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1

Density functional theory study of the oligomerization of carboxylic acids.  

PubMed

We present a density functional theory [M06-2X/6-31+G(d,p)] study of the structures and free energies of formation of oligomers of four carboxylic acids (formic acid, acetic acid, tetrolic acid, and benzoic acid) in water, chloroform, and carbon tetrachloride. Solvation effects were treated using the SMD continuum solvation model. The low-lying energy structures of molecular complexes were located by adopting an efficient search procedure to probe the potential energy surfaces of the oligomers of carboxylic acids (CA)n (n = 2-6). The free energies of the isomers of (CA)n in solution were determined as the sum of the electronic energy, vibrational-rotational-translational gas-phase contribution, and solvation free energy. The assessment of the computational protocol adopted in this study with respect to the dimerization of acetic acid, (AA)2, and formic acid, (FA)2, located new isomers of (AA)2 and (FA)2 and gave dimerization constants in good agreement with the experimental values. The calculation of the self-association of acetic acid, tetrolic acid, and benzoic acid shows the following: (i) Classic carboxylic dimers are the most stable isomer of (CA)2 in both the gas phase and solution. (ii) Trimers of carboxylic acid are stable in apolar aprotic solvents. (iii) Molecular clusters consisting of two interacting classic carboxylic dimers (CA)4,(D+D) are the most stable type of tetramers, but their formation from the self-association of classic carboxylic dimers is highly unfavorable. (iv) For acetic acid and tetrolic acid the reactions (CA)2 + 2CA ? (CA)4,(D+D) and (CA)3 + CA ? (CA)4,(D+D) are exoergonic, but these aggregation pathways go through unstable clusters that could hinder the formation of tetrameric species. (v) For tetrolic acid the prenucleation species that are more likely to form in solution are dimeric and trimeric structures that have encoded structural motifs resembling the ? and ? solid forms of tetrolic acid. (vi) Stable tetramers of benzoic acid could form in carbon tetrachloride from the aggregation of trimers and monomers. (vii) Higher order clusters such as acetic acid pentamers and tetrolic acid hexamers are highly unstable in all solvation environments. PMID:25357019

Di Tommaso, Devis; Watson, Ken L

2014-11-20

2

Gas-Phase Reactivity of Carboxylic Acid Functional Groups with Carbodiimides  

NASA Astrophysics Data System (ADS)

Gas-phase modification of carboxylic acid functionalities is performed via ion/ion reactions with carbodiimide reagents [ N-cyclohexyl- N'-(2-morpholinoethyl)carbodiimide (CMC) and [3-(3-Ethylcarbodiimide-1-yl)propyl]trimethylaminium (ECPT)]. Gas-phase ion/ion covalent chemistry requires the formation of a long-lived complex. In this instance, the complex is stabilized by an electrostatic interaction between the fixed charge quaternary ammonium group of the carbodiimide reagent cation and the analyte dianion. Subsequent activation results in characteristic loss of an isocyanate derivative from one side of the carbodiimide functionality, a signature for this covalent chemistry. The resulting amide bond is formed on the analyte at the site of the original carboxylic acid. Reactions involving analytes that do not contain available carboxylic acid groups (e.g., they have been converted to sodium salts) or reagents that do not have the carbodiimide functionality do not undergo a covalent reaction. This chemistry is demonstrated using PAMAM generation 0.5 dendrimer, ethylenediaminetetraacetic acid (EDTA), and the model peptide DGAILDGAILD. This work demonstrates the selective gas-phase covalent modification of carboxylic acid functionalities.

Prentice, Boone M.; Gilbert, Joshua D.; Stutzman, John R.; Forrest, William P.; McLuckey, Scott A.

2013-01-01

3

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

E-print Network

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.

B. J. Powell

2004-08-24

4

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

PubMed

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 BF3/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(-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. PMID:18022412

Dron, Julien; Eyglunent, Gregory; Temime-Roussel, Brice; Marchand, Nicolas; Wortham, Henri

2007-12-12

5

Carboxylic Acid Unknowns and Titration 90 CARBOXYLIC ACID UNKNOWN  

E-print Network

Point/Boiling Point If your carboxylic acid is a solid, take its melting point. If it is a liquid, take its micro- boiling point. C. Titration/Neutralization EquivalenceMolecular Weight Determination WeighCarboxylic Acid Unknowns and Titration 90 CARBOXYLIC ACID UNKNOWN A. Solubility Tests: Water, Na

Jasperse, Craig P.

6

Carboxylic acid sorption regeneration process  

DOEpatents

Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine. 10 figs.

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

1995-05-02

7

Carboxylic acid sorption regeneration process  

DOEpatents

Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine.

King, C. Judson (Kensington, CA); Poole, Loree J. (Baton Rouge, LA)

1995-01-01

8

Piperazine and its carboxylic acid derivatives-functionalized mesoporous silica as nanocarriers for gemcitabine: Adsorption and release study.  

PubMed

Piperazine-functionalized SBA-15 nanorods were synthesized by post grafting method with methyldimethoxysilylpropylpiperazine (MDSP). The carboxylic acid derivatives of piperazine-functionalized SBA-15 nanorods were obtained using two different kinds of precursors (bromoacetic acid and succinic anhydride). The prepared materials were used as nanocarriers for the anticancer drug (gemcitabine). The obtained samples were characterized by SAXS, N2 adsorption-desorption, SEM, TEM, DLS, thermogravimetric analysis, FTIR, Raman and UV spectroscopies. The adsorption and release properties of all samples were investigated. In vitro study included cell toxicity. It was found that the surface functionalization increases the interaction between the carrier and gemcitabine and results in the loading enhancement of the drug. In addition, the adsorption of gemcitabine on the modified mesoporous matrix depends 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 36wt.% that it is related to PC2-SBA-15 sample which obtained using succinic anhydride. The obtained results reveal that the surface functionalization leads toward a significant decrease of the drug release rate without any appreciable cytotoxicity. No significant differences are observed among the drug release rate from the modified samples. PMID:25686928

Bahrami, Zohreh; Badiei, Alireza; Atyabi, Fatemeh; Darabi, Hossein Reza; Mehravi, Bita

2015-04-01

9

Molecular Structure of Cyclopropane carboxylic acid  

NSDL National Science Digital Library

Cyclopropane carboxylic acid is a clear liquid used as an intermediate for agrochemicals, pharmaceuticals, and other organic synthesis such as for the applications of electronics, chemicals, polymer additives, coatings, adhesives, surfactants, and other applications. Also, derivatives of cyclopropane-carboxylic acid are used against parasites in plants and animals. For example, the alkynyl esters of cyclopropane-carboxylic acid are used as pesticides. Similarly, cyclopropane carboxylic acid esters containing a polyhalogenated substituent are used as fungicides.

2003-04-11

10

Synthesis, bifunctionalization, and remarkable adsorption performance of benzene-bridged periodic mesoporous organosilicas functionalized with high loadings of carboxylic acids.  

PubMed

Highly ordered benzene-bridged periodic mesoporous organosilicas (PMOs) that were functionalized with exceptionally high loadings of carboxylic acid groups (COOH), up to 80?mol?% based on silica, have been synthesized and their use as adsorbents for the adsorption of methylene blue (MB), a basic dye pollutant, and for the loading and release of doxorubicin (DOX), an anticancer drug, is demonstrated. These COOH-functionalized benzene-silicas were synthesized by the co-condensation of 1,4-bis(triethoxysilyl) benzene (BTEB) and carboxyethylsilanetriol sodium salt (CES), an organosilane that contained a carboxylic acid group, in the presence of non-ionic oligomeric surfactant Brij?76 in acidic medium. The materials thus obtained were characterized by a variety of techniques, including powder X-ray diffraction (XRD), nitrogen-adsorption/desorption isotherms, TEM, and (13)C and (29)Si solid-state NMR spectroscopy. Owing to the exceptionally high loadings of COOH groups, their high surface areas, and possible ?-?-stacking interactions, these adsorbents have very high adsorption capacities and extremely rapid adsorption rates for MB removal and for the controlled loading/release of DOX, thus manifesting their great potential for environmental and biomedical applications. PMID:23512281

Wu, Hao-Yiang; Shieh, Fa-Kuen; Kao, Hsien-Ming; Chen, Yi-Wen; Deka, Juti Rani; Liao, Shih-Hsiang; Wu, Kevin C-W

2013-05-10

11

Spectroscopic studies on sidewall carboxylic acid functionalization of multi-walled carbon nanotubes with valine.  

PubMed

The valine functionalized multi-walled carbon nanotubes (MWCNTS) were prepared and characterized by using XRD, UV-Vis, FT-IR, EPR, SEM, and EDX, spectroscopic techniques. The enhanced XRD peak (002) intensity was observed for valine functionalized MWCNTs compared with oxidized MWCNTs, which is likely due to sample purification by acid washing. UV-Vis study shows the formation of valine functionalized MWCNTs. FT-IR study confirms the presence of functional groups of oxidized MWCNTs and valine functionalized MWCNTs. The ESR line shape analysis indicates that the observed EPR line shape is a Gaussian line shape. The g-values indicate that the systems are isotropic in nature. The morphology study was carried out for oxidized MWCNTs and valine functionalized MWCNTs by using SEM. The EDX spectra revealed that the high purity of oxidized MWCNTs and valine functionalized MWCNTs. The functionalization has been chosen because, functionalization of CNTs with amino acids makes them soluble and biocompatible. Thus, they have potential applications in the field of biosensors and targeted drug delivery. PMID:25554963

Deborah, M; Jawahar, A; Mathavan, T; Dhas, M Kumara; Benial, A Milton Franklin

2015-03-15

12

Synergistic effect of self-assembled carboxylic acid-functionalized carbon nanotubes and carbon fiber for improved electro-activated polymeric shape-memory nanocomposite  

NASA Astrophysics Data System (ADS)

The present work studies the synergistic effect of self-assembled carboxylic acid-functionalized carbon nanotube (CNT) and carbon fiber on the electrical property and electro-activated recovery behavior of shape memory polymer (SMP) nanocomposites. The combination of CNT and carbon fiber results in improved electrical conductivity in the SMP nanocomposites. Carboxylic acid-functionalized CNTs are grafted onto the carbon fibers and then self-assembled by deposition to significantly enhance the reliability of the bonding between carbon fiber and SMP via van der Waals and covalent crosslink. Furthermore, the self-assembled carboxylic acid-functionalized CNTs and carbon fibers enable the SMP nanocomposites for Joule heating triggered shape recovery.

Lu, Haibao; Min Huang, Wei

2013-06-01

13

Peptide coupling between amino acids and the carboxylic acid of a functionalized chlorido-gold(I)-phosphane.  

PubMed

We have developed a protocol for the direct coupling between methyl ester protected amino acids and the chlorido-gold(I)-phosphane (p-HOOC(C6H4)PPh2)AuCl. By applying the EDC·HCl/NHS strategy (EDC·HCl = N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide hydrochloride, NHS = N-hydroxysuccinimide), the methyl esters of l-phenylalanine, glycine, l-leucine, l-alanine, and l-methionine are coupled with the carboxylic acid of the gold complex in moderate to good yields (62-88%). All amino acid tagged gold complexes were characterized by (1)H and (13)C NMR spectroscopy and high-resolution mass spectrometry. As corroborated by measurement of the angle of optical rotation, no racemization occurred during the reaction. The molecular structure of the leucine derivative was determined by single-crystal X-ray diffraction. In the course of developing an efficient coupling protocol, the acyl chlorides (p-Cl(O)C(C6H4)PPh2)AuX (X = Cl, Br) were also prepared and characterized. PMID:25203269

Kriechbaum, Margit; List, Manuela; Himmelsbach, Markus; Redhammer, Günther J; Monkowius, Uwe

2014-10-01

14

A Novel Plant Cysteine Protease Has a Dual Function as a Regulator of 1-Aminocyclopropane-1-Carboxylic Acid  

E-print Network

-Carboxylic Acid Synthase Gene Expression W Noa Matarasso, Silvia Schuster, and Adi Avni1 Department of Plant Sciences, Tel Aviv University, Tel Aviv 69978, Israel The hormone ethylene influences plant growth Ethylene as a plant hormone influences many aspects of plant growth and development (Mattoo and Suttle

Avni, Adi

15

Aqueous infrared carboxylate absorbances: Aliphatic di-acids  

USGS Publications Warehouse

Aqueous attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of 18 aliphatic di-carboxylic acids are reported as a function of pH. The spectra show isosbestic points and intensity changes which indicate that Beer's law is obeyed, and peak frequencies lie within previously reported ranges for aqueous carboxylates and pure carboxylic acids. Intensity sharing from the symmetric carboxylate stretch is evident in many cases, so that bands which are nominally due to alkyl groups show increased intensity at higher pH. The asymmetric stretch of the HA- species is linearly related to the microscopic acidity constant of the H2A species, with ??pK 2 intervening atoms). The results suggest that aqueous ATR-FTIR may be able to estimate 'intrinsic' pKa values of carboxylic acids, in addition to providing quantitative estimates of ionization. ?? 1998 Elsevier Science B.V. All rights reserved.

Cabaniss, S.E.; Leenheer, J.A.; McVey, I.F.

1998-01-01

16

An experimental and density functional study on conformational and spectroscopic analysis of 5-methoxyindole-2-carboxylic acid  

NASA Astrophysics Data System (ADS)

In this article, a brief conformational and spectroscopic characterization of 5-methoxyindole-2-carboxylic acid (5-MeOICA) via experimental techniques and applications of quantum chemical methods is presented. The conformational analysis of the studied molecule was determined theoretically using density functional computations for ground state, and compared with previously reported experimental findings. The vibrational transitions were examined by measured FT-IR and FT-Raman spectroscopic data, and also results obtained from B3LYP and CAM-B3LYP functionals in combination with 6-311++G(d,p) basis set. The recorded proton and carbon NMR spectra in DMSO solution were analyzed to obtain the exact conformation. Due to intermolecular hydrogen bondings, NMR calculations were performed for the dimeric form of 5-MeOICA and so chemical shifts of those protons were predicted more accurately. Finally, electronic properties of steady compound were identified by a comparative study of UV absorption spectra in ethanol and water solution and TD-DFT calculations.

Cinar, Mehmet; Karabacak, Mehmet; Asiri, Abdullah M.

2015-02-01

17

Carboxylic acid accelerated formation of diesters  

DOEpatents

This invention pertains to accelerating the rate of formation of 1,1-dicarboxylic esters from the reaction of an aldehyde with a carboxylic acid anhydride or a ketene in the presence of a non-iodide containing a strong Bronsted acid catalyst by the addition of a carboxylic acid at about one bar pressure and between about 0 and 80 C in the substantial absence of a hydrogenation or carbonylation catalyst.

Tustin, G.C.; Dickson, T.J.

