molecular dynamics (MD) simulations to obtain two distinct plausible models of CB1 Ct in the CB1-Gi complex. The resulting models were consistent with the NMR-determined helical structure (H9) in the middle region of the CB1 Ct. The CB1 Ct directly interacted with both Gα and Gβ and stabilized the receptor at the Gi interface. The results of site-directed mutagenesis studies of Glu416(Ct), Asp423(Ct), Asp428(Ct), and Arg444(Ct) of CB1 Ct suggested that the CB1 Ct can influence receptor-G protein coupling by stabilizing the receptor at the Gi interface. This research provided, for the first time, models of the CB1 Ct in contact with the G protein.

  1. Porous Coordination Polymer Based on Bipyridinium Carboxylate Linkers with High and Reversible Ammonia Uptake.

    Science.gov (United States)

    Leroux, Maxime; Mercier, Nicolas; Allain, Magali; Dul, Marie-Claire; Dittmer, Jens; Kassiba, Abdel Hadi; Bellat, Jean-Pierre; Weber, Guy; Bezverkhyy, Igor

    2016-09-01

    The zwitterionic bipyridinium carboxylate ligand 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium (pc1) in the presence of cadmium chloride affords novel porous coordination polymers (PCPs): [Cd4(pc1)3Cl6]·CdCl4·guest (1) crystallizing in the P3̅1c space group. In the structure, [Cd4Cl6(CO2)6] building units are linked together by six pc1 ligands, leading to a 3D high-symmetrical network exhibiting hexagonal channels along the c axis. The walls of this PCP consist of cationic electron-acceptor bipyridinium units. The PCP 1 reversibly adsorbs H2O and CH3OH up to about 0.1 g/g at saturation showing the adsorption isotherms characteristic of a moderately hydrophilic sorbent. Adsorption of ammonia (NH3) follows a different pattern, reaching an exceptional uptake of 0.39 g/g (22.3 mmol/g) after the first adsorption cycle. Although the crystalline structure of 1 collapses after the first adsorption, the solid can be regenerated and maintains the capacity of 0.29 g/g (17 mmol/g) in the following cycles. We found that the high NH3 uptake is due to a combination of pore filling taking place below 150 h·Pa and chemisorption occurring at higher pressures. The latter process was shown to involve two phenomena: (i) coordination of NH3 molecules to Cd(2+) cations as follows from (113)Cd NMR and (ii) strong donor-acceptor interactions between NH3 molecules and pc1 ligands. PMID:27500980

  2. Comprehensive evaluation of carboxylated nanodiamond as a topical drug delivery system

    Science.gov (United States)

    Lim, Dae Gon; Kim, Ki Hyun; Kang, Eunah; Lim, Sun Hee; Ricci, Jeremy; Sung, Si Kwon; Kwon, Myoung Taek; Jeong, Seong Hoon

    2016-01-01

    The best strategy in the development of topical drug delivery systems may be to facilitate the permeation of drugs without any harmful effects, while staying on the skin surface and maintaining stability of the system. Nanodiamonds (NDs) play a key role with their excellent physicochemical properties, including high biocompatibility, physical adsorption, reactive oxygen species (ROS) scavenging capability, and photostabilizing activity. Z-average sizes of carboxylated ND (ND–COOH) agglutinate decreased significantly as the pH increased. Fluorescein-conjugated ND was observed only on the stratum corneum, and no sample diffused into the dermal layer even after 48 hours. Moreover, ND–COOH and ND–COOH/eugenol complex did not show significant toxic effects on murine macrophage cells. ND improved in vitro skin permeation >50% acting as a “drug reservoir” to maintain a high drug concentration in the donor chamber, which was supported by quartz crystal microbalance results. Moreover, ND–COOH could adsorb a drug amount equivalent to 80% of its own weight. A photostability study showed that ND–COOH increased the photostability ~47% with regard to rate constant of the eugenol itself. A significant decrease in ROS was observed in the ND–COOH and ND–COOH/eugenol complex compared with the negative control during intracellular ROS assay. Moreover, ROS and cupric reducing antioxidant capacity evaluation showed that ND–COOH had synergistic effects of antioxidation with eugenol. Therefore, ND–COOH could be used as an excellent topical drug delivery system with improved permeability, higher stability, and minimized safety issue. PMID:27307736

  3. Carbon Isotope Fractionation during Photorespiration and Carboxylation in Senecio1[W][OA

    Science.gov (United States)