1998-04-28

18

Development of an Electrogenerated Chemiluminescence Biosensor using Carboxylic acid-functionalized MWCNT and Au Nanoparticles  

PubMed Central

A COOH-F-MWCNT-Nafion-Ru(bpy)32+-Au-ADH electrogenerated chemiluminescence (ECL) electrode using COOH-functionalized MWCNT (COOH-F-MWCNT) and Au nanoparticles synthesized by the radiation method was fabricated for ethanol sensing. A higher sensing efficiency for ethanol for the ECL biosensor prepared by PAAc-g-MWCNT was measured compared to that of the ECL biosensor prepared by PMAc-g-MWCNT, and purified MWCNT. Experimental parameters affecting ethanol detection were also examined in terms of pH and the content of PAAc-g-MWCNT in Nafion. Little interference of other compounds was observed for the assay of ethanol. Results suggest this ECL biosensor could be applied for ethanol detection in real samples. PMID:22573979

Piao, Ming-Hua; Yang, Dae-Soo; Yoon, Kuk-Ro; Lee, Seung-Ho; Choi, Seong-Ho

2009-01-01

19

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

SciTech Connect

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 counterparts of similar thickness (Nafion{trademark} 111). Additionally, nitric acid separation efficiencies ({alpha}) were approximately one order of magnitude higher for the carboxylate solution cast films when compared to Nafion{trademark} 111. The second phase of our work included the generation of thin carboxylate films made by the chemical synthesis perfluoro sulfonate and mixed sulfonate/carboxylate polymers from a perfluoro sulfonyl fluoride precursor, the characterization of the newly generated material, and a study of the transport characteristics of these membranes. Transport studies consisted of the dehydration of nitric acid feeds by pervaporation. In addition, the initial hypothesis was expanded to include demonstration that transmembrane flux and separation efficiencies are a function of the ratio between sulfonate and carboxylate terminated side chains of the perfluoro ionomer. Investigations demonstrated the ability to generate in- house films with varying sulfonate/carboxylate concentrations from commercially available perfluoro sulfonyl fluoride material, and showed that the converted films could be characterized using Fourier transform infrared (FTIR) and x-ray fluorescence (XRF) spectroscopy. Finally, the mixed films where subjected to nitric acid dehydration transport tests and a relationship was found to exist between sulfonate/carboxylate pendant chain ratio and both flux and water separation capability. In summary, experimental results confirmed that, when compared to Nafion 111{trademark}, the mixed film's bulk fluxes decrease by approximately three orders of magnitude and the water separation factor increases by as much as two orders of magnitude as the carboxylate side-chain content was increased from 0 (pure sulfonate film) to 53 mole%, supporting the hypothesis given for this effort. It was observed that the water selectivity improved for both the solution cast perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films when judged against similar perfluoro sulfonate materials. Of great benefit was that during the investigation a number of research tools w

R.L. Ames

2004-09-01

20

Metabolism of Cyclohexane Carboxylic Acid by Alcaligenes Strain W1  

PubMed Central

Thirty-three microorganisms capable of growth with cyclohexane carboxylate as the sole source of carbon were isolated from mud, water, and soil samples from the Aberystwyth area. Preliminary screening and whole-cell oxidation studies suggested that, with one exception, all of the strains metabolized the growth substrate by beta-oxidation of the coenzyme A ester. This single distinctive strain, able to oxidize rapidly trans-4-hydroxycyclohexane carboxylate, 4-ketocyclohexane carboxylate, p-hydroxybenzoate, and protocatechuate when grown with cyclohexane carboxylate, was classified as a strain of Alcaligenes and given the number W1. Enzymes capable of converting cyclohexane carboxylate to p-hydroxybenzoate were induced by growth with the alicyclic acid and included the first unambiguous specimen of a cyclohexane carboxylate hydroxylase. Because it is a very fragile protein, attempts to stabilize the cyclohexane carboxylate hydroxylase so that a purification procedure could be developed have consistently failed. In limited studies with crude cell extracts, we found that hydroxylation occurred at the 4 position, probably yielding the trans isomer of 4-hydroxycyclohexane carboxylate. Simultaneous measurement of oxygen consumption and reduced nicotinamide adenine dinucleotide oxidation, coupled with an assessment of reactant stoichiometry, showed the enzyme to be a mixed-function oxygenase. Mass spectral analysis enabled the conversion of cyclohexane carboxylate to p-hydroxybenzoate by cell extracts to be established unequivocally, and all of our data were consistent with the pathway: cyclohexane carboxylate ? trans-4-hydroxycyclohexane carboxylate ? 4-ketocyclohexane carboxylate ? p-hydroxybenzoate. The further metabolism of p-hydroxybenzoate proceeded by meta fission and by the oxidative branch of the 2-hydroxy-4-carboxymuconic semialde-hyde-cleaving pathway. PMID:207665

Taylor, David G.; Trudgill, Peter W.

1978-01-01

21

Molecular level computational studies of polyethylene and polyacrylonitrile composites containing single walled carbon nanotubes: effect of carboxylic acid functionalization on nanotube-polymer interfacial properties  

PubMed Central

Molecular dynamics (MD) and molecular mechanics (MM) methods have been used to investigate additive-polymer interfacial properties in single walled carbon nanotube (SWNT)—polyethylene and SWNT—polyacrylonitrile composites. Properties such as the interfacial shear stress and bonding energy are similar for the two composites. In contrast, functionalizing the SWNT with carboxylic acid groups leads to an increase in these properties, with a larger increase for the polar polyacrylonitrile composite. Increasing the percentage of carbon atoms that were functionalized from 1 to 5% also leads to an increase in the interfacial properties. In addition, the interfacial properties depend on the location of the functional groups on the SWNT wall. PMID:25229056

Haghighatpanah, Shayesteh; Bohlén, Martin; Bolton, Kim

2014-01-01

22

40 CFR 721.10679 - Carboxylic acid, substituted alkylstannylene ester, reaction products with inorganic acid tetra...  

... 2014-07-01 false Carboxylic acid, substituted alkylstannylene ester, reaction products with inorganic acid tetra alkyl ester (generic). 721...Substances § 721.10679 Carboxylic acid, substituted alkylstannylene...

2014-07-01

23

Behavior of carboxylic acids upon complexation with beryllium compounds.  

PubMed

A significant acidity enhancement and changes on aromaticity were previously observed in squaric acid and its derivatives when beryllium bonds are present in those systems. In order to know if these changes on the chemical properties could be considered a general behavior of carboxylic acids upon complexation with beryllium compounds, complexes between a set of representative carboxylic acids RCOOH (formic acid, acetic acid, propanoic acid, benzoic acid, and oxalic acid) and beryllium compounds BeX2 (X = H, F, Cl) were studied by means of density functional theory calculations. Complexes that contain a dihydrogen bond or a OH···X interaction are the most stable in comparison with other possible BeX2 complexation patterns in which no other weak interactions are involved apart from the beryllium bond. Formic, acetic, propanoic, benzoic, and oxalic acid complexes with BeX2 are much stronger acids than their related free forms. The analysis of the topology of the electron density helps to clarify the reasons behind this acidity enhancement. Importantly, when the halogen atom is replaced by hydrogen in the beryllium compound, the dihydrogen bond complex spontaneously generates a new neutral complex [RCOO:BeH] in which a hydrogen molecule is lost. This seems to be a trend for carboxylic acids on complexing BeX2 compounds. PMID:25010490

Mykolayivna-Lemishko, Kateryna; Montero-Campillo, M Merced; Mó, Otilia; Yáñez, Manuel

2014-07-31

24

An efficient tandem approach for the synthesis of functionalized 2-pyridone-3-carboxylic acids using three-component reaction in aqueous media.  

PubMed

Novel analogs of 2-pyridone-3-carboxylic acids 4a-l have been prepared by the three-component reaction of 3-formyl chromone, Meldrum's acid, and primary amines in the presence of a catalytic amount of diammonium hydrogen phosphate in water. Good-to-high yields, easy work-up, and an environmentally friendly profile are the advantages of this method for the synthesis of 2-pyridone-3-carboxylic acid derivatives. PMID:24792225

Mehrparvar, Saber; Balalaie, Saeed; Rabbanizadeh, Mahnaz; Ghabraie, Elmira; Rominger, Frank

2014-08-01

25

The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery  

ERIC Educational Resources Information Center

The conversion of carboxylic acids to ketones is a useful chemical transformation with a long history. Several chemists have claimed that they discovered the conversion of carboxylic acids to ketones yet in fact the reaction is actually known for centuries.

Nicholson, John W.; Wilson, Alan D.

2004-01-01

26

40 CFR 721.10255 - Vinyl carboxylic acid ester (generic).  

Code of Federal Regulations, 2012 CFR

...2012-07-01 false Vinyl carboxylic acid ester (generic). 721.10255...721.10255 Vinyl carboxylic acid ester (generic). (a...generically as vinyl carboxylic acid ester (PMN P-09-400...as specified in § 721.80(s) (100,000 kilograms)....

2012-07-01

27

40 CFR 721.10255 - Vinyl carboxylic acid ester (generic).  

Code of Federal Regulations, 2013 CFR

...2013-07-01 false Vinyl carboxylic acid ester (generic). 721.10255...721.10255 Vinyl carboxylic acid ester (generic). (a...generically as vinyl carboxylic acid ester (PMN P-09-400...as specified in § 721.80(s) (100,000 kilograms)....

2013-07-01

28

40 CFR 721.10255 - Vinyl carboxylic acid ester (generic).  

...2014-07-01 false Vinyl carboxylic acid ester (generic). 721.10255...721.10255 Vinyl carboxylic acid ester (generic). (a...generically as vinyl carboxylic acid ester (PMN P-09-400...as specified in § 721.80(s) (100,000 kilograms)....

2014-07-01

29

Production of carboxylic acid and salt co-products  

DOEpatents

This invention provide processes for producing carboxylic acid product, along with useful salts. The carboxylic acid product that is produced according to this invention is preferably a C.sub.2-C.sub.12 carboxylic acid. Among the salts produced in the process of the invention are ammonium salts.

Hanchar, Robert J.; Kleff, Susanne; Guettler, Michael V.

2014-09-09

30

Chiral metal-organic frameworks bearing free carboxylic acids for organocatalyst encapsulation.  

PubMed

Two chiral carboxylic acid functionalized micro- and mesoporous metal-organic frameworks (MOFs) are constructed by the stepwise assembly of triple-stranded heptametallic helicates with six carboxylic acid groups. The mesoporous MOF with permanent porosity functions as a host for encapsulation of an enantiopure organic amine catalyst by combining carboxylic acids and chiral amines in situ through acid-base interactions. The organocatalyst-loaded framework is shown to be an efficient and recyclable heterogeneous catalyst for the asymmetric direct aldol reactions with significantly enhanced stereoselectivity in relative to the homogeneous organocatalyst. PMID:25382736

Liu, Yan; Xi, Xiaobing; Ye, Chengcheng; Gong, Tengfei; Yang, Zhiwei; Cui, Yong

2014-12-01

31

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 1. Minor structures  

USGS Publications Warehouse

An investigation of the strong-acid characteristics (pKa 3.0 or less) of fulvic acid from the Suwannee River, Georgia, was conducted. Quantitative determinations were made for amino acid and sulfur-containing acid structures, oxalate half-ester structures, malonic acid structures, keto acid structures, and aromatic carboxyl-group structures. These determinations were made by using a variety of spectrometric (13C-nuclear magnetic resonance, infrared, and ultraviolet spectrometry) and titrimetric characterizations on fulvic acid or fulvic acid samples that were chemically derivatized to indicate certain functional groups. Only keto acid and aromatic carboxyl-group structures contributed significantly to the strong-acid characteristics of the fulvic acid; these structures accounted for 43% of the strong-acid acidity. The remaining 57% of the strong acids are aliphatic carboxyl groups in unusual and/or complex configurations for which limited model compound data are available.

Leenheer, J.A.; Wershaw, R.L.; Reddy, M.M.

1995-01-01

32

Preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters  

DOEpatents

Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

Gogate, Makarand Ratnakar (Durham, NC); Spivey, James Jerry (Cary, NC); Zoeller, Joseph Robert (Kingsport, TN)

1998-01-01

33

Preparation of {alpha},{beta}-unsaturated carboxylic acids and esters  

DOEpatents

Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.

1998-09-15

34

Boron-containing amino carboxylic acid compounds and uses thereof  

DOEpatents

Novel compounds which are useful for boron neutron capture therapy (BNCT) are disclosed. The compounds comprise a stable boron-containing group and an aminocycloalkane carboxylic acid group or a boronated acyclic hydrocarbon-linked amino carboxylic acid. Methods for synthesis of the compounds and for use of the compounds in BNCT are disclosed.

Kabalka, George W. (Knoxville, TN); Srivastava, Rajiv R. (Knoxville, TN)

2000-03-14

35

MICROBIAL TRANSFORMATION OF ESTERS OF CHLORINATED CARBOXYLIC ACIDS  

EPA Science Inventory

Two groups of compounds were selected for microbial transformation studies. In the first group were carboxylic acid esters having a fixed aromatic moiety and an increasing length of the alkyl component. Ethyl esters of chlorine-substituted carboxylic acids were in the second grou...

36

Functional modulation of cerebral gamma-aminobutyric acidA receptor/benzodiazepine receptor/chloride ion channel complex with ethyl beta-carboline-3-carboxylate: Presence of independent binding site for ethyl beta-carboline-3-carboxylate  

SciTech Connect

Effect of ethyl beta-carboline-3-carboxylate (beta-CCE) on the function of gamma-aminobutyric acid (GABA)A receptor/benzodiazepine receptor/chloride ion channel complex was studied. Beta-CCE noncompetitively and competitively inhibited (3H)flunitrazepam binding to benzodiazepine receptor, but not (3H)muscimol binding to GABAA receptor as well as t-(3H)butylbicycloorthobenzoate (( 3H) TBOB) binding to chloride ion channel, in particulate fraction of the mouse brain. Ro15-1788 also inhibited competitively (3H) flunitrazepam binding. On the other hand, the binding of beta-(3H)CCE was inhibited noncompetitively and competitively by clonazepam and competitively by Ro15-1788. In agreement with these results, benzodiazepines-stimulated (3H)muscimol binding was antagonized by beta-CCE and Ro15-1788. Gel column chromatography for the solubilized fraction from cerebral particulate fraction by 0.2% sodium deoxycholate (DOC-Na) in the presence of 1 M KCl indicated that beta-(3H)CCE binding site was eluted in the same fraction (molecular weight, 250,000) as the binding sites for (3H)flunitrazepam, (3H)muscimol and (3H)TBOB. GABA-stimulated 36Cl- influx into membrane vesicles prepared from the bovine cerebral cortex was stimulated and attenuated by flunitrazepam and beta-CCE, respectively. These effects of flunitrazepam and beta-CCE on the GABA-stimulated 36Cl- influx were antagonized by Ro15-1788. The present results suggest that the binding site for beta-CCE, which resides on GABAA receptor/benzodiazepine receptor/chloride ion channel complex, may be different from that for benzodiazepine. Possible roles of beta-CCE binding site in the allosteric inhibitions on benzodiazepine binding site as well as on the functional coupling between chloride ion channel and GABAA receptor are also suggested.

Taguchi, J.; Kuriyama, K. (Kyoto Prefectural Univ. of Medicine (Japan))

1990-05-01

37

Addressing Mechanistic Issues in the Coupling of Isonitriles and Carboxylic Acids: Potential Routes to Peptidic Constructs  

PubMed Central

Mechanistic issues surrounding the 2CC (two component coupling) reaction of carboxylic acids with isonitriles have been investigated. Experimental details suggest the FCMA (formimidate carboxylate mixed anhydride) intermediate exists in both interdictable and non-interdictable form. Furthermore, the 2CC reaction has been applied to the synthesis of a tripeptide featuring two formyl functional groups. PMID:18783225

Li, Xuechen; Yuan, Yu; Kan, Cindy; Danishefsky, Samuel J.

2008-01-01

38

Calixarene based chiral solvating agents for ?-hydroxy carboxylic acids  

NASA Astrophysics Data System (ADS)

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.

Bozkurt, Selahattin

2013-09-01

39

Phytotoxicity of low-weight carboxylic acids.  