    Lanigan, Gary J.; Betson, Nicholas; Griffiths, Howard; Seibt, Ulli

    2008-01-01

    The magnitude of fractionation during photorespiration and the effect on net photosynthetic 13C discrimination (Δ) were investigated for three Senecio species, S. squalidus, S. cineraria, and S. greyii. We determined the contributions of different processes during photosynthesis to Δ by comparing observations (Δobs) with discrimination predicted from gas-exchange measurements (Δpred). Photorespiration rates were manipulated by altering the O2 partial pressure (pO2) in the air surrounding the leaves. Contributions from 13C-depleted photorespiratory CO2 were largest at high pO2. The parameters for photorespiratory fractionation (f), net fractionation during carboxylation by Rubisco and phosphoenolpyruvate carboxylase (b), and mesophyll conductance (gi) were determined simultaneously for all measurements. Instead of using Δobs data to obtain gi and f successively, which requires that b is known, we treated b, f, and gi as unknowns. We propose this as an alternative approach to analyze measurements under field conditions when b and gi are not known or cannot be determined in separate experiments. Good agreement between modeled and observed Δ was achieved with f = 11.6‰ ± 1.5‰, b = 26.0‰ ± 0.3‰, and gi of 0.27 ± 0.01, 0.25 ± 0.01, and 0.22 ± 0.01 mol m−2 s−1 for S. squalidus, S. cineraria, and S. greyii, respectively. We estimate that photorespiratory fractionation decreases Δ by about 1.2‰ on average under field conditions. In addition, diurnal changes in Δ are likely to reflect variations in photorespiration even at the canopy level. Our results emphasize that the effects of photorespiration must be taken into account when partitioning net CO2 exchange of ecosystems into gross fluxes of photosynthesis and respiration. PMID:18923019

  4. Formation of 4'-carboxyl acid metabolite of imrecoxib by rat liver microsomes

    Institute of Scientific and Technical Information of China (English)

    Hai-yan XU; Peng ZHANG; Ai-shen GONG; Yu-ming SUN; Feng-ming CHU; Zong-ru GUO; Da-fang ZHONG

    2006-01-01

    Aim:Imrecoxib is a novel and moderately selective COX-2 inhibitor.The aim of the present in vitro investigation was to study the formation of the major metabolite 4'-carboxylic acid imrecoxib (M2) and identify the enzyrne(s) involved in the reaction.Methods:The formation of M2 was studied in rat liver cytosol in the absence or presence of liver microsomes.The formed metabolite was identified and quantified by LC/MSn.In addition,to characterize the cytochrome P450 (CYP) isozymes involved in M2 formation,the effects of typical CYP inhibitors (such as ketoconazle,quinine,α-naphthoflavone, methylpyrazole,and cimetidine) on the formation rate of M2 were investigated.Results:The formation of M2 from 4'hydroxymethyl imrecoxib (M4) was completely dependent on rat liver microsomes and NADPH.Enzyme kinetic studies demonstrated that the formation rate of M2 conformed to monophasic Michaelis-Menten kinetics.Additional experiments showed that the formation of M2 was induced significantly by dexamethasone and lowered by ketoconazole strongly and concentration-dependently.By comparison.other CYP inhibitors.such as α-naphthoflavone,cimetidine,quinine,and methylpyrazole had no inhibitory effects on this metabolic pathway.Conclusion:These biotransformation studies of M4 and imrecoxib in rat liver at the subcellular level showed that the formation of M2 occurs in rat liver microsomes and is NADPH-dependent.The reaction was mainly catalyzed by CYP 3A in untreated rats and in dexamethasone-induced rats.Other CYP,such as CYP 1A,2C,2D,and 2E,seem unlikely to participate in this metabolic pathway.

  5. Carboxylic Esterase and Its Associations With Long-term Effects of Organophosphorus Pesticides

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Objective To examine a) the effect of organophosphorus pesticide exposure on activity of carboxylic esterases, namely butyrylcholinesterase (BChE), carboxylesterase (CarbE) and paraoxonase (PonE); and b) the association of polymorphisms of BChE and PonE with individual genetic susceptibility to organophosphorus pesticide exposure. Methods A cross-sectional study was conducted in 75 workers exposed to organophosphorus pesticides and 100 non-exposed controls. The serum activity of these enzymes was measured. Variant forms of BCHE-K, PON-192, and PON-55 were detected. A symptom score was developed as a proxy measure of clinical outcomes. Results Activities of both BChE and CarbE were lower in exposed exposed workers with BCHE-K genotype UU (61 cases), genotype UK (12 cases) and genotype KK (2 cases) was 105.05, 84.42 activity in the exposed workers with PON-192 genotype BB (37), genotype AB (27) and genotype AA (11) was 116.8, 91.2, and 9.20. The symptom score was the highest in individuals with abnormal homozygote for each of the three gene loci. Conclusions Long-term exposure to organophosphorus pesticides can inhibit BChE and CarbE activity, but exerts no inhibitory effect on PonE activity. Different genotypes of BCHE-K, PON-192, and PON-55 may be related to the severity of adverse health effects of organophosphorus pesticide exposure. Implications of potentially higher susceptibility of workers with mutant homozygotes should be evaluated to reduce health risks.

  6. From crab shells to smart systems: chitosan-alkylethoxy carboxylate complexes.

    Science.gov (United States)

    Chiappisi, Leonardo; Prévost, Sylvain; Grillo, Isabelle; Gradzielski, Michael

    2014-09-01

    In this work, self-assembly of alkyl ethylene oxide carboxylates and the biopolymer chitosan into supramolecular structures with various shapes is presented. Our investigations were done at pH 4.0, where the chitosan is almost fully charged and the surfactants are partially deprotonated. By changing the alkyl chain length and the number of ethylenoxide units very different water-soluble complexes can be obtained, ranging from globular micelles incorporated in a chitosan network to formation of ordered multiwalled vesicles. The structural characteristics of these complexes can be finely controlled by the mixing ratio of chitosan and surfactant, i.e., simply by the solutions composition. For instance, the vesicle wall thickness can be varied between 5 and 50 nm just by varying the mixing ratio. Accordingly, we expect this system to be an outstanding carrier for hydrophilic compounds with tunable release time option. Moreover, an easy route for preparation of chitosan-based complexes in the solid state with controlled mesoscopic order is presented. This work opens the way to prepare biofriendly materials on the basis of chitosan and mild anionic surfactants which are rather versatile with respect to their structure and properties, allowing for preparation of complexes with highly variable structures in both aqueous and solid phase. Formation of such different structures can be exploited for preparation of carriers, which are able to transport hydrophilic as well as hydrophobic molecules. Furthermore, as chitosan is well known to exhibit antibacterial and anti-inflammatory properties, different applications of these complexes can be indicated, i.e., as drug delivery systems or as coatings for medical implants.

  7. Spectral and biological evaluation of a synthetic antimicrobial peptide derived from 1-aminocyclohexane carboxylic acid.

    Science.gov (United States)

    Abercrombie, J J; Leung, Kai P; Chai, Hanbo; Hicks, Rickey P

    2015-03-15

    Ac-GF(A6c)G(A6c)K(A6c)G(A6c)F(A6c)G(A6c)GK(A6c)KKKK-amide (A6c=1-aminocyclohexane carboxylic acid) is a synthetic antimicrobial peptide (AMP) that exhibits in vitro inhibitory activity against drug resistant strains of Staphylococcus aureus, Acinetobacter baumannii, Klebsiella pneumoniae, Pseudomonas aeruginosa, Enterobacter aerogenes, and Enterococcus faecium at concentrations ranging from 10.9 to 43μM. Spectroscopic investigations were conducted to determine how this AMP interacts with simple membrane model systems in order to provide insight into possible mechanisms of action. CD and 2D-(1)H NMR experiments indicated this AMP on binding to SDS and DPC micelles adopts conformations with varying percentages of helical and random coil conformers. CD investigations in the presence of three phospholipid SUVs consisting of POPC, 4:1 POPC/POPG, and 60% POPE/21%POPG/19%POPC revealed: (1) The interactions occurring with POPC SUVs have minimal effect on the conformational diversity of the AMP yielding conformations similar to those observed in buffer. (2) The interactions with 4:1 POPC/POPG, and 60% POPE/21%POPG/19%POPC SUVs exhibited a greater influence on the percentage of different conformers contributing to the CD spectra. (3) The presence of a high of percentage of helical conformers was not observed in the presence of SUVs as was the case with micelles. This data indicates that the diversity of surface bound conformations adopted by this AMP are very different from the diversity of conformations adopted by this AMP on insertion into the lipid bilayer. CD spectra of this AMP in the presence of SUVs consisting of LPS isolated from P. aeruginosa, K. pneumoniae and Escherichia coli exhibited characteristics associated with various helical conformations.