PubMed

Presence of low-weight carboxylic acids (LWCAs) can be the reason for phytotoxicity of green manures, treated bio-waste or digestates from biogas production applied to soils. As the phytotoxic concentrations of LWCA are poorly known, this work presents data on six acids (C(1)C(6): formic, acetic, propionic, butyric, valeric, and caproic). Phytotoxicity was measured in acute (72 or 120 h) and subchronic (21 d) assays for seed germination, seedling elongation, and plant growth for garden cress Lepidium sativum and ryegrass Lolium multiflorum. The dose-response relationship was modeled using Weibull model. Results showed a trend that toxicity of LWCA increases with the length of the carbon chain, formic acid (C(1)) being the least and caproic acid (C(6)) the most toxic. EC50 values in the acute seed germination of cress ranged between 1.9 and 4.2mM and for ryegrass between 1.8 and 6.4mM. In subchronic assays EC50 values for germination were in a range from 11 to 46mMkg(-1)dm for cress, and from 18 to 127 mM kg(-1) dm for ryegrass. EC50 values for early seedling growth of cress based on acute assays ranged from 0.7 to 2.3mM and that of ryegrass from 1.2 to 1.8mM. Range of EC50 values for shoot biomass of cress was between 8 and 40 mM kg(-1) dm and of ryegrass between 12 and 93 mM kg(-1) dm. PMID:22440635

Himanen, Marina; Prochazka, Petr; Hänninen, Kari; Oikari, Aimo

2012-07-01

40

Fabrication of sulfonated poly(ether ether ketone)-based hybrid proton-conducting membranes containing carboxyl or amino acid-functionalized titania by in situ sol-gel process  

NASA Astrophysics Data System (ADS)

Functionalized titania are used as fillers to modify the sulfonated poly(ether ether ketone) (SPEEK) membrane for improved proton conductivity and methanol barrier property. The functionalized titania sol which contains proton conductive carboxylic acid groups or amino acid groups are derived from a facile chelation method using different functional additives. Then the novel SPEEK/carboxylic acid-functionalized titania (SPEEK/TC) and SPEEK/amino acid-functionalized titania (SPEEK/TNC) hybrid membranes are fabricated via in situ sol-gel method. The anti-swelling property and thermal stability of hybrid membranes are enhanced owing to the formation of electrostatic force between SPEEK and titania nanoparticles. The hybrid membranes exhibit higher proton conductivity than plain SPEEK membrane because more proton transfer sites are provided by the functionalized titania nanoparticles. Particularly, the proton conductivity of SPEEK/TNC membrane with 15% filler content reaches up to 6.24 × 10-2 S cm-1, which is 3.5 times higher than that of the pure SPEEK membrane. For methanol permeability, the SPEEK/TNC membranes possess the lowest values because the acid-base interaction between sulfonic acid groups in SPEEK and amino groups in functionalized titania leads to a more compact membrane structure.

Yin, Yongheng; Xu, Tao; He, Guangwei; Jiang, Zhongyi; Wu, Hong

2015-02-01

41

Preparation of .alpha., .beta.-unsaturated carboxylic acids and anhydrides  

DOEpatents

Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

Spivey, James Jerry (Cary, NC); Gogate, Makarand Ratnakav (Durham, NC); Zoeller, Joseph Robert (Kingsport, TN); Tustin, Gerald Charles (Kingsport, TN)

1998-01-01

42

Preparation of {alpha}, {beta}-unsaturated carboxylic acids and anhydrides  

DOEpatents

Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Tustin, G.C.

1998-01-20

43

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

SciTech Connect

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.

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

1991-11-01

44

Olfactory Sensitivity and Odor Structure-Activity Relationships for Aliphatic Carboxylic Acids in CD-1 Mice  

PubMed Central

Using a conditioning paradigm, the olfactory sensitivity of CD-1 mice for a homologous series of aliphatic n-carboxylic acids (ethanoic acid to n-octanoic acid) and several of their isomeric forms was investigated. With all 14 odorants, the animals significantly discriminated concentrations as low as 0.03 ppm (parts per million) from the solvent, and with four odorants the best-scoring animals even detected concentrations as low as 3 ppt (parts per trillion). Analysis of odor structure-activity relationships showed that the correlation between olfactory detection thresholds of the mice for the unbranched carboxylic acids and carbon chain length can best be described as a U-shaped function with the lowest threshold values at n-butanoic acid. A significant positive correlation between olfactory detection thresholds and carbon chain length of the carboxylic acids with their branching next to the functional carboxyl group was found. In contrast, no such correlation was found for carboxylic acids with their branching at the distal end of the carbon chain relative to the functional carboxyl group. Finally, a significant correlation was found between olfactory detection thresholds and the position of the branching of the carboxylic acids. Across-species comparisons suggest that mice are more sensitive for short-chained (C2 to C4) aliphatic n-carboxylic acids than other mammalian species, but not for longer-chained ones (C5 to C8). Further comparisons suggest that odor structure-activity relationships are both substance class- and species-specific. PMID:22479594

Can Güven, Selçuk; Laska, Matthias

2012-01-01

45

Olfactory sensitivity and odor structure-activity relationships for aliphatic carboxylic acids in CD-1 mice.  

PubMed

Using a conditioning paradigm, the olfactory sensitivity of CD-1 mice for a homologous series of aliphatic n-carboxylic acids (ethanoic acid to n-octanoic acid) and several of their isomeric forms was investigated. With all 14 odorants, the animals significantly discriminated concentrations as low as 0.03 ppm (parts per million) from the solvent, and with four odorants the best-scoring animals even detected concentrations as low as 3 ppt (parts per trillion). Analysis of odor structure-activity relationships showed that the correlation between olfactory detection thresholds of the mice for the unbranched carboxylic acids and carbon chain length can best be described as a U-shaped function with the lowest threshold values at n-butanoic acid. A significant positive correlation between olfactory detection thresholds and carbon chain length of the carboxylic acids with their branching next to the functional carboxyl group was found. In contrast, no such correlation was found for carboxylic acids with their branching at the distal end of the carbon chain relative to the functional carboxyl group. Finally, a significant correlation was found between olfactory detection thresholds and the position of the branching of the carboxylic acids. Across-species comparisons suggest that mice are more sensitive for short-chained (C(2) to C(4)) aliphatic n-carboxylic acids than other mammalian species, but not for longer-chained ones (C(5) to C(8)). Further comparisons suggest that odor structure-activity relationships are both substance class- and species-specific. PMID:22479594

Can Güven, Selçuk; Laska, Matthias

2012-01-01

46

Direct enantioselective conjugate addition of carboxylic acids with chiral lithium amides as traceless auxiliaries.  

PubMed

Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B. PMID:25562717

Lu, Ping; Jackson, Jeffrey J; Eickhoff, John A; Zakarian, Armen

2015-01-21

47

Langmuir 1985,1,725-740 725 Acid-Base Behavior of Carboxylic Acid Groups Covalently  

E-print Network

using chromic acid/sulfuric acid introduces a high density of covalently attached carboxylic acid groupsLangmuir 1985,1,725-740 725 Acid-Base Behavior of Carboxylic Acid Groups Covalently Attached: August 7, 1985 Oxidation of polyethylene with chromic acidfsulfuric acid generates a material (PE-C02H

Deutch, John

48

Microtribological properties of molecularly thin carboxylic acid functionalized imidazolium ionic liquid film on single-crystal silicon  

NASA Astrophysics Data System (ADS)

A series of 1-alkyl-3-ethylcarboxylic acid imidazolium chloride ([AEImi][Cl]) ionic liquids was synthesized and evaluated as a new kind of lubricant for microelectromechanical system (MEMS). In this research, novel molecular thin ionic liquid films (ILs) with various bonding percentages were prepared with different annealing temperatures and times. Film wettability was determined by measurement of contact angle and thickness with the ellipsometric method. The chemical composition, structure and morphology were characterized by the means of multi-technique X-ray photoelectron spectrometric, and atomic force microscopic analysis, respectively. The nano- and microtribological properties of the ionic liquid film were investigated. The morphologies of wear tracks of IL films were examined using a 3D non-contact profilometer. The influence of chain length on friction in nano-scale, and the effect of bonding percentage and sliding frequency on friction coefficient, carry-bearing capacity and durability in micro-scale were studied. Data are compared to the perfluoropolyether lubricant Z Dol. The [AEImi][Cl] ionic liquid films with appropriate bonding percentage exhibited comparable load-bearing capacity and durability than Z Dol 3800 at thickness level of several nanometers. Therefore, the [AEImi][Cl] ionic liquid film shows strong potential applications involving the lubrication and protection of MEMS.

Mo, Yufei; Yu, Bo; Zhao, Wenjie; Bai, Mingwu

2008-12-01

49

40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).  

...2014-07-01 2014-07-01 false Cobalt iron manganese oxide, carboxylic acid-modified...Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid-modified...substance identified generically as cobalt iron manganese oxide, carboxylic...

2014-07-01

50

40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).  

Code of Federal Regulations, 2013 CFR

...2013-07-01 2013-07-01 false Cobalt iron manganese oxide, carboxylic acid-modified...Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid-modified...substance identified generically as cobalt iron manganese oxide, carboxylic...

2013-07-01

51

Direct esterification of ammonium salts of carboxylic acids  

DOEpatents

A non-catalytic process for producing esters, the process comprising reacting an ammonium salt of a carboxylic acid with an alcohol and removing ammonia from the reaction mixture. Selectivities for the desired ester product can exceed 95 percent.

Halpern, Yuval (Skokie, IL)

2003-06-24

52

ESTIMATION OF CARBOXYLIC ACID ESTER HYDROLYSIS RATE CONSTANTS  

EPA Science Inventory

SPARC chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid esters from molecular structure. The energy differences between the initial state and the transition state for a molecule of interest are factored into internal and external...

53

Separation of certain carboxylic acids utilizing cation exchange membranes  

DOEpatents

A method of substantially separating monofunctional lower carboxylic acids from a liquid mixture containing the acids wherein the pH of the mixture is adjusted to a value in the range of from about 1 to about 5 to form protonated acids. The mixture is heated to an elevated temperature not greater than about 100.degree. C. and brought in contact with one side of a perfluorinated cation exchange membrane having sulfonate or carboxylate groups or mixtures thereof with the mixture containing the protonated acids. A pressure gradient can be established across the membrane with the mixture being under higher pressure, so that protonated monofunctional lower carboxylic acids pass through the membrane at a substantially faster rate than the remainder of the mixture thereby substantially separating the acids from the mixture.

Chum, Helena L. (Arvada, CO); Sopher, David W. (Maarssenbroek, NL)

1984-01-01

54

Separation of certain carboxylic acids utilizing cation exchange membranes  

DOEpatents

A method of substantially separating monofunctional lower carboxylic acids from a liquid mixture containing the acids wherein the pH of the mixture is adjusted to a value in the range of from about 1 to about 5 to form protonated acids. The mixture is heated to an elevated temperature not greater than about 100/sup 0/C and brought in contact with one side of a perfluorinated cation exchange membrane having sulfonate or carboxylate groups or mixtures thereof with the mixture containing the protonated acids. A pressure gradient can be established across the membrane with the mixture being under higher pressure, so that protonated monofunctional lower carboxylic acids pass through the membrane at a substantially faster rate than the remainder of the mixture thereby substantially separating the acids from the mixture.

Chum, H.L.; Sopher, D.W.

1983-05-09

55

Corrosion inhibition of steel in concrete by carboxylic acids  

Microsoft Academic Search

Water soluble carboxylic acids have been used as corrosion inhibitors. They remain largely soluble after curing in cement for up to 90d. Corrosion current measurements are presented showing malonic acid, a dicarboxylic acid, to be a very effective corrosion inhibitor even in the presence of 2.5 wt % chloride. Unfortunately, it has an initial retarding effect on the set of

K. K. Sagoe-Crentsil; F. P. Glasser; V. T. Yilmaz

1993-01-01

56

Current methods used for the production of carboxylic acid  

E-print Network

preventing consumption of inorganic acids and bases and the associated production of inorganic waste salt. Conventional versus New Method Most bacterial acid fermentations are carried out at neutral p that some relevant bio-based carboxylic acids, and hence their esters, are projected to become multi

Langendoen, Koen

57

Carboxylic acid functionalization prevents the translocation of multi-walled carbon nanotubes at predicted environmentally relevant concentrations into targeted organs of nematode Caenorhabditis elegans  

NASA Astrophysics Data System (ADS)

Carboxyl (-COOH) surface modified multi-walled carbon nanotubes (MWCNTs-COOH) can be used for targeted delivery of drugs and imaging. However, whether MWCNTs-COOH at environmentally relevant concentrations exert certain toxic effects on multicellular organisms and the underlying mechanisms are still largely unclear. In the present study, we applied the nematode Caenorhabditis elegans to evaluate the properties of MWCNTs-COOH at environmentally relevant concentrations by comparing the effects of MWCNTs and MWCNTs-COOH exposure on C. elegans from L1-larvae to adult at concentrations of 0.001-1000 ?g L-1. Exposure to MWCNTs could potentially damage the intestine (primary targeted organ) at concentrations greater than 0.1 ?g L-1 and functions of neurons and reproductive organ (secondary targeted organs) at concentrations greater than 0.001 ?g L-1. Carboxyl modification prevented the toxicity of MWCNTs on the primary and the secondary targeted organs at concentrations less than 100 ?g L-1, suggesting that carboxyl modification can effectively prevent the adverse effects of MWCNTs at environmentally relevant concentrations. After exposure, MWCNTs-COOH (1 mg L-1) were translocated into the spermatheca and embryos in the body through the primary targeted organs. However, MWCNTs-COOH (10 ?g L-1) were not observed in spermatheca and embryos in the body of nematodes. Moreover, relatively high concentrations of MWCNTs-COOH exposed nematodes might have a hyper-permeable intestinal barrier, whereas MWCNTs-COOH at environmentally relevant concentrations effectively sustained the normally permeable state for the intestinal barrier. Therefore, we elucidated the cellular basis of carboxyl modification to prevent toxicity of MWCNTs at environmentally relevant concentrations. Our data highlights the key role of biological barriers in the primary targeted organs to block toxicity formation from MWCNTs, which will be useful for the design of effective prevention strategies against MWCNTs toxicity.Carboxyl (-COOH) surface modified multi-walled carbon nanotubes (MWCNTs-COOH) can be used for targeted delivery of drugs and imaging. However, whether MWCNTs-COOH at environmentally relevant concentrations exert certain toxic effects on multicellular organisms and the underlying mechanisms are still largely unclear. In the present study, we applied the nematode Caenorhabditis elegans to evaluate the properties of MWCNTs-COOH at environmentally relevant concentrations by comparing the effects of MWCNTs and MWCNTs-COOH exposure on C. elegans from L1-larvae to adult at concentrations of 0.001-1000 ?g L-1. Exposure to MWCNTs could potentially damage the intestine (primary targeted organ) at concentrations greater than 0.1 ?g L-1 and functions of neurons and reproductive organ (secondary targeted organs) at concentrations greater than 0.001 ?g L-1. Carboxyl modification prevented the toxicity of MWCNTs on the primary and the secondary targeted organs at concentrations less than 100 ?g L-1, suggesting that carboxyl modification can effectively prevent the adverse effects of MWCNTs at environmentally relevant concentrations. After exposure, MWCNTs-COOH (1 mg L-1) were translocated into the spermatheca and embryos in the body through the primary targeted organs. However, MWCNTs-COOH (10 ?g L-1) were not observed in spermatheca and embryos in the body of nematodes. Moreover, relatively high concentrations of MWCNTs-COOH exposed nematodes might have a hyper-permeable intestinal barrier, whereas MWCNTs-COOH at environmentally relevant concentrations effectively sustained the normally permeable state for the intestinal barrier. Therefore, we elucidated the cellular basis of carboxyl modification to prevent toxicity of MWCNTs at environmentally relevant concentrations. Our data highlights the key role of biological barriers in the primary targeted organs to block toxicity formation from MWCNTs, which will be useful for the design of effective prevention strategies against MWCNTs toxicity. Electronic supplementary information (ESI) available. See DOI: 10

Nouara, Abdelli; Wu, Qiuli; Li, Yinxia; Tang, Meng; Wang, Haifang; Zhao, Yuliang; Wang, Dayong

2013-06-01

58

Synthesis, spectroscopy and computational studies of selected hydroxyquinoline carboxylic acids and their selected fluoro-, thio-, and dithioanalogues  

NASA Astrophysics Data System (ADS)

The faster and more efficient new synthetic methodologies of crystalline hydroxyquinoline carboxylic acids and their fluoro-, thio- and dithioanalogues were elaborated. The FTIR, multinuclear NMR, UV-Vis and single crystal X-ray characteristics of the series of quinoline carboxylic acids have been determined experimentally and rationalized on the basis of DFT calculation method with B3LYP functional.