  8. New insights into 1-aminocyclopropane-1-carboxylate (ACC deaminase phylogeny, evolution and ecological significance.

    Directory of Open Access Journals (Sweden)

    Francisco X Nascimento

    Full Text Available The main objective of this work is the study of the phylogeny, evolution and ecological importance of the enzyme 1-aminocyclopropane-1-carboxylate (ACC deaminase, the activity of which represents one of the most important and studied mechanisms used by plant growth-promoting microorganisms. The ACC deaminase gene and its regulatory elements presence in completely sequenced organisms was verified by multiple searches in diverse databases, and based on the data obtained a comprehensive analysis was conducted. Strain habitat, origin and ACC deaminase activity were taken into account when analyzing the results. In order to unveil ACC deaminase origin, evolution and relationships with other closely related pyridoxal phosphate (PLP dependent enzymes a phylogenetic analysis was also performed. The data obtained show that ACC deaminase is mostly prevalent in some Bacteria, Fungi and members of Stramenopiles. Contrary to previous reports, we show that ACC deaminase genes are predominantly vertically inherited in various bacterial and fungal classes. Still, results suggest a considerable degree of horizontal gene transfer events, including interkingdom transfer events. A model for ACC deaminase origin and evolution is also proposed. This study also confirms the previous reports suggesting that the Lrp-like regulatory protein AcdR is a common mechanism regulating ACC deaminase expression in Proteobacteria, however, we also show that other regulatory mechanisms may be present in some Proteobacteria and other bacterial phyla. In this study we provide a more complete view of the role for ACC deaminase than was previously available. The results show that ACC deaminase may not only be related to plant growth promotion abilities, but may also play multiple roles in microorganism's developmental processes. Hence, exploring the origin and functioning of this enzyme may be the key in a variety of important agricultural and biotechnological applications.

  9. Distinct pathways of ERK1/2 activation by hydroxy-carboxylic acid receptor-1.

    Directory of Open Access Journals (Sweden)

    Guo Li

    Full Text Available Mechanistic investigations have shown that, upon agonist activation, hydroxy-carboxylic acid receptor-1(HCA1 couples to a Gi protein and inhibits adenylate cyclase activity, leading to inhibition of liberation of free fatty acid. However, the underlying molecular mechanisms for HCA1 signaling remain largely unknown. Using CHO-K1 cells stably expressing HCA1, and L6 cells, which endogenously express rat HCA1 receptors, we found that activation of ERK1/2 by HCA1 was rapid, peaking at 5 min, and was significantly blocked by pertussis toxin. Furthermore, time course experiments with different kinase inhibitors demonstrated that HCA1 induced ERK1/2 activation via the extracellular Ca2+, PKC and IGF-I receptor transactivation-dependent pathways. In addition, we observed that pretreated the cells with M119K, an inhibitor of Gβγ subunit-dependent signaling, effectively attenuated the ERK1/2 activation triggered by HCA1, suggesting a critical role for βγ-subunits in HCA1-activated ERK1/2 phosphorylation. Furthermore, the present results also indicated that the arrestin2/3 were not required for ERK1/2 activation. In conclusion, our findings demonstrate that upon binding to agonist, HCA1 receptors initially activate Gi, leading to dissociation of the Gβγ subunit from activated Gi, and subsequently induce ERK1/2 activation via two distinct pathways: one PKC-dependent pathway and the other IGF-IR transactivation-dependent pathway. Our results provide the first in-depth evidence that defines the molecular mechanism of HCA1-mediated ERK1/2 activation.

  10. Influence of chain length and double bond on the aqueous behavior of choline carboxylate soaps.

    Science.gov (United States)

    Rengstl, Doris; Diat, Olivier; Klein, Regina; Kunz, Werner

    2013-02-26

    In preceding studies, we demonstrated that choline carboxylates ChC(m) with alkyl chain lengths of m = 12 - 18 are highly water-soluble (for m = 12, soluble up to 93 wt % soap and 0 °C). In addition, choline soaps are featured by an extraordinary lyotropic phase behavior. With decreasing water concentration, the following phases were found: micellar phase (L(1)), discontinuous cubic phase (I(1)' and I(1)"), hexagonal phase (H(1)), bicontinuous cubic phase (V(1)), and lamellar phase (L(α)). The present work is also focused on the lyotropic phase behavior of choline soaps but with shorter alkyl chains or different alkyl chain properties. We have investigated the aqueous phase behavior of choline soaps with C(8) and C(10) chain-lengths (choline octanoate and choline decanoate) and with a C(18) chain-length with a cis-double bond (choline oleate). We found that choline decanoate follows the lyotropic phase behavior of the longer-chain homologues mentioned above. Choline octanoate in water shows no discontinuous cubic phases, but an extended, isotropic micellar solution phase. In addition, choline octanoate is at the limit between a surfactant and a hydrotrope. The double bond in choline oleate leads also to a better solubility in water and a decrease of the solubilization temperature. It also influences the Gaussian curvature of the aggregates which results in a loss of discontinuous cubic phases in the binary phase diagram. The different lyotropic mesophases were identified by the penetration scan technique with polarizing light microscope and visual observations. To clarify the structural behavior small (SAXS) and wide (WAXS) angle X-ray scattering were performed. To further characterize the extended, isotropic micellar solution phase in the binary phase diagram of choline octanoate viscosity and conductivity measurements were also carried out.

  11. Papain adulteration in 11-nor-Delta9-tetrahydrocannabinol- 9-carboxylic acid-positive urine samples.

    Science.gov (United States)

    Larson, Scott J; Holler, Justin M; Magluilo, Joseph; Dunkley, Christopher S; Jacobs, Aaron

    2008-01-01

    The adulteration of urine samples is an ongoing problem in forensic drug-testing laboratories, even in the military where the practice of observed collections is performed. These adulterants are used to produce a false-negative result when samples are analyzed for drugs of abuse. It has been reported that papain, a cysteine protease, could be successfully used as a urine adulterant, altering the concentration of 11-nor-Delta9-tetrahydrocannabinol-9- carboxylic acid (THCCOOH) in urine samples. The current study analyzes the effects of latex papain (Sigma, 10 mg/mL) and Lawry's Adolph's Meat Tenderizer (papain is an active ingredient, 10 mg/mL) on immunoassays (FPIA, EMIT, KIMS) and gas chromatography-mass spectrometry (GC-MS) analysis for biological samples. The samples were analyzed initially between 2 and 4 h and then at 1-, 3-, 7-, and 10-day time intervals after the addition of papain. A decrease in response averaged over the course of the study was observed with FPIA (Abbott, 22%) and EMIT (Syva) Dade Behring, 26%, Microgenics, 10%) screening assays by the addition of latex papain to the samples. An increase in response was found using the KIMS (Roche) assay (156% increase). In addition, the GC-MS results (27% decrease) demonstrate that papain affects both the screening and confirmation assays. The addition of meat tenderizer caused decrease in the FPIA (Abbott, 11%) screening assay and GC-MS results (22%) similar to the latex papain while having varied results on the other screening assays. This study confirms papain could be a potential problem for urine drug-testing programs. PMID:18652751

  12. Ion exchange studies of alpha-hydroxy carboxylic acid-lanthanide and actinide systems

    International Nuclear Information System (INIS)

    Alpha-hydroxy carboxylic acids have been used extensively for the separation of lanthanide and actinide elements with cation exchange resins. Sorption of these elements in the same solutions occurs on strong base anion-exchange resins. A study has been made by elution and equilibrium distribution techniques of the behaviour at tracer-level concentrations of these anion-exchange systems. One objective was to measure the separation factors to assess anion exchange as a possible complement to cation exchange separation. Since very little attention has been given to characterizing the complexed species present in these separation systems, a second objective was to attempt such characterization through interpretation of both cation and anion exchange data. Glycolic, lactic and alpha-hydroxy isobutyric acids were used together with radioactive tracers of Ce, Pm, Eu, Tb, Tm, Y, Cm and Cf. The elutions and equilibrium distributions were performed both at 25o C and 87o C. In all three eluants, the separation factors were smaller for the anion exchange than for the analogous cation exchange. In the glycolate solutions, the separation factors were largest and the values of the distribution coefficient Kd. indicated that these were the most stable complexes. The plots of log Kd against log anion concentration pass through a maximum and then approach a slope of -1, indicating the presence of an anionic complex MX4-. The existence of this negative complex in the solution phase was demonstrated by electromigration studies of Tm170 tracer in these solutions. At the solution concentration corresponding to the maximum Kd value, it can be shown that the predominant solution species is MX3. Approximate successive stability constants have been calculated for these systems and with these it is possible to construct diagrams showing the relative concentration of the species M+3, MX+2, MX2+, MX3 and MX4- as a function of the concentration of X-. (author)

  13. Synthesis, crystal structure and electrochemical and DNA binding studies of oxygen bridged-copper(II) carboxylate

    Science.gov (United States)

    Iqbal, Muhammad; Ali, Saqib; Tahir, Muhammad Nawaz; Muhammad, Niaz; Shah, Naseer Ali; Sohail, Manzar; Pandarinathan, Vedapriya