Nycz, Jacek E.; Malecki, Grzegorz J.

2013-01-01

59

Quinoline based receptor in fluorometric discrimination of carboxylic acids  

PubMed Central

Summary Quinoline and naphthalene-based fluororeceptors 1 and 2 have been designed and synthesized for detection of hydroxy carboxylic acids in less polar solvents. The receptor 1 shows monomer emission quenching followed by excimer emission upon hydrogen bond-mediated complexation of carboxylic acids. The excimer emission distinguishes aromatic dicarboxylic acids from aliphatic dicarboxylic acids and even long chain aliphatic dicarboxylic acids from short chain aliphatic dicarboxylic acids. The receptor 1 is found to be selective for citric acid with a strong excimer emission in CHCl3. On the contrary, the receptor 2 exhibited less binding constant value and did not form any excimer upon complexation with the same acids under similar conditions. This established the role of quinoline ring nitrogen in binding with the acids. PMID:19190738

Adhikari, Suman; Chattopadhyay, Asoke P; Chowdhury, Purnendu Roy

2008-01-01

60

Dissolving Carboxylic Acids and Primary Amines on the Overhead Projector  

ERIC Educational Resources Information Center

Liquid carboxylic acids (or primary amines) with limited solubility in water are dissolved by addition of aqueous sodium hydroxide (or hydrochloric acid) on the stage of an overhead projector using simple glassware and very small quantities of chemicals. This effective and colorful demonstration can be used to accompany discussions of the…

Solomon, Sally D.; Rutkowsky, Susan A.

2010-01-01

61

Novel Lactate Transporters from Carboxylic Acid-Producing Rhizopus  

Technology Transfer Automated Retrieval System (TEKTRAN)

The fungus Rhizopus is frequently used for fermentative production of lactic acid, but little is known about the mechanisms or proteins for transporting this carboxylic acid. Since transport of the lactate anion across the plasma membrane is critical to prevent acidification of the cytoplasm, we ev...

62

Origins and variations of light carboxylic acids in polar precipitation  

NASA Astrophysics Data System (ADS)

Central Greenland and East Antarctic ice cores have been studied to investigate the carboxylic acid (acetate, CH3COO-; formate, HCOO-; glycolate, C2H3O3-; and oxalate, C2O4--) content of high-latitude precipitation. The two records cover the end of the last glacial age, the last great climatic change having occurred between 10,000 and 15,000 years B.P., and the Holocene period which started some 10,000 years ago. Carboxylic acids were measured using ion chromatography. These measurements are more difficult and require more stringent precautions to prevent sample contamination than inorganic trace species measurements. Carboxylic acids account for up to 25% of the free acidity in Greenland and are one order of magnitude more abundant in Greenland than in Antarctic precipitation. In Greenland precipitation deposited under present climatic conditions, formic and acetic acids are both present at the 10 ng g-1 level and are the most abundant carboxylic acids, while glycolic and oxalic acids with concentrations close to 1 ng g-1 represent minor carboxylic acid species. The level of formic, and to a lesser extent acetic, acid is also found to be strongly pH dependent. There is less formic acid at depths corresponding to periods when the acidity of the atmosphere was enhanced by a volcanic activity. Over the last 12,700 years, the carboxylic acid level of Greenland precipitation has often been sporadically enhanced by several orders of magnitude. Such large perturbations, which are accompanied by large increases of NH4+ concentrations, are probably caused by biomass-burning events which occurred at high northern latitudes. A particular chemical feature appears in snow layers corresponding to biomass-burning events which occurred during the Younger Dryas (11,550 to 12,700 years B.P.). During this cold stage, the precipitation was alkaline and the events were accompanied by an input of nitrite suggesting that peroxyacetyl nitrate (PAN) was present in the atmosphere and was hydrolyzed in alkaline cloud water. Formate and acetate profiles indicate that background levels of these carboxylic acids were 5 and 2 times lower, respectively, during the last glacial maximum (15,000 to 34,000 years B.P.) than during the Holocene stage in Greenland precipitation. The increases of the acetate and formate snow contents in response to the glacial-interglacial climatic transition exhibit a time lag of some 5000 years. In particular, the formic acid increase follows perfectly the timing of the retreat of the Laurentide ice sheet from 18,000 years B.P. to the mid-Holocene stage (6000 years B.P.). Our data suggest therefore that carboxylic acids in Greenland precipitation are mainly linked to emissions from the high-latitude continental biosphere. In contrast, the incloud oxidation of formaldehyde produced from methane oxidation under acidic conditions likely represents the main source of formic acid in East Antarctica. Finally, the study of recent Greenland snow deposits indicates that the expected trend of carboxylic acid concentrations due to man-made activities is counteracted by a simultaneous increase of the acidity related to growing fossil fuel combustion, which leads to a less efficient uptake of carboxylic acids into precipitation.

Legrand, Michel; de Angelis, Martine

1995-01-01

63

Metabolic engineering of biocatalysts for carboxylic acids production  

PubMed Central

Fermentation of renewable feedstocks by microbes to produce sustainable fuels and chemicals has the potential to replace petrochemical-based production. For example, carboxylic acids produced by microbial fermentation can be used to generate primary building blocks of industrial chemicals by either enzymatic or chemical catalysis. In order to achieve the titer, yield and productivity values required for economically viable processes, the carboxylic acid-producing microbes need to be robust and well-performing. Traditional strain development methods based on mutagenesis have proven useful in the selection of desirable microbial behavior, such as robustness and carboxylic acid production. On the other hand, rationally-based metabolic engineering, like genetic manipulation for pathway design, has becoming increasingly important to this field and has been used for the production of several organic acids, such as succinic acid, malic acid and lactic acid. This review investigates recent works on Saccharomyces cerevisiae and Escherichia coli, as well as the strategies to improve tolerance towards these chemicals. PMID:24688671

Liu, Ping; Jarboe, Laura R.

2012-01-01

64

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl  

E-print Network

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation-functionalized polysty- rene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K

Roden, Eric E.

65

Enhance decarboxylation reaction of carboxylic acids in clay minerals.  

NASA Astrophysics Data System (ADS)

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 Brønsted 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 cariers. 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 enhance by gamma radiation in several orders of magnitude.

Negrón-Mendoza, A.; Ramos, S.; Albarrán, G.

1995-02-01

66

40 CFR 721.10381 - Cyclic carboxylic acid, polymer with dihydroxy dialkyl ether, hydroxy substituted alkane and...  

Code of Federal Regulations, 2013 CFR

...dihydroxy dialkyl ether, hydroxy substituted alkane and carboxylic acid anhydride, methacrylate...dihydroxy dialkyl ether, hydroxy substituted alkane and carboxylic acid anhydride, methacrylate...dihydroxy dialkyl ether, hydroxy substituted alkane and carboxylic acid anhydride,...

2013-07-01

67

40 CFR 721.10381 - Cyclic carboxylic acid, polymer with dihydroxy dialkyl ether, hydroxy substituted alkane and...  

Code of Federal Regulations, 2012 CFR

...dihydroxy dialkyl ether, hydroxy substituted alkane and carboxylic acid anhydride, methacrylate...dihydroxy dialkyl ether, hydroxy substituted alkane and carboxylic acid anhydride, methacrylate...dihydroxy dialkyl ether, hydroxy substituted alkane and carboxylic acid anhydride,...

2012-07-01

68

40 CFR 721.10381 - Cyclic carboxylic acid, polymer with dihydroxy dialkyl ether, hydroxy substituted alkane and...  

...dihydroxy dialkyl ether, hydroxy substituted alkane and carboxylic acid anhydride, methacrylate...dihydroxy dialkyl ether, hydroxy substituted alkane and carboxylic acid anhydride, methacrylate...dihydroxy dialkyl ether, hydroxy substituted alkane and carboxylic acid anhydride,...

2014-07-01

69

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

ERIC Educational Resources Information Center

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)

Leung, Sam H.

2000-01-01

70

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 2. Major structures  

USGS Publications Warehouse

Polycarboxylic acid structures that account for the strong-acid characteristics (pKa1 near 2.0) were examined for fulvic acid from the Suwannee River. Studies of model compounds demonstrated that pKa values near 2.0 occur only if the ??-ether or ??-ester groups were in cyclic structures with two to three additional electronegative functional groups (carboxyl, ester, ketone, aromatic groups) at adjacent positions on the ring. Ester linkage removal by alkaline hydrolysis and destruction of ether linkages through cleavage and reduction with hydriodic acid confirmed that the strong carboxyl acidity in fulvic acid was associated with polycarboxylic ??-ether and ??-ester structures. Studies of hypothetical structural models of fulvic acid indicated possible relation of these polycarboxylic structures with the amphiphilic and metal-binding properties of fulvic acid.

Leenheer, J.A.; Wershaw, R.L.; Reddy, M.M.

1995-01-01

71

Bimolecular decomposition pathways for carboxylic acids of relevance to biofuels.  

PubMed

The bimolecular thermal reactions of carboxylic acids were studied using quantum mechanical molecular modeling. Previous work1 investigated the unimolecular decomposition of a variety of organic acids, including saturated, ?,?-unsaturated, and ?,?-unsaturated acids, and showed that the type and position of the unsaturation resulted in unique branching ratios between dehydration and decarboxylation, [H2O]/[CO2]. In this work, the effect of bimolecular chemistry (water-acid and acid-acid) is considered with a representative of each acid class. In both cases, the strained 4-centered, unimolecular transition state, typical of most organic acids, is opened up to 6- or 8-centered bimolecular geometries. These larger structures lead to a reduction in the barrier heights (20-45%) of the thermal decomposition pathways for organic acids and an increase in the decomposition kinetics. In some cases, they even cause a shift in the branching ratio of the corresponding product slates. PMID:25513721

Clark, Jared M; Nimlos, Mark R; Robichaud, David J

2015-01-22

72

Acidity distribution of carboxyl groups in Loy Yang brown coal: its analysis and the change by heat treatment  

Microsoft Academic Search

Brown coals have a considerable number of acidic functional groups of which the main component is carboxyl groups, and the acidity has a wide distribution. In this paper, changes of the acidity distribution were examined by aqueous titration when brown coal was heat-treated to control its acidity distribution. For Loy Yang brown coal from Australia dried at 50°C under vacuum

Kenji Murakami; Ryuhei Kondo; Kiyoshi Fuda; Toshiaki Matsunaga

2003-01-01

73

Gallium-catalyzed reductive chlorination of carboxylic acids with copper(II) chloride.  

PubMed

Described herein is the direct chlorination of carboxylic acids using copper(II) chloride via a gallium(III)-catalyzed reduction in the presence of a hydrosiloxane. During this reductive chlorination, the counteranions of CuCl2 functioned as a chloride source. PMID:25295703

Sakai, Norio; Nakajima, Takumi; Yoneda, Shinichiro; Konakahara, Takeo; Ogiwara, Yohei

2014-11-01

74

Extraction chemistry of fermentation product carboxylic acids  

SciTech Connect

Within the framework of a program aiming to improve the existing extractive recovery technology of fermentation products, the state of the art is critically reviewed. The acids under consideration are propionic, lactic, pyruvic, succinic, fumaric, maleic, malic, itaconic, tartaric, citric, and isocitric, all obtained by the aerobic fermentation of glucose via the glycolytic pathways and glyoxylate bypass. With no exception, it is the undissociated monomeric acid that is extracted into carbon-bonded and phosphorus-bonded oxygen donor extractants. In the organic phase, the acids are usually dimerized. The extractive transfer process obeys the Nernst law, and the measured partition coefficients range from about 0.003 for aliphatic hydrocarbons to about 2 to 3 for aliphatic alcohols and ketones to about 10 or more for organophosphates. Equally high distribution ratios are measured when long-chain tertiary amines are employed as extractants, forming bulky salts preferentially soluble in the organic phase.

Kertes, A.S.; King, C.J.

1986-02-01

75

Extraction chemistry of fermentation product carboxylic acid  

SciTech Connect

Within the framework of a program aiming to improve the existing extractive recovery technology of fermentation products, the state of the art is critically reviewed. The acids under consideration are propionic, lactic, pyruvic, succinic, fumaric, maleic, malic, itaconic, tartaric, citric, and isocitric, all obtained by the aerobic fermentation of glucose via the glycolytic pathway and glyoxylate bypass. With no exception, it is the undissociated monomeric acid that is extracted into carbon-bonded and phosphorus-bonded oxygen donor extractants. In the organic phase, the acids are usually dimerized. The extractive transfer process obeys the Nernst law, and the measured partition coefficients range from about 0.003 for aliphatic hydrocarbons to about 2 to 3 for aliphatic alcohols and ketones to about 10 or more for organophosphates. Equally high distribution ratios are measured when long-chain tertiary amines are employed as extractants, forming bulky salts preferentially soluble in the organic phase. 123 references.

Kertes, A.S.; King, C.J.

1986-02-01

76

40 CFR 721.10550 - Rare earth salt of a carboxylic acid (generic).  

Code of Federal Regulations, 2013 CFR

...2013-07-01 2013-07-01 false Rare earth salt of a carboxylic acid (generic...Chemical Substances § 721.10550 Rare earth salt of a carboxylic acid (generic...substance identified generically as rare earth salt of a carboxylic acid (PMN...

2013-07-01

77

40 CFR 721.10550 - Rare earth salt of a carboxylic acid (generic).  

...2014-07-01 2014-07-01 false Rare earth salt of a carboxylic acid (generic...Chemical Substances § 721.10550 Rare earth salt of a carboxylic acid (generic...substance identified generically as rare earth salt of a carboxylic acid (PMN...

2014-07-01

78

On The Two Component Microwave Mediated Reaction of Isonitriles with Carboxylic Acids: Regarding Alleged Formimidate Carboxylate Mixed Anhydrides  

PubMed Central

Microwave induced two component coupling (2CC) reaction of carboxylic acids with isonitriles gives rise to various N-formylamides. The formimidate carboxylate mixed anhydride (FCMA) is proposed as the reactive intermediate, which undergoes 1,3-O ? N acyl transfer to give the observed product. The formation and survival of the labile FCMA system has been evaluated. PMID:18783224

Li, Xuechen; Yuan, Yu; Berkowitz, William F.; Todaro, Louis J.; Danishefsky, Samuel J.

2008-01-01

79

On the two-component microwave-mediated reaction of isonitriles with carboxylic acids: regarding alleged formimidate carboxylate mixed anhydrides.  