    2015-08-01

    A new binuclear O-bridged Cu(II) complex with 4-chlorophenyl acetate and 2,2‧-bipyridine has been synthesized and characterized using FT-IR, powder and single crystal XRD and electrochemical solution studies. The results revealed that the two penta-coordinated Cu(II) centers are linked by two carboxylate ligands in end-on bonding fashion. The coordination geometry is slightly distorted square pyramidal (SP) with bridging oxygen atoms occupying the apical position and other ligands lying in the equatorial plane. The striking difference in Cu-O bond distance of the bridging oxygen atom in the complex may be responsible for the SP geometry of Cu(II) ion. The complex gave rise to metal centered irreversible electro-activity where one electron Cu(II)/Cu(III) oxidation process and a single step two electron Cu(II)/Cu(0) reduction process was observed. The redox processes were found predominantly adsorption controlled. The values of diffusion coefficient and heterogeneous rate constant for oxidation process were 6.98 × 10-7 cm2 s-1 and 4.60 × 10-5 cm s-1 while the corresponding values for reduction were 5.30 × 10-8 cm2 s-1 and 5.41 × 10-6 cm s-1, respectively. The formal potential and charge transfer coefficient were also calculated. The DNA-binding ability was explored through cyclic voltammetry and UV-Visible spectroscopy. Diminution in the value of Do for oxidation indicated the binding of the complex with DNA corresponding to Kb = 8.58 × 104 M-1. UV-Visible spectroscopy yielded ε = 49 L mol-1 cm-1 and Kb = 2.96 × 104 M-1. The data of both techniques support each other. The self-induced redox activation of the complex, as indicated by cyclic voltammetry heralds its potential applications in redox catalysis and anticancer activity.

  14. Effects of temperature and sodium carboxylate additives on mineralization of calcium oxalate in silica gel systems

    Institute of Scientific and Technical Information of China (English)

    OUYANG; Jianming; DENG; Suiping; LI; Xiangping; TAN; Yanh

    2004-01-01

    [1]Ouyang, J. M., Yao, X. Q., Su, Z. X. et al., Simulation of calcium oxalate stone in Vitro, Science in China, Ser. B, 2003, 46(3):234-242.[2]Xu, S. H., Chen, J. Q., Zhou, H., Nepidemiological study of renal calculus in Shenshen region, Chin. J. Urol. (in Chinese), 1999,20(11): 655-657.[3]Bretherton, T., Rodgers, A., Crystallization of calcium oxalate in minimally diluted urine, J. Crystal Growth, 1998, 192: 448-455.[4]Grover, P. K., Ryall, R. L., Effect of seed crystals of uric acid and monosodium urate on the crystallization of CaOxa in undiluted human urine in vitro, Clin. Sci., 1997, 92: 205-213.[5]Laube, N., Mohr, B., Hesse, A., Laser-probe-based investigation of the evolution of particle size distributions of calcium oxalate particles formed in artificial urines, J. Crystal Growth, 2001, 233:367-374.[6]Tunik, L., Fueredi-Milhofer, H., Garti, N., Adsorption of sodium diisooctyl sulfosuccinate onto calcium oxalate crystals, Langmuir,1998, 14: 3351-3355.[7]Cody, A. M., Cody, R. D., Calcium oxalate trihydrate phase control by structurally-specific carboxylic acids, J. Cryst. Growth,1994, 135: 234-245.[8]Ouyang, J. M., Duan, L., Tieke, B., Effects of carboxylic acids on the crystal growth of calcium oxalate nanoparticles in lecithin-water liposome systems, Langmuir, 2003, 19: 8980-8985.[9]Guo, S., Ward, M. D., Wesson, J. A., Direct visualization of calcium oxalate monohydrate crystallization and dissolution with atomic force microscopy and the role of polymeric additives,Langmuir, 2002, 18:4284-4291.[10]Yasui, T., Sato, M., Fujita, K., Effects of citrate on renal stone formation and osteopontin expression in a rat urolithiasis model,Urol. Res., 2001,29: 50-56.[11]Ouyang, J. M., Deng, S. P., Controlled and uncontrolled crystallization of calcium oxalate monohydrate in the presence of citric acid, Dalton Transactions, 2003, (14): 2846-2851.[12]Khan, S. R., Whalen, P. O., Glenton, P. A., Heterogeneous nucleation of

  15. DFT Study of Binding and Electron Transfer from a Metal-Free Dye with Carboxyl, Hydroxyl, and Sulfonic Anchors to a Titanium Dioxide Nanocluster

    Directory of Open Access Journals (Sweden)

    Corneliu I. Oprea

    2013-01-01

    Full Text Available We report results of density functional theory (DFT calculations of a metal-free dye, 5-(4-sulfophenylazosalicylic acid disodium salt, known as Mordant Yellow 10 (MY-10, used as sensitizer for TiO2 dye-sensitized solar cells (DSSCs. Given the need to better understand the behavior of the dyes adsorbed on the TiO2 nanoparticle, we studied various single and double deprotonated forms of the dye bound to a TiO2 cluster, taking advantage of the presence of the carboxyl, hydroxyl, and sulfonic groups as possible anchors. We discuss various binding configurations to the TiO2 substrate and the charge transfer from the pigment to the oxide by means of DFT calculations. In agreement with other reports, we find that the carboxyl group tends to bind in bidentate bridging configurations. The salicylate uses both the carboxyl and hydroxyl substituent groups for either a tridentate binding to adjacent Ti(IV ions or a bidentate Ti-O binding together with an O-H-O binding, due to the rotation of the carboxyl group out of the plane of the dye. The sulfonic group prefers a tridentate binding. We analyze the propensity for electron transfer of the various dyes and find that for MY-10, as a function of the anchor group, the DSSC performance decreases in the order hydroxyl + carboxyl > carboxyl > sulfonate.

  16. Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling

    Science.gov (United States)

    Duncan, Kyle D.; Volmer, Dietrich A.; Gill, Chris G.; Krogh, Erik T.

    2016-03-01

    Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H]-) ions with limited selective fragmentation. However, carboxylates cationized with Ba2+ have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba]+ precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH]+ and [BaOH]+). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

  17. Comparison of Three Solid Phase Materials for the Extraction of Carboxylic Acids from River Water Followed by 2D GC × GC-TOFMS Determination.

    Science.gov (United States)

    Bosire, G O; Ngila, J C; Parshotam, H

    2016-01-01

    The extraction and determination of aliphatic and aromatic carboxylic acids as well as their influence on the aromaticity and molecularity relationship of natural organic matter (NOM) in water are reported in this study. Three solid phase extraction (SPE) sorbents were used and their extraction efficiencies evaluated after chromatographic determinations (using gas chromatography with a time of flight mass spectrometer (GC × GC-TOFMS) and liquid chromatography with organic carbon detector (LC-OCD)). More than 42 carboxylic acids were identified in raw water from the Vaal River, which feeds the Lethabo Power Generation Station, South Africa, with cooling water. The aromatic carboxylic acid efficiency (28%) was achieved by using Strata™ X SPE while the highest aliphatic carboxylic acid efficiency (92.08%) was achieved by silica SPE. The hydrophobic nature of NOM in water depends on the nature of organic compounds in water, whether aromatic or aliphatic. The LC-OCD was used to assess the hydrophobicity levels of NOM as a function of these carboxylic acids in cooling water. The LC-OCD results showed that the aromatic nature of NOM in SPE filtered water followed the order Silica>Strata X>C-18. From the results, the hydrophobicity degree of the samples depended on the type and number of carboxylic acids that were removed by the SPE cartridges. PMID:27274730

  18. Effect of carboxyl anchoring groups in asymmetric zinc phthalocyanine with large steric hindrance on the dye-sensitized solar cell performance

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Wenye; Peng, Bosi; Lin, Li; Li, Renjie; Zhang, Jing, E-mail: jzhang03@whu.edu.cn; Peng, Tianyou, E-mail: typeng@whu.edu.cn

    2015-08-01

    Asymmetric zinc phthalocyanines containing tribenzonaphtho-condensed porphyrazine with six bulky diphenylphenoxy and one or two carboxyl groups are used as sensitizers for dye-sensitized solar cells (DSSCs). It is found that Zn-tri-PcNc-4 having two carboxyl groups shows a slight redshift in the Q-band absorption but a significantly decreased absorbance as compared with Zn-tri-PcNc-8 having one carboxyl group, and Zn-tri-PcNc-4 can be more stably and perpendicularly grafted onto the TiO{sub 2} surface than Zn-tri-PcNc-8, which further leads to the differences in the interfacial charge transfer dynamics and dye-loaded amount. Zn-tri-PcNc-4 with two carboxyl groups grafted onto the TiO{sub 2} electrode surface of DSSC results in a photovoltaic conversion efficiency of 3.22%, higher than that (3.01%) of the analog with one carboxyl group (Zn-tri-PcNc-8), which exhibits a lower short-circuit current but much higher open-circuit voltage. The additional carboxyl group in Zn-tri-PcNc-4 leads to the enhanced dye-loaded amount and the molecular orbital energy level shift toward positive direction, causing more efficient electron injection and higher short-circuit current than Zn-tri-PcNc-8; while the two carboxyl groups of Zn-tri-PcNc-4 would cause more protonation of TiO{sub 2} surface, which possibly leads to the downward shift of TiO{sub 2} conduction band edge, and then to the decreased open-circuit voltage. The present results demonstrate the molecular engineering aspect of ZnPc dyes in which the fine tuning of the energy levels and molecular structures is crucial for high conversion efficiency of DSSCs. - Highlights: • ZnPcs with six diphenylphenoxy and one/two carboxyl groups are used as dyes for DSSCs. • Effect of carboxyl group number on the ZnPc-sensitized cell property are scrutinized. • Grafting two carboxyl groups on ZnPc leads to the enhanced photocurrent and efficiency. • ZnPc with one COOH has a higher open-circuit voltage than its analog with two