PubMed

Microwave induced two-component coupling (2CC) reaction of carboxylic acids with isonitriles gives rise to various N-formylamides. The formimidate carboxylate mixed anhydride (FCMA) is proposed as the reactive intermediate, which undergoes 1,3-O-->N acyl transfer to give the observed product. The formation and survival of the labile FCMA system has been evaluated. PMID:18783224

Li, Xuechen; Yuan, Yu; Berkowitz, William F; Todaro, Louis J; Danishefsky, Samuel J

2008-10-01

80

Extraction chemistry of fermentation product carboxylic acids  

Microsoft Academic Search

Within the framework of a program aiming to improve the existing extractive recovery technology of fermentation products, the state of the art is critically reviewed. The acids under consideration are propionic, lactic, pyruvic, succinic, fumaric, maleic, malic, itaconic, tartaric, citric, and isocitric, all obtained by the aerobic fermentation of glucose via the glycolytic pathways and glyoxylate bypass. With no exception,

A. S. Kertes; C. J. King

1986-01-01

81

Highly visible-light luminescence properties of the carboxyl-functionalized short and ultrashort MWNTs  

SciTech Connect

Luminescence of the short multiwalled carbon nanotubes (MWNTs) conjugated with carboxylic acid groups has been studied. The results show that the carboxyl-functionalized short MWNTs could emit luminescence and the emission peak appears at 500 nm with a corresponding optimal excitation wavelength centering at 310 nm. When the short MWNTs are filtered through 0.15 {mu}m polytetrafluoroethylene (PTFE) membrane, the ultrashort MWNTs are obtained from the filtrate. An interesting feature for the ultrashort MWNTs is that the emission intensity is strengthened and the peak is slightly blue shifted to 460 nm. This result indicates that the luminescence properties of MWNTs are strongly affected by the tube length. After chemical oxidization cutting, defects and carboxylic acid groups at the tube end and/or sidewall can be produced; the more shorten of MWNTs, the better dispersion and carboxylic passivation of the nanotubes, and the more intense luminescence emissions. The broad emissions are logically attributed to the trapping of excitation energy by defect sites in the carboxyl-functionalized nanotube structure. - Graphical abstract: Luminescence of the short and ultrashort multiwalled carbon nanotubes (MWNTs) conjugated with carboxylic acid groups, which is logically attributed to the trapping of excitation energy by defect sites, has been studied.

Luo Yongsong [Department of Physics, Central China Normal University, Wuhan 430079 (China); Department of Physics, XinYang Normal University, Xinyang 464000 (China)], E-mail: ysluo@mails.ccnu.edu.cn; Xia Xiaohong [Department of Physics, Central China Normal University, Wuhan 430079 (China); Liang Ying [Department of Physics, Central China Normal University, Wuhan 430079 (China); Zhang Yonggang [Department of Physics, Central China Normal University, Wuhan 430079 (China); Ren Qinfeng [Department of Physics, Central China Normal University, Wuhan 430079 (China); Li Jialin [Department of Physics, Central China Normal University, Wuhan 430079 (China)], E-mail: lijl@phy.ccnu.edu.cn; Jia Zhijie [Department of Physics, Central China Normal University, Wuhan 430079 (China); Tang Yiwen [Department of Physics, Central China Normal University, Wuhan 430079 (China)

2007-06-15

82

Toxicity of perfluorinated carboxylic acids for aquatic organisms  

PubMed Central

Toxicity of perfluorinated carboxylic acids with carbon chain C8 to C12 were tested with oligochaeta Tubifex tubifex. Toxicity was evaluated as the exposure time ET50 from onset of damage of the oligochaeta in saturated aqueous solutions. The ET50 fluctuated between 25 and 257 minutes. No statistically significant difference was found among the C8, C9 and C12 acids (ET50 between 143 and 257 minutes with large standard deviation). The acids with carbon chain C10 and C11 induced the effect significantly quicker (25 to 47 minutes). No acute toxicity measured in the three-minute test was observed in any case. PMID:21217876

Tichý, Milo?; Valigurová, Radka; ?abala, Radomír; Uzlová, Rut; Rucki, Marián

2010-01-01

83

Toxicity of perfluorinated carboxylic acids for aquatic organisms.  

PubMed

Toxicity of perfluorinated carboxylic acids with carbon chain C(8) to C(12) were tested with oligochaeta Tubifex tubifex. Toxicity was evaluated as the exposure time ET(50) from onset of damage of the oligochaeta in saturated aqueous solutions. The ET(50) fluctuated between 25 and 257 minutes. No statistically significant difference was found among the C(8), C(9) and C(12) acids (ET(50) between 143 and 257 minutes with large standard deviation). The acids with carbon chain C(10) and C(11) induced the effect significantly quicker (25 to 47 minutes). No acute toxicity measured in the three-minute test was observed in any case. PMID:21217876

Tichý, Milo?; Valigurová, Radka; Cabala, Radomír; Uzlová, Rut; Rucki, Marián

2010-06-01

84

Carboxylic acids permeases in yeast: two genes in Kluyveromyces lactis.  

PubMed

Two new genes KlJEN1 and KlJEN2 were identified in Kluyveromyces lactis. The deduced structure of their products is typical of membrane-bound carriers and displays high similarity to Jen1p, the monocarboxylate permease of Saccharomyces cerevisiae. Both KlJEN1 and KlJEN2 are under the control of glucose repression mediated by FOG1 and FOG2, corresponding to S. cerevisiae GAL83 and SNF1 respectively, and KlCAT8, proteins involved in glucose signalling cascade in K. lactis. KlJEN1, but not KlJEN2, is induced by lactate. KlJEN2 in contrast is expressed at high level in ethanol and succinate. The physiological characterization of null mutants showed that KlJEN1 is the functional homologue of ScJEN1, whereas KlJEN2 encodes a dicarboxylic acids transporter. In fact, KlJen1p [transporter classification (TC) number: 2.A.1.12.2.] is required for lactate uptake and therefore for growth on lactate. KlJen2p is required for succinate transport, as demonstrated by succinate uptake experiments and by inability of Kljen2 mutant to grow on succinate. This carrier appears to transport also malate and fumarate because the Kljen2 mutant cannot grow on these substrates and the succinate uptake is competed by these carboxylic acids. We conclude that KlJEN2 is the first yeast gene shown to encode a dicarboxylic acids permease. PMID:15363851

Lodi, Tiziana; Fontanesi, Flavia; Ferrero, Iliana; Donnini, Claudia

2004-09-15

85

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids  

PubMed Central

Summary The near-unlimited availability of CO2 has stimulated a growing research effort in creating value-added products from this greenhouse gas. This paper presents the trends on the most important methods used in the electrochemical synthesis of carboxylic acids from carbon dioxide. An overview is given of different substrate groups which form carboxylic acids upon CO2 fixation, including mechanistic considerations. While most work focuses on the electrocarboxylation of substrates with sacrificial anodes, this review considers the possibilities and challenges of implementing other synthetic methodologies. In view of potential industrial application, the choice of reactor setup, electrode type and reaction pathway has a large influence on the sustainability and efficiency of the process. PMID:25383120

Matthessen, Roman; Fransaer, Jan; Binnemans, Koen

2014-01-01

86

Silver-Catalyzed Arylation of (Hetero)arenes by Oxidative Decarboxylation of Aromatic Carboxylic Acids.  

PubMed

A long-standing challenge in Minisci reactions is achieving the arylation of heteroarenes by oxidative decarboxylation of aromatic carboxylic acids. To address this challenge, the silver-catalyzed intermolecular Minisci reaction of aromatic carboxylic acids was developed. With an inexpensive silver salt as a catalyst, this new reaction enables a variety of aromatic carboxylic acids to undergo decarboxylative coupling with electron-deficient arenes or heteroarenes regardless of the position of the substituents on the aromatic carboxylic acid, thus eliminating the need for ortho-substituted aromatic carboxylic acids, which were a limitation of previously reported methods. PMID:25537369

Kan, Jian; Huang, Shijun; Lin, Jin; Zhang, Min; Su, Weiping

2015-02-01

87

Integrated process for preparing a carboxylic acid from an alkane  

Microsoft Academic Search

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,

Abraham Benderly; Nitin Chadda; Douglass Sevon

2011-01-01

88

Carboxylate-functionalized phosphomolybdates: ligand-directed conformations.  

PubMed

The [HPMo6O21](2-) units and carboxylate linkers can be combined to build novel polyanions by a carefully designed complementary system in self-assembly processes depending only on the number of carboxyl groups and the nature of carboxylic acids. Complexes (NH4)5[HPMo6O21(O2CC6H4OH)3]·4H2O (1), (NH4)8H2[(HPMo6O21)2(C2O4)3]·13H2O (2), (NH4)20[(HPMo6O21)4(O2CCH2CO2)6]·17H2O (3), and Cs2(NH4)10[(HPMo6O21)2(HPO3){C6H3(CO2)3}2]·5H2O (4) have been synthesized by a simple one-pot reaction of (NH4)6Mo7O24·4H2O, H3PO3, and carboxylic acid ligands in aqueous solution. Formation of these compounds is critically dependent on the identifying carboxylic acids, which play the important templated role in assembly processes. The stability of these clusters was explored using electrospray ionization mass spectrometry (ESI-MS) and (31)P NMR spectroscopy, and electron paramagnetic resonance (EPR) experiments further demonstrated the result of the interesting photochromic property. PMID:23844943

Yang, Donghui; Li, Suzhi; Ma, Pengtao; Wang, Jingping; Niu, Jingyang

2013-08-01

89

Lipase catalyzed resolution of chiral acids or alcohols using mixed carboxylic-carbonic anhydrides  

Microsoft Academic Search

Mixed carboxylic-carbonic anhydrides are efficient irreversible acyl transfer reagents for lipase catalyzed esterification in organic media, and can be used for the resolution of chiral carboxylic acids or alcohols.

Eryka Guibé-Jampel; Zbigniew Chalecki; Mohamed Bassir; Mirjana Gelo-Pujic

1996-01-01

90

Molecular Ecology of Carboxylic Acids in Hydrothermal Environments  

NASA Astrophysics Data System (ADS)

Hydrothermal environments in the primitive ocean on the Earth must have played an important role for harnessing a molecular ecology processing various carbon through-flows in the pre-RNA world. Even carboxylic acids alone could have maintained a primitive evolutionary ecology near hot vents on the seafloor. We examined whether the citric acid cycle could run in a simulated hydrothermal environment with the aid of neither reducing agents nor enzymes of biological origin under the premise that pyruvate was already available. When the major carboxylic acid molecules constituting the citric acid cycle including pyruvate were prepared in a flow reactor and the reaction fluid was circulated between hot and cold regions in a cyclic manner, the member molecules of the cycle were found to increase with the operation of the reactor. The cycle was found robust enough to synthesize the member molecules from within even in the face of adverse or hostile disturbances from the outside. The cycle was oxidative instead of being reductive, and the effective oxidant was water molecules. Underlying the operation of a molecular ecology running on the oxidative citric acid cycle is the physical pruning principle of the faster temperature drop going with the greater stored latent heat applied to any reactants crossing sharp temperature gradients.

Matsuno, K.

2005-12-01

91

Functionalized carboxyl nanoparticles enhance mucus dispersion and hydration  

PubMed Central

Luminal accumulation of viscous, poorly hydrated, and less transportable mucus has been associated with altered mucus rheology and reduced mucociliary clearance. These symptoms are some of the cardinal clinical manifestations found throughout major respiratory diseases as well as gastrointestinal and digestive disorders. Applications of current mucolytics may yield short-term improvements but are continuously challenged by undesirable side-effects. While nanoparticles (NPs) can interact with mucin polymers, whether functionalized NPs can rectify mucus rheology is unknown. Herein, we report that carboxyl-functionalized NPs (24?nm and 120?nm) dramatically reduced mucin gel size and accelerated mucin matrix hydration rate (diffusivity). Our results suggest that carboxyl-functionalized NPs disperse mucin gels possibly by enhancing network hydration. This report highlights the prospective usages of carboxyl-functionalized NPs as a novel mucus dispersant or mucolytic agent in adjusting mucus rheological properties and improving mucociliary transport to relieve clinical symptoms of patients suffering from relevant diseases. PMID:22355725

Chen, Eric Y.; Daley, David; Wang, Yung-Chen; Garnica, Maria; Chen, Chi-Shuo; Chin, Wei-Chun

2012-01-01

92

Functionalized carboxyl nanoparticles enhance mucus dispersion and hydration  

NASA Astrophysics Data System (ADS)

Luminal accumulation of viscous, poorly hydrated, and less transportable mucus has been associated with altered mucus rheology and reduced mucociliary clearance. These symptoms are some of the cardinal clinical manifestations found throughout major respiratory diseases as well as gastrointestinal and digestive disorders. Applications of current mucolytics may yield short-term improvements but are continuously challenged by undesirable side-effects. While nanoparticles (NPs) can interact with mucin polymers, whether functionalized NPs can rectify mucus rheology is unknown. Herein, we report that carboxyl-functionalized NPs (24 nm and 120 nm) dramatically reduced mucin gel size and accelerated mucin matrix hydration rate (diffusivity). Our results suggest that carboxyl-functionalized NPs disperse mucin gels possibly by enhancing network hydration. This report highlights the prospective usages of carboxyl-functionalized NPs as a novel mucus dispersant or mucolytic agent in adjusting mucus rheological properties and improving mucociliary transport to relieve clinical symptoms of patients suffering from relevant diseases.

Chen, Eric Y.; Daley, David; Wang, Yung-Chen; Garnica, Maria; Chen, Chi-Shuo; Chin, Wei-Chun

2012-01-01

93

Transcriptomic analysis of the role of carboxylic acids in metabolite signaling in Arabidopsis leaves.  

PubMed

The transcriptional response to metabolites is an important mechanism by which plants integrate information about cellular energy and nutrient status. Although some carboxylic acids have been implicated in the regulation of gene expression for select transcripts, it is unclear whether all carboxylic acids have the same effect, how many transcripts are affected, and how carboxylic acid signaling is integrated with other metabolite signals. In this study, we demonstrate that perturbations in cellular concentrations of citrate, and to a lesser extent malate, have a major impact on nucleus-encoded transcript abundance. Functional categories of transcripts that were targeted by both organic acids included photosynthesis, cell wall, biotic stress, and protein synthesis. Specific functional categories that were only regulated by citrate included tricarboxylic acid cycle, nitrogen metabolism, sulfur metabolism, and DNA synthesis. Further quantitative real-time polymerase chain reaction analysis of specific citrate-responsive transcripts demonstrated that the transcript response to citrate is time and concentration dependent and distinct from other organic acids and sugars. Feeding of isocitrate as well as the nonmetabolizable citrate analog tricarballylate revealed that the abundance of selected marker transcripts is responsive to citrate and not downstream metabolites. Interestingly, the transcriptome response to citrate feeding was most similar to those observed after biotic stress treatments and the gibberellin biosynthesis inhibitor paclobutrazol. Feeding of citrate to mutants with defects in plant hormone signaling pathways did not completely abolish the transcript response but hinted at a link with jasmonic acid and gibberellin signaling pathways. Our results suggest that changes in carboxylic acid abundances can be perceived and signaled in Arabidopsis (Arabidopsis thaliana) by as yet unknown signaling pathways. PMID:23487434

Finkemeier, Iris; König, Ann-Christine; Heard, William; Nunes-Nesi, Adriano; Pham, Phuong Anh; Leister, Dario; Fernie, Alisdair R; Sweetlove, Lee J

2013-05-01

94

Overexpression of salicylic acid carboxyl methyltransferase reduces salicylic acid-mediated pathogen resistance in Arabidopsis thaliana  

Microsoft Academic Search

We cloned a salicylic acid\\/benzoic acid carboxyl methyltransferase gene, OsBSMT1, from Oryza sativa. A recombinant OsBSMT1 protein obtained by expressing the gene in Escherichia coli exhibited carboxyl methyltransferase activity in reactions with salicylic acid (SA), benzoic acid (BA), and de-S-methyl benzo(1,2,3)thiadiazole-7-carbothioic acid (dSM-BTH), producing methyl salicylate (MeSA), methyl benzoate (MeBA),\\u000a and methyl dSM-BTH (MeBTH), respectively. Compared to wild-type plants, transgenic

Yeon Jong Koo; Myeong Ae Kim; Eun Hye Kim; Jong Tae Song; Choonkyun Jung; Joon-Kwan Moon; Jeong-Han Kim; Hak Soo Seo; Sang Ik Song; Ju-Kon Kim; Jong Seob Lee; Jong-Joo Cheong; Yang Do Choi

2007-01-01

95

Carboxylic Acid Deprotonation on the Ag(110) and Ag(111) Bryan Parker  

E-print Network

with that of perfluorinated carboxylic acids on the Ag(110) and Ag(111) surfaces. The hydrocarbon acids adsorb reversibly of the perfluorinated acids is quite different from that of the hydrocarbon acids in the sense that they deprotonate

Gellman, Andrew J.

96

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

ERIC Educational Resources Information Center

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)

Forster, Denis; DeKleva, Thomas W.

1986-01-01

97

THE SOLVENT EXTRACTION OF RARE-EARTH METALS BY CARBOXYLIC ACIDS  

Microsoft Academic Search

The solvent extraction of the trivalent lanthanides and yttrium from nitrate media by solutions of carboxylic acids in xylene has been studied. Commercially available carboxylic acids such as Versatic 10 and naphthenic acids were used, as well as model compounds of known structure, such as 2-ethylhexanoic and 3-cyclohexylpropanoic acids. In a few cases, extraction of the metals from sulphate and

A. C. du Preez; J. S. Preston

1992-01-01

98

Two Dimensional Polyamides Prepared From Unsaturated Carboxylic Acids And Amines.  

DOEpatents

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.

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

99

Functionalization of poly-SNS-anchored carboxylic acid with Lys and PAMAM: surface modifications for biomolecule immobilization/stabilization and bio-sensing applications.  

PubMed

Poly(2-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl) (SNS) acetic acid) was electrochemically deposited on graphite electrodes and functionalized with lysine (Lys) amino acid and poly(amidoamine) derivatives (PAMAM G2 and PAMAM G4) to investigate their matrix properties for biosensor applications. Glucose oxidase (GOx) was immobilized onto the modified surface as the model enzyme. X-Ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used to report the surface properties of the matrices in each step of the biosensor construction. The biosensors were characterized in terms of their operational and storage stabilities and the kinetic parameters (K(app)(m) and I(max)). Three new glucose biosensors revealed good stability, featuring low detection limits (19.0 ?M, 3.47 ?M and 2.93 ?M for lysine-, PAMAM G2- and PAMAM G4-functionalized electrodes, respectively) and prolonged the shelf lives (4, 5, and 6 weeks for Lys-, PAMAM G2- and PAMAM G4-modified electrodes, respectively). The proposed biosensors were tested for glucose detection on real human blood serum samples. PMID:22832474

Demirci, Sema; Emre, Fatma Bilge; Ekiz, Fulya; O?uzkaya, Funda; Timur, Suna; Tanyeli, Cihangir; Toppare, Levent

2012-09-21

100

Catalytic amide formation from non-activated carboxylic acids and amines.  

PubMed

The amide functionality is found in a wide variety of biological and synthetic structures such as proteins, polymers, pesticides and pharmaceuticals. Due to the fact that synthetic amides are still mainly produced by the aid of coupling reagents with poor atom-economy, the direct catalytic formation of amides from carboxylic acids and amines has become a field of emerging importance. A general, efficient and selective catalytic method for this transformation would meet well with the increasing demands for green chemistry procedures. This review covers catalytic and synthetically relevant methods for direct condensation of carboxylic acids and amines. A comprehensive overview of homogeneous and heterogeneous catalytic methods is presented, covering biocatalysts, Lewis acid catalysts based on boron and metals as well an assortment of other types of catalysts. PMID:24430887

Lundberg, Helena; Tinnis, Fredrik; Selander, Nicklas; Adolfsson, Hans

2014-04-21

101

Separation of linear hydrocarbons and carboxylic acids from ethanol and hexane solutions by reverse osmosis  

Microsoft Academic Search

In this study, asymmetric cellulose acetate membranes with moderate NaCl rejection (85.5%) were prepared and used to study the influence of the chemical nature of organic solutes in different organic solvents. The solute rejection and the solvent flux of linear hydrocarbons (Mw=226–563g\\/mol) and linear carboxylic acids (Mw=228–340g\\/mol) in ethanol and hexane were studied as a function of the molecular weight,

G. H. Koops; S. Yamada; S.-I. Nakao

2001-01-01

102

New approaches to the synthesis of selected hydroxyquinolines and their hydroxyquinoline carboxylic acid analogues  

NASA Astrophysics Data System (ADS)

New approaches to the synthesis of selected crystalline hydroxyquinolines and their carboxylic acid analogues were elaborated in this paper with the auxiliary of computational and spectroscopic characterization, such as FTIR, NMR and single crystal X-ray measurements. The experimental data were further rationalized based on a DFT calculation method with B3LYP functional, which reflected the impact of electron donating or withdrawing groups on the energy level of HOMO orbitals and the reactivity of the substituted hydroxyquinolines.

Szala, Marcin; Nycz, Jacek E.; Malecki, Grzegorz J.

2014-08-01

103

Determination of Carboxylic Acids from Plant Root Exudates by Ion Exclusion Chromatography with ESI-MS  

Microsoft Academic Search

Ion-exclusion chromatography (IEC) coupled with electrospray ionization quadrupole mass spectrometry (ESI-MS) has been used\\u000a for the analysis of carboxylic acids. The use of ESI-MS provides increased specificity and sensitivity compared to existing\\u000a detection methods. This paper applies IEC-ESI-MS to the analysis of carboxylic acids in commonly found root exudates and shows\\u000a that the separation of nine carboxylic acids (pyruvic, oxalic,

Zuliang Chen; Kwon-Rae Kim; Gary Owens; Ravendra Naidu

2008-01-01

104

Integrated process for preparing a carboxylic acid from an alkane  

DOEpatents

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.

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

2011-12-20

105

Aug-MIA-QSPR modeling of the soil sorption of carboxylic acid herbicides.  

PubMed

Soil sorption, described as logK OC (the logarithm of the soil/water partition coefficient normalized to organic carbon), was modeled using the augmented multivariate image analysis applied to quantitative structure-property relationship method for a series of 11 carboxylic acid herbicides. The statistical model was found to be highly predictive and reliable to estimate logK OC of other persistent organic pollutants in the soil, which are analogues of the carboxylic acids used in the QSPR model. The QSPR model derived from images corresponding to the chemical structures of the 11 herbicides is superior to the uniparameter model based on the octanol/water partition coefficient (logP) and, in addition, a pattern recognition model was built using principal component analysis. This model allowed clustering and separating compounds with low/moderate soil sorption from those with moderate/high soil sorption (compounds with the aryloxy function) using the second principal component. PMID:25134926

Freitas, Mirlaine R; Freitas, Matheus P; Macedo, Renato L G

2014-10-01

106

Titania-Promoted Carboxylic Acid Alkylations of Alkenes and Cascade Addition–Cyclizations  

PubMed Central

Photochemical reactions employing TiO2 and carboxylic acids under dry anaerobic conditions led to several types of C–C bond-forming processes with electron-deficient alkenes. The efficiency of alkylation varied appreciably with substituents in the carboxylic acids. The reactions of aryloxyacetic acids with maleimides resulted in a cascade process in which a pyrrolochromene derivative accompanied the alkylated succinimide. The selectivity for one or other of these products could be tuned to some extent by employing the photoredox catalyst under different conditions. Aryloxyacetic acids adapted for intramolecular ring closures by inclusion of 2-alkenyl, 2-aryl, or 2-oximinyl functionality reacted rather poorly. Profiles of reactant consumption and product formation for these systems were obtained by an in situ NMR monitoring technique. An array of different catalyst forms were tested for efficiency and ease of use. The proposed mechanism, involving hole capture at the TiO2 surface by the carboxylates followed by CO2 loss, was supported by EPR spectroscopic evidence of the intermediates. Deuterium labeling indicated that the titania likely donates protons from surface hydroxyl groups as well as supplying electrons and holes, thus acting as both a catalyst and a reaction partner. PMID:24437519

2014-01-01

107

Titania-promoted carboxylic acid alkylations of alkenes and cascade addition-cyclizations.  

PubMed

Photochemical reactions employing TiO2 and carboxylic acids under dry anaerobic conditions led to several types of C-C bond-forming processes with electron-deficient alkenes. The efficiency of alkylation varied appreciably with substituents in the carboxylic acids. The reactions of aryloxyacetic acids with maleimides resulted in a cascade process in which a pyrrolochromene derivative accompanied the alkylated succinimide. The selectivity for one or other of these products could be tuned to some extent by employing the photoredox catalyst under different conditions. Aryloxyacetic acids adapted for intramolecular ring closures by inclusion of 2-alkenyl, 2-aryl, or 2-oximinyl functionality reacted rather poorly. Profiles of reactant consumption and product formation for these systems were obtained by an in situ NMR monitoring technique. An array of different catalyst forms were tested for efficiency and ease of use. The proposed mechanism, involving hole capture at the TiO2 surface by the carboxylates followed by CO2 loss, was supported by EPR spectroscopic evidence of the intermediates. Deuterium labeling indicated that the titania likely donates protons from surface hydroxyl groups as well as supplying electrons and holes, thus acting as both a catalyst and a reaction partner. PMID:24437519

Manley, David W; McBurney, Roy T; Miller, Phillip; Walton, John C; Mills, Andrew; O'Rourke, Christopher

2014-02-01

108

Separation of Aliphatic and Aromatic Carboxylic Acids by Conventional and Ultra High Performance Ion Exclusion Chromatography  

PubMed Central

An ion exclusion chromatography (IELC) comparison between a conventional ion exchange column and an ultra-high performance liquid chromatography (UHPLC) dynamically surfactant modified C18 column for the separation of an aliphatic carboxylic acid and two aromatic carboxylic acids is presented. Professional software is used to optimize the conventional IELC separation conditions for acetylsalicylic acid and the hydrolysis products: salicylic acid and acetic acid. Four different variables are simultaneously optimized including H2SO4 concentration, pH, flow rate, and sample injection volume. Thirty different runs are suggested by the software. The resolutions and the time of each run are calculated and feed back to the software to predict the optimum conditions. Derringer’s desirability functions are used to evaluate the test conditions and those with the highest desirability value are utilized to separate acetylsalicylic acid, salicylic acid, and acetic acid. These conditions include using a 0.35 mM H2SO4 (pH 3.93) eluent at a flow rate of 1 mL min-1 and an injection volume of 72 ?L. To decrease the run time and improve the performance, a UHPLC C18 column is used after dynamic modification with sodium dodecyl sulfate. Using pure water as a mobile phase, a shorter analysis time and better resolution are achieved. In addition, the elution order is different from the IELC method which indicates the contribution of the reversed-phase mode to the separation mechanism. PMID:24285874

Mansour, Fotouh R.; Kirkpatrick, Christine L.; Danielson, Neil D.

2013-01-01

109

Molecular Self-Assembly of Enantiopure Heptahelicene-2-Carboxylic Acid on Calcite (1014)  

E-print Network

Molecular Self-Assembly of Enantiopure Heptahelicene-2-Carboxylic Acid on Calcite (1014)-heptahelicene-2-carboxylic acid ((M)-[7]HCA) on the calcite (1014) cleavage plane under ultrahigh vacuum along the calcite [0110] direction. Here, we investigate the enantiopure (M)- [7]HCA compound, resulting

Kühnle, Angelika

110

Direct Condensation of Carboxylic Acids with Alcohols Catalyzed by Hafnium(IV) Salts  

Microsoft Academic Search

In order to promote atom efficiency in synthesis and to avoid the generation of environmental waste, the use of stoichiometric amounts of condensing reagents or excess substrates should be avoided. In esterification, excesses of either carboxylic acids or alcohols are normally needed. We show that the direct condensation of equimolar amounts of carboxylic acids and alcohols can be achieved with

Kazuaki Ishihara; Suguru Ohara; Hisashi Yamamoto

2000-01-01

111

Photophysical properties of dysprosium complexes with aromatic carboxylic acids by molecular spectroscopy  

Microsoft Academic Search

A series of luminescent dysprosium complexes with different aromatic carboxylic acids have been synthesized and characterized. The photophysical properties of these complexes have been studied with all kinds of molecular spectroscopy such as infrared spectra, ultraviolet spectra, phosphorescence spectra and fluorescence spectra. Especially the energy match and intramolecular energy transfer process between the triplet state energies of aromatic carboxylic acids

Bing Yan; Bing Zhou

2005-01-01

112

Recovery of Carboxylic Acids from Fermentation Broth via Acid Springing  

E-print Network

................................................................ 50 3-39 pH of distillate samples collected from tripropyl ammonium acetate with tri-n-octylamine at different bottom temperatures ............................. 51 3-40 Acetic acid concentration of distillate samples collected from tributyl.... The results indicated that tributylamine is the best choice among several kinds of low-molecular-weight tertiary amine. The optimal temperature for concentrating tributyl ammonium acetate is about 110 oC, and the optimal temperature for recovering acetic...

Dong, Jipeng

2010-01-14

113

Investigation of Carboxylic Acid-Neodymium Conversion Films on Magnesium Alloy  

NASA Astrophysics Data System (ADS)

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.

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

2015-01-01

114

Electron mobility enhancement in ZnO thin films via surface modification by carboxylic acids  

NASA Astrophysics Data System (ADS)

Modifying the surface of polycrystalline ZnO films using a monolayer of organic molecules with carboxylic acid attachment groups increases the field-effect electron mobility and zero-bias conductivity, resulting in improved transistors and transparent conductors. The improvement is consistent with the passivation of defects via covalent bonding of the carboxylic acid and is reversible by exposure to a UV-ozone lamp. The properties of the solvent used for the attachment are crucial because solvents with high acid dissociation constants (Ka) for carboxylic acids lead to high proton activities and etching of the nanometers-thick ZnO films, masking the electronic effect.

Spalenka, Josef W.; Gopalan, Padma; Katz, Howard E.; Evans, Paul G.

2013-01-01

115

A Zn-based, pillared paddlewheel MOF containing free carboxylic acids via covalent post-synthesis elaborationw  

E-print Network

A Zn-based, pillared paddlewheel MOF containing free carboxylic acids via covalent post to functionalize each cavity. Thus, we chose the Zn-based, mixed-ligand (pillared paddlewheel) MOF 1 (Scheme 1 Article on the web 26th May 2009 DOI: 10.1039/b823392f A Zn-based, mixed-ligand (pillared paddlewheel

116

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

SciTech Connect

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.

Tung, L.A.

1993-08-01

117

Influence of carboxylic acid functionalities in ruthenium (II) polypyridyl complexes on DNA binding, cytotoxicity and antioxidant activity: synthesis, structure and in vitro anticancer activity.  