  19. Arabidopsis ETO1 specifically interacts with and negatively regulates type 2 1-aminocyclopropane-1-carboxylate synthases

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    Saito Koji

    2005-08-01

    Full Text Available Abstract Background In Arabidopsis, ETO1 (ETHYLENE-OVERPRODUCER1 is a negative regulator of ethylene evolution by interacting with AtACS5, an isoform of the rate-limiting enzyme, 1-aminocyclopropane-1-carboxylate synthases (ACC synthase or ACS, in ethylene biosynthetic pathway. ETO1 directly inhibits the enzymatic activity of AtACS5. In addition, a specific interaction between ETO1 and AtCUL3, a constituent of a new type of E3 ubiquitin ligase complex, suggests the molecular mechanism in promoting AtACS5 degradation by the proteasome-dependent pathway. Because orthologous sequences to ETO1 are found in many plant species including tomato, we transformed tomato with Arabidopsis ETO1 to evaluate its ability to suppress ethylene production in tomato fruits. Results Transgenic tomato lines that overexpress Arabidopsis ETO1 (ETO1-OE did not show a significant delay of fruit ripening. So, we performed yeast two-hybrid assays to investigate potential heterologous interaction between ETO1 and three isozymes of ACC synthases from tomato. In the yeast two-hybrid system, ETO1 interacts with LE-ACS3 as well as AtACS5 but not with LE-ACS2 or LE-ACS4, two major isozymes whose gene expression is induced markedly in ripening fruits. According to the classification of ACC synthases, which is based on the C-terminal amino acid sequences, both LE-ACS3 and AtACS5 are categorized as type 2 isozymes and possess a consensus C-terminal sequence. In contrast, LE-ACS2 and LE-ACS4 are type 1 and type 3 isozymes, respectively, both of which do not possess this specific C-terminal sequence. Yeast two-hybrid analysis using chimeric constructs between LE-ACS2 and LE-ACS3 revealed that the type-2-ACS-specific C-terminal tail is required for interaction with ETO1. When treated with auxin to induce LE-ACS3, seedlings of ETO1-OE produced less ethylene than the wild type, despite comparable expression of the LE-ACS3 gene in the wild type. Conclusion These results suggest that ETO1

  20. Polyethoxylated carboxylic surfactant for ion foam flotation: fundamental study from solution to foam

    International Nuclear Information System (INIS)

    Ion foam flotation allows to concentrate ions in a foam phase formed by a soap. For classical systems, the strong interaction between ions and surfactant generally leads to the formation of precipitates and of froth. When the froth collapses, the solid residue thus recovered requires a recycling or conversion. In order to remedy this, the present work uses as collector a polyethoxylated carboxylic surfactant, AKYPO RO 90 VG, which forms soluble ion/surfactant complexes, even with multi-charge ions. This work presents a detailed study of the fundamental mechanisms that govern the extraction of ions by foaming. In the first part, surface activity and acid/base properties of the surfactant in solution are determined by combining numerous independent techniques which are pH-metric dosage, tensiometry and small angle scattering. The evolution of these properties in the presence of different nitrate salts (Nd, Eu, Ca, Sr, Cu, Li, Na, Cs) coupled with electrophoretic measurements give a first approach to selectivity. Finally, all of these data combined with a study of the formation of surfactant/ion complexes allow us to determine the speciation of Nd/AKYPO system as a function of pH. In the second part, the analysis of the foam by conductivity and neutron scattering provides information on the wetness and foam film thickness, parameters governing foam stability. The pH and the nature of the added ions, their number of charge and also their chemical nature thus appear to be major parameters that governed wetness and foam film thickness. The last part is devoted to the understanding of the ion extraction/separation experiments by flotation based on all previous results. It is shown that the flotation of neodymium is strongly related to its speciation, which could lead to its re-extraction or its flotation in precipitated form. It is shown that, neodymium induces a phenomenon of mono-charge ion depletion in the foam. This ionic specificity allows to consider the studied