PubMed

Four new Ru(II) complexes [RuHCl(bpy)(PPh(3))(CO)] (1), [RuHCl(bpy)(AsPh(3))(CO)] (2) (bpy = 2,2'-bipyridine), [RuCl(HL)(PPh(3))(2)(CO)] (3) and [RuCl(HL)(AsPh(3))(2)(CO)] (4) (HL = 2,2'-bipyridine-4,4'-dicarboxylic acid) were synthesized and characterized. X-ray diffraction was used to characterize 3 in solid state. The interactions of these complexes with DNA were explored by different techniques which revealed that the complexes could bind to CT-DNA through non-intercalation. The in vitro cytotoxic and antioxidant activities of the complexes validated against a panel of cancer cell lines and free radicals showed that 3 and 4 possess quite high anticancer and antioxidant activities over 1, 2 and standard drugs. An apparent dependence of biological activities on incorporation of COOH in bipyridine moiety was noticed: Inclusion of COOH caused significant differences in DNA binding, cytotoxicity and antioxidant activity. PMID:23234855

Sathiya Kamatchi, Thangavel; Chitrapriya, Nataraj; Kim, Seog K; Fronczek, Frank R; Natarajan, Karuppannan

2013-01-01

118

Gustatory Responses of Eel Palatine Receptors to Amino Acids and Carboxylic Acids  

E-print Network

ABSTRACT The gustatory receptors of the eel palate were found to be extremely sensitive to amino acids and carboxylic acids. The results obtained are as follows: (a) 11 amino acids which are among naturally occurring amino acids elicited responses in the palatine nerve, but 9 amino acids did not elicit a response even at a high concentration. The effect of D-amino acids was always much less than that of their corresponding L-isomers. There was no appreciable difference in the effectiveness of an a-amino acid (a-alanine) and fl-amino acid (fl-alanine). (b) The threshold concentrations of the most potent amino acids (arginine, glycine) were between 10-s and 10-aM. A linear relation between the magnitude of the response and log stimulus concentration held for a wide concentration range for all the amino acids examined. (c) The palatine receptors responded sensitively to various carboxylic acid solutions whose pH was adjusted to neutral. The threshold concentrations varied between 10-4 and 10-7M. The magnitude of the response at 10-2M increased with an increase of carbon chain length. (d) The extent of cross-adaptation was examined with various combinations of amino acids. A variety of the response patterns showing complete cross-adaptation, no cross-adaptation, or synergetic interaction was observed. The synergetic interaction was also observed when one amino acid below its threshold concentration was added to the other amino acid. No cross-adaptation was observed between amino acids and fatty acids. (e) The treatment of the palate with papain led to loss of the responses to arginine, glycine, and histidine without affecting those to proline and acetic acid. The treatment with pronase E eliminated selectively the response to proline. The possibility that the eel gustatory receptors are responsible for sensing food at a distance was discussed.

Kiyonori Yoshii; Naoki Kamo; Kenzo Kurihara

119

Heat capacity, saturation vapor pressure, and thermodynamic functions of ethyl esters of C3-C5 and C18 carboxylic acids  

NASA Astrophysics Data System (ADS)

The heat capacities of ethyl propanoate (EPr), ethyl n-pentanoate (EPen), and ethyl n-octadecanoate (ethyl stearate, ESt) were measured by vacuum adiabatic calorimetry in the temperature range of 6 to 373 K. Triple point temperatures, fusion enthalpies and entropies, and purity of the samples of the sub-stances under study were determined. The saturation vapor pressures for EPr and EPen were determined by comparative ebulliometry in an atmospheric pressure range of 4.0 to 101.7 kPa. The normal boiling points and vaporization enthalpies vs. temperature were obtained. The standard thermodynamic functions ( S, H, and G) were calculated for the condensed and ideal gas states on the basis of the experimental data. The vapor pressures of the atmospheric range were extrapolated to entire ranges of the liquid phases of EPr and EPen using the principle of corresponding states and the combined processing of pT parameters and low-temperature differences in the heat capacities of an ideal gas and liquid.

Agafonova, L. E.; Varushchenko, R. M.; Druzhinina, A. I.; Polyakova, O. V.; Kolesov, Yu. S.

2011-09-01

120

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.  

PubMed

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 biological carboxylic acids, such as lactic acid (LA), 3-hydroxybutylic acid, maric acid, succinic acid, ?-ketoglutalic acid, and citric acid, were clearly identified in the saliva of healthy persons and diabetic patients. Furthermore, the ratio of D-LA in diabetic patients was higher than that in normal subjects. Judging from these results, PCP2 seems to be a useful chiral derivatization reagent for the determination not only of chiral, but also achiral, carboxylic acids in real samples. PMID:24500756

Kuwabara, Tomohiro; Takayama, Takahiro; Todoroki, Kenichiro; Inoue, Koichi; Min, Jun Zhe; Toyo'oka, Toshimasa

2014-04-01

121

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

SciTech Connect

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-based distribution ratios increase from 0.11 to 0.46 as the aqueous phase pH increases from 7.18 to 8.15. Regeneration of the organic extractant solution was carried out by stripping at elevated temperatures to remove the ammonia, with 99% recovery of the ammonia being obtained at 125 C.

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

1990-03-01

122

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

PubMed

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. PMID:25342454

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

2014-10-24

123

The study of 8-Hydroxyquinoline-2-Carboxyllic acid and its metal ion complexing properties.  

E-print Network

??The metal ion coordinating properties of the ligand HQC (8-hydroxyquinoline-2- carboxylic acid) were studied by UV-visible spectroscopy and X-ray crystallography. The protonation constants of HQC… (more)

McDonald, F. Crisp Jr.

2009-01-01

124

Facile and efficient synthesis of quinoline-4-carboxylic acids under microwave irradiation  

Microsoft Academic Search

A facile and efficient method for the preparation of 2-non-substituted quinoline-4-carboxylic acids is described via the Pfitzinger reaction of isatins with sodium pyruvate following consequent decarboxylation under microwave irradiation.

Hui Zhu; Ri Fang Yang; Liu Hong Yun; Jin Li

2010-01-01

125

The effect of carboxylic acid anions on the stability of framework mineral grains in petroleum reservoirs  

SciTech Connect

This paper presents experimental and empirical evidence to show that carboxylic acid anions (CAA's) are a major diagenetic control on first-cycle basins in Jurassic-to-Pleistocene reservoirs in the 80-to-120{degrees}C thermal window.

MacGowan, D.B.; Surdam, R.C.; Ewing, R.E. (Wyoming Univ., Laramie, WY (USA))

1990-06-01

126

Identification of Amides as Carboxylic Acid Surrogates for Quinolizidinone-Based M1 Positive Allosteric Modulators  

PubMed Central

Selective activation of the M1 muscarinic receptor via positive allosteric modulation represents an approach to treat the cognitive decline in patients with Alzheimer's disease. A series of amides were examined as a replacement for the carboxylic acid moiety in a class of quinolizidinone carboxylic acid M1 muscarinic receptor positive allosteric modulators, and leading pyran 4o and cyclohexane 5c were found to possess good potency and in vivo efficacy. PMID:24900430

2012-01-01

127

Surface Functionalization of Poly(ethylene terephthalate) Film and Membrane by Controlled Wet Chemistry: Chemical Characterization of Carboxylated Surfaces  

Microsoft Academic Search

Surface functionalization of poly(ethylene terephthalate) (PET) film or track-etched membrane was performed using the methods of organic synthesis conducted at the solid-liquid interface. Basic hydrolysis in aqueous acetonitrile followed by permanganate oxidation in diluted sulfuric acid created new carboxylic chain-ends. These reactive functions were assayed as follows: (i) activation with water soluble carbodiimide; (ii) coupling to 3 H-labeled amino acids;

Jacqueline Marchand-Brynaert; Michéle Deldime; Isabelle Dupont; Jean-Luc Dewez; Yves-Jacques Schneider

1995-01-01

128

Determination of perfluorinated carboxylic acids in biological samples by high-performance liquid chromatography  

Microsoft Academic Search

This paper describes a method for the quantitative determination of perfluorinated carboxylic acids (PFCAs), perfluorohexanoic acid (C6-PFCA), perfluoroheptanoic acid (C7-PFCA), perfluorooctanoic acid (C8-PFCA), perfluorononanoic acid (C9-PFCA) and perfluorodecanoic acid (C10-PFCA), in biological samples. PFCA in liver homogenates was extracted as an ion pair with tetrabutylammonium (TBA) ion into organic solvent, then the PFCA was derivatized with 3-bromoacetyl-7-methoxycoumarin (BrAMC) and quantified

Takeshi Ohya; Naomi Kudo; Erika Suzuki; Yoichi Kawashima

1998-01-01

129

Sorption of carboxylic acid from carboxylic salt solutions at pHs close to or above the pK[sub a] of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine  

DOEpatents

Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH[sub a] into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. The acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carboxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia. 8 figs.

King, C.J.; Tung, L.A.

1992-07-21

130

The 5,6-dihydroxyindole-2-carboxylic acid (DHICA) oxidase activity of human tyrosinase.  

PubMed Central

Melanin synthesis in mammals is catalysed by at least three enzymic proteins, tyrosinase (monophenol dihydroxyphenylalanine:oxygen oxidoreductase, EC 1.14.18.1) and tyrosinase-related proteins (tyrps) 1 and 2, whose genes map to the albino, brown and slaty loci in mice, respectively. Tyrosinase catalyses the rate-limiting generation of L-dopaquinone from L-tyrosine and is also able to oxidize L-dopa to L-dopaquinone. Conversely, mouse tyrp1, but not tyrosinase, catalyses the oxidation of the indolic intermediate 5,6-dihydroxyindole-2-carboxylic acid (DHICA) into the corresponding 5,6-indolequinone-2-carboxylic acid, thus promoting the incorporation of DHICA units into eumelanin. The catalytic activities of the human melanogenic enzymes are still debated. TYRP1 has been reported to lack DHICA oxidase activity, whereas tyrosinase appears to accelerate DHICA consumption, thus raising the question of DHICA metabolism in human melanocytes. Here we have used two different approaches, comparison of the catalytic activities of human melanocytic cell lines expressing the full set of melanogenic enzymes or deficient in TYRP1, and transient expression of TYR and tyr genes in COS7 cells, to demonstrate that human tyrosinase actually functions as a DHICA oxidase, as opposed to the mouse enzyme. Therefore, human tyrosinase displays a broader substrate specificity than its mouse counterpart, and might be at least partially responsible for the incorporation of DHICA units into human eumelanins. PMID:11171088

Olivares, C; Jiménez-Cervantes, C; Lozano, J A; Solano, F; García-Borrón, J C

2001-01-01

131

Carboxylic acids in secondary aerosols from oxidation of cyclic monoterpenes by ozone  

SciTech Connect

A series of smog chamber experiments have been conducted in which five cyclic monoterpenes were oxidized by ozone. The evolved secondary aerosol was analyzed by GC-MS and HPLC-MS for nonvolatile polar oxidation products with emphasis on the identification of carboxylic acids. Three classes of compounds were determined at concentration levels corresponding to low percentage molar yields: i.e., dicarboxylic acids, oxocarboxylic acids, and hydroxyketocarboxylic acids. Carboxylic acids are highly polar and have lower vapor pressures than their corresponding aldehydes and may thus play an important role in secondary organic aerosol formation processes. The most abundant carboxylic acids were the following: cis-pinic acid AB1(cis-3-carboxy-2,2-dimethylcyclobutylethanoic acid) from {alpha} and {beta}-pinene; cis-pinonic acid A3 (cis-3-acetyl-2,2-dimethylcyclobutylethanoic acid) and cis-10-hydroxypinonic acid Ab6 (cis-2,2-dimethyl-3-hydroxyacetylcyclobutyl-ethanoic acid) from {alpha}-pinene and {beta}-pinene; cis-3-caric acid C1 (cis-2,2-dimethyl-1,3-cyclopropyldiethanoic acid), cis-3-caronic acid C3 (2,2-dimethyl-3-(2-oxopropyl)cyclopropanylethanoic acid), and cis-10-hydroxy-3-caronic acid C6 (cis-2,2-dimethyl-3(hydroxy-2-oxopropyl)cyclopropanylethanoic acid) from 3-carene; cis-sabinic acid S1 (cis-2-carboxy-1-isopropylcyclopropylethanoic acid) from sabinene; limonic acid L1 (3-isopropenylhexanedioic acid), limononic acid L3 (3-isopropenyl-6-oxo-heptanoic acid), 7-hydroxy-limononic acid L6 (3-isopropenyl-7-hydroxy-6-oxoheptanoic acid), and 7-hydroxylimononic acid Lg{prime} (7-hydroxy-3-isopropenyl-6-oxoheptanoic acid) from limonene.

Glasius, M.; Lahaniati, M.; Calogirou, A.; Di Bella, D.; Jensen, N.R.; Hjorth, J.; Kotzias, D.; Larsen, B.R.

2000-03-15

132

The lactam of alpha-guanidinoglutaric acid (1-amidino-2-pyrrolidone-5-carboxylic acid).  

PubMed

alpha-Guanidinoglutaric acid (alpha-GGA) has been reported to occur in the cerebral cortex after epileptic seizures. No physical characteristics of alpha-GGA have been given. A practical procedure for the preparation of alpha-GGA is reported here. alpha-GGA forms a lactam in aqueous solution at 80 degrees C. It is proposed to substitute this lactam, 1-amidino-2-pyrrolidone-5-carboxylic acid (pAGlu), for pyroglutamic acid (pGlu) at the N-terminal position in neuropeptides to modify their biological characteristics. L(+)-Glutamic acid was reacted with S-methylisothiourea (I) at pH 10 in aqueous solution to form L(-)-alpha-guanidinoglutaric acid: mp 165-168 degrees C, [alpha]22D = -22.7 (C = 4, 2 M HCl). alpha-GGA reacted promptly with excess reagent to form a salt, S-methylisothiourea-alpha-guanidinoglutarate: mp 209-210 degrees C, [alpha]22D = -13.0 (C = 4, 2 M HCl). I was removed from the salt with aqueous picric acid, since I readily formed an insoluble picrate, S-methylisothiourea picrate (mp 225-228 degrees C). Alternatively, the salt was added to a cation exchange column, and the alpha-GGA was eluted with molar ammonium acetate buffer, pH 9.5. Its lactam, 1-amidino-2-pyrrolidone-5-carboxylic acid, mp 248-249 degrees C, [alpha]22D = +2.1 (C = 4, 2 M HCl), formed a picrate (mp 196-199 degrees C). PMID:2874749

Natelson, S

1986-07-01

133

Anti-inflammatory, antiproteolytic, and antihemolytic properties of pyrrole carboxylic acids.  

PubMed

Eight substituted pyrrole carboxylic acids were evaluated for their anti-inflammatory activity against carageenin-induced edema in rats. The protection afforded by seven of these compounds at a dose of 100 mg/kg i.p. ranged from 11 to 42%. Indomethacin (10 mg/kg i.p.), used as a reference drug, possessed 45% anti-inflammatory activity under similar experimental conditions. The ability of these compounds to exhibit in vitro antiproteolytic activity was reflected by their ability to inhibit trypsin-induced hydrolysis of bovine serum albumin. The inhibition of the activity of trypsin by these substituted pyrrole carboxylic acids (1 mM) ranged from 42 to 90% while such an inhibition with indomethacin (1 mM) was 95%. The in vitro membrane stabilizing property of these substituted pyrrole carboxylic acids was observed by their ability to provide protection against heat-induced dog erythrocyte hemolysis. The I50 value of these compounds, representing the concentration required to inhibit one-half of heat-induced erythrocyte hemolysis, ranged from 0.29 to 6.0 mM. Such an inhibition was concentration-dependent and biphasic in nature. The I50 value for indomethacin, showing greater antihemolytic activity was found to be 0.02 mM under similar experimental conditions. These results have provided some correlation of anti-inflammatory activity with antiproteolytic and membrane stabilizing properties for substituted pyrrole-3-carboxylic acids alone but not for pyrrole-2-carboxylic acids. PMID:7291298

Davis, J S; Waters, J A; Parmar, S S

1981-01-01

134

Reaction Of ?,?-Unsaturated Carboxylic Acids With Thallium Triacetate (Tta): Lactonization VS Oxidative Decarboxylation  

Microsoft Academic Search

The reaction of six ?,?-unsaturated carboxylic acids with thallium triacetate (TTA) was studied. The nature of the products is highly sensitive to the substitution pattern of the substrates. Aliphatic acids gave mainly lactones, while those bearing an aromatic ring furnished only decarboxylation products.

Helena M. C. Ferraz; M?nica V. A. Grazini; Luiz F. Silva Jr; Luiz S. Longo Jr

1999-01-01

135

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

PubMed Central

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 current measurements in Fischer rat thyroid (FRT) cells expressing human TMEM16A. IC50 values were calculated using YFP fluorescence plate reader assay. Final compounds, having free carboxylic group displayed significant inhibition. Eight of the novel compounds B02, B13, B21, B23, B25, B27, B28, B29 exhibit excellent CaCCs inhibition with IC50 value <6 ?M, with compound B25 exhibiting the lowest IC50 value of 2.8 ± 1.3 ?M. None of the tested ester analogs of final benzofuran derivatives displayed TMEM16A/CaCCs inhibition. PMID:22739085

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

2013-01-01

136

The Biosynthetic Pathway of Indole-3-Carbaldehyde and Indole-3-Carboxylic Acid Derivatives in Arabidopsis.  

PubMed

Indolic secondary metabolites play an important role in pathogen defense in cruciferous plants. In Arabidopsis (Arabidopsis thaliana), in addition to the characteristic phytoalexin camalexin, derivatives of indole-3-carbaldehyde (ICHO) and indole-3-carboxylic acid (ICOOH) are synthesized from tryptophan via the intermediates indole-3-acetaldoxime and indole-3-acetonitrile. Based on feeding experiments combined with nontargeted metabolite profiling, their composition in nontreated and silver nitrate (AgNO3)-treated leaf tissue was comprehensively analyzed. As major derivatives, glucose conjugates of 5-hydroxyindole-3-carbaldehyde, ICOOH, and 6-hydroxyindole-3-carboxylic acid were identified. Quantification of ICHO and ICOOH derivative pools after glucosidase treatment revealed that, in response to AgNO3 treatment, their total accumulation level was similar to that of camalexin. ARABIDOPSIS ALDEHYDE OXIDASE1 (AAO1), initially discussed to be involved in the biosynthesis of indole-3-acetic acid, and Cytochrome P450 (CYP) 71B6 were found to be transcriptionally coexpressed with camalexin biosynthetic genes. CYP71B6 was expressed in Saccharomyces cerevisiae and shown to efficiently convert indole-3-acetonitrile into ICHO and ICOOH, thereby releasing cyanide. To evaluate the role of both enzymes in the biosynthesis of ICHO and ICOOH derivatives, knockout and overexpression lines for CYP71B6 and AAO1 were established and analyzed for indolic metabolites. The observed metabolic phenotypes suggest that AAO1 functions in the oxidation of ICHO to ICOOH in both nontreated and AgNO3-treated leaves, whereas CYP71B6 is relevant for ICOOH derivative biosynthesis specifically after induction. In summary, a model for the biosynthesis of ICHO and ICOOH derivatives is presented. PMID:24728709

Böttcher, Christoph; Chapman, Alexandra; Fellermeier, Franziska; Choudhary, Manisha; Scheel, Dierk; Glawischnig, Erich

2014-04-11

137

A mechanistic analysis of the increase in the thermal stability of proteins in aqueous carboxylic acid salt solutions.  

PubMed Central

The stability of proteins is known to be affected significantly in the presence of high concentration of salts and is highly pH dependent. Extensive studies have been carried out on the stability of proteins in the presence of simple electrolytes and evaluated in terms of preferential interactions and increase in the surface tension of the medium. We have carried out an in-depth study of the effects of a series of carboxylic acid salts: ethylene diamine tetra acetate, butane tetra carboxylate, propane tricarballylate, citrate, succinate, tartarate, malonate, and gluconate on the thermal stability of five different proteins that vary in their physico-chemical properties: RNase A, cytochrome c, trypsin inhibitor, myoglobin, and lysozyme. Surface tension measurements of aqueous solutions of the salts indicate an increase in the surface tension of the medium that is very strongly correlated with the increase in the thermal stability of proteins. There is also a linear correlation of the increase in thermal stability with the number of carboxylic groups in the salt. Thermal stability has been found to increase by as much as 22 C at 1 M concentration of salt. Such a high thermal stability at identical concentrations has not been reported before. The differences in the heat capacities of denaturation, deltaCp for RNase A, deduced from the transition curves obtained in the presence of varying concentrations of GdmCl and that of carboxylic acid salts as a function of pH, indicate that the nature of the solvent medium and its interactions with the two end states of the protein control the thermodynamics of protein denaturation. Among the physico-chemical properties of proteins, there seems to be an interplay of the hydrophobic and electrostatic interactions that lead to an overall stabilizing effect. Increase in surface free energy of the solvent medium upon addition of the carboxylic acid salts appears to be the dominant factor in governing the thermal stability of proteins. PMID:10210200

Kaushik, J. K.; Bhat, R.

1999-01-01

138

Communication: spectroscopic measurement of the binding energy of a carboxylic acid-water dimer.  

PubMed

Infrared-ultraviolet two color pump-probe spectroscopy is used to measure the binding energy, D(0,) of a carboxylic acid-water dimer where the acid is 9-hydroxy-9-fluorenecarboxylic acid. The acid-water configuration presents a standard structure for the general acid-water interaction where the water bonds to the carboxylic acid group through two intermolecular hydrogen bonds. Photodissociation studies with product vibrational state resolution have enabled an accurate determination of the binding energy for this acid-water system to be D(0) = 2975 ± 30 cm(-1). Quantum chemical calculations are performed to compare with the experimental observations and a recent measurement on the water dimer (D(0) = 1105 ± 10 cm(-1)). PMID:22583203

Gu, Quanli; Knee, J L

2012-05-01

139

Automatic analyzer for highly polar carboxylic acids based on fluorescence derivatization-liquid chromatography.  

PubMed

A sensitive, versatile, and reproducible automatic analyzer for highly polar carboxylic acids based on a fluorescence derivatization-liquid chromatography (LC) method was developed. In this method, carboxylic acids were automatically and fluorescently derivatized with 4-(N,N-dimethylaminosulfonyl)-7-piperazino-2,1,3-benzoxadiazole (DBD-PZ) in the presence of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride by adopting a pretreatment program installed in an LC autosampler. All of the DBD-PZ-carboxylic acid derivatives were separated on the ODS column within 30?min by gradient elution. The peak of DBD-PZ did not interfere with the separation and the quantification of all the acids with the exception of lactic acid. From the LC-MS/MS analysis, we confirmed that lactic acid was converted to an oxytriazinyl derivative, which was further modified with a dimethoxy triazine group of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM). We detected this oxytriazinyl derivative to quantify lactic acid. The detection limits (signal-to-noise ratio?=?3) for the examined acids ranged from 0.19 to 1.1?µm, which correspond to 95-550 fmol per injection. The intra- and inter-day precisions of typical, highly polar carboxylic acids were all <9.0%. The developed method was successfully applied to the comprehensive analysis of carboxylic acids in various samples, which included fruit juices, red wine and media from cultured tumor cells. Copyright © 2014 John Wiley & Sons, Ltd. PMID:25082081

Todoroki, Kenichiro; Nakano, Tatsuki; Ishii, Yasuhiro; Goto, Kanoko; Tomita, Ryoko; Fujioka, Toshihiro; Min, Jun Zhe; Inoue, Koichi; Toyo'oka, Toshimasa

2015-03-01

140

Peripherally and axially carboxylic acid substituted subphthalocyanines for dye-sensitized solar cells.  

PubMed

A series of subphthalocyanines (SubPcs) bearing a carboxylic acid group either at the peripheral or axial position have been designed and synthesized to investigate the influence of the COOH group positions on the dye-sensitized solar cell (DSSC) performance. The DSSC devices based on SubPcs with axially substituted carboxylic acid groups showed low photovoltaic performance, whereas peripherally substituted one exhibited higher power conversion efficiency owing to improved injection from LUMO of SubPcs to the TiO2 conduction band. PMID:24443172

Ince, Mine; Medina, Anaïs; Yum, Jun-Ho; Yella, Aswani; Claessens, Christian G; Martínez-Díaz, M Victoria; Grätzel, Michael; Nazeeruddin, Mohammad K; Torres, Tomás

2014-02-10

141

Thiol containing carboxylic acids remove the CTAB surfactant onto the surface of gold nanorods: An FTIR spectroscopic study  

NASA Astrophysics Data System (ADS)

Gold nanorods are mostly synthesized by chemical methods, using a directing agent: CTAB (cetyl-trimethyl-ammonium bromide). Due to the various applications of gold nanorods, the necessity to modify the surface functionalization appears. Thiol containing molecules are used as direct or cross-linking agents in the functionalization of gold nanorods. In this study we show that a thiol containing carboxylic acid mixture is able to remove a large part of CTAB molecules that surround the gold nanorods, and not only to cover the CTAB protecting layer. Using a simple FTIR spectroscopic method, it is possible to quantitatively determine the percentage of CTAB that is replaced by the functionalizing agent.

Garabagiu, Sorina; Bratu, Ioan

2013-11-01

142

Merging photoredox and nickel catalysis: decarboxylative cross-coupling of carboxylic acids with vinyl halides.  

PubMed

Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of ?-oxy and ?-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions. PMID:25521443

Noble, Adam; McCarver, Stefan J; MacMillan, David W C

2015-01-21

143

Enantioselective protonation of ?-hetero carboxylic acid-derived ketene disilyl acetals under chiral ionic Brønsted acid catalysis.  

PubMed

Highly enantioselective protonation of ?-halo and alkoxy carboxylic acid-derived ketene disilyl acetals is achieved by using P-spiro chiral diaminodioxaphosphonium barfate as a Brønsted acid catalyst, where the enantiofacial discrimination by the catalyst mainly stems from the recognition of the electronic difference between two substituents on the ketene disilyl acetal. PMID:25234847

Uraguchi, Daisuke; Kizu, Tomohito; Ohira, Yuki; Ooi, Takashi

2014-11-14

144

Interconversion of biologically important carboxylic acids by radiation  

NASA Technical Reports Server (NTRS)

The interconversion of a group of biologically important polycarboxylic acids (acetic, fumaric, malic, malonic, succinic, citric, isocitric, tricarballylic) under gamma-ray or ultraviolet radiation was investigated. The formation of high molecular weight compounds was observed in all cases. Succinic acid was formed in almost all radiolysis experiments. Citric, malonic, and succinic acids appeared to be relatively insensitive to radiation. Interconversion of the polycarboxylic acids studied may have occurred under the effect of radiation in the prebiotic earth.

Negron-Mendoza, A.; Ponnamperuma, C.

1978-01-01

145

Functionalised carboxylic acids in atmospheric particles: An annual cycle revealing seasonal trends and possible sources  

NASA Astrophysics Data System (ADS)

Carboxylic acids represent a major fraction of the water soluble organic carbon (WSOC) in atmospheric particles. Among the particle phase carboxylic acids, straight-chain monocarboxylic acids (MCA) and dicarboxylic acids (DCA) with 2-10 carbon atoms have extensively been studied in the past. However, only a few studies exist dealing with functionalised carboxylic acids, i.e. having additional hydroxyl-, oxo- or nitro-groups. Regarding atmospheric chemistry, these functionalised carboxylic acids are of particular interest as they are supposed to be formed during atmospheric oxidation processes, e.g. through radical reactions. Therefore they can provide insights into the tropospheric multiphase chemistry. During this work 28 carboxylic acids (4 functionalised aliphatic MCAs, 5 aromatic MCAs, 3 nitroaromatic MCAs, 6 aliphatic DCAs, 6 functionalised aliphatic DCAs, 4 aromatic DCAs) were quantitatively determined in 256 filter samples taken at the rural research station Melpitz (Saxony, Germany) with a PM10 Digitel DHA-80 filter sampler. All samples were taken in 2010 covering a whole annual cycle. The resulting dataset was examined for a possible seasonal dependency of the acid concentrations. Furthermore the influence of the air mass origin on the acid concentrations was studied based on a simple two-sector classification (western or eastern sector) using a back trajectory analysis. Regarding the annual average, adipic acid was found to be the most abundant compound with a mean concentration of 7.8 ng m-3 followed by 4-oxopimelic acid with 6.1 ng m-3. The sum of all acid concentrations showed two maxima during the seasonal cycle; one in summer and one in winter, whereas the highest overall acid concentrations were found in summer. In general the target acids could be divided into two different groups, where one group has its maximum concentration in summer and the other group during winter. The first group contains all investigated aliphatic mono- and dicarboxylic acids. The high concentrations in summer could lead to the conclusion that these acids are mostly formed during photochemical processes in the atmosphere. However, the concentrations in autumn were often exceeded by the ones in winter. Therefore probably other sources beside photochemical processes have to be considered. The second group consists of aromatic compounds. Because of the high concentrations in winter it can be concluded that photochemical formation plays a minor role and primary emission sources e.g., wood combustion are likely. Further evidence in determining sources of the carboxylic acids could be obtained from the air mass origin. In general, air masses transported from East have a more anthropogenic influence than the air mass inflow from West. For all aromatic carboxylic acids higher concentrations were determined during eastern inflow, indicating anthropogenic sources. This presumption is supported by high correlations with the elemental carbon (EC). Regarding the aliphatic carboxylic there is one group with higher concentrations when the air mass is transported from West and one with higher concentrations when air mass is transported from East. In summary the findings of this study reveal a clear difference in the seasonal trends of the single target acids indicating a variety of different sources.

Teich, Monique; van Pinxteren, Dominik; Herrmann, Hartmut

2013-04-01

146

Sorption of carboxylic acid from carboxylic salt solutions at PHS close to or above the pK.sub.a of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine  

DOEpatents

Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH.sub.a into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. the acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carobxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia.

King, C. Judson (Kensington, CA); Tung, Lisa A. (El Cerrito, CA)

1992-01-01

147

Sources and distribution of CuO-derived benzene carboxylic acids in soils and sediments  

Microsoft Academic Search

Cupric oxide (CuO) oxidation is a powerful tool for tracing different forms of organic carbon (OC), particularly vascular plant-derived OC, through the environment. The method produces a suite of benzene carboxylic acids (BCAs) whose sources have been unclear, but some of which have been used as tracers of soil OC in the ocean. In particular, some evidence suggested they might

Angela F. Dickens; Jack A. Gudeman; Yves Gélinas; Jeffrey A. Baldock; Willy Tinner; Feng Sheng Hu; John I. Hedges

2007-01-01

148

Ligand-free palladium-catalyzed aerobic oxidative coupling of carboxylic anhydrides with arylboronic acids.  

PubMed

We report a new, effective and environmentally friendly protocol for selective aerobic oxidative coupling of arylboronic acids with carboxylic anhydrides in the presence of ligand-free palladium catalyst. The aryl benzoates are obtained in good to excellent yields. PMID:24910234

Yin, Weiyan; He, Haifeng; Zhang, Yani; Long, Tong

2014-09-01

149

Relationship between chromatographic properties of aromatic carboxylic acids and their structure.  

PubMed

The retention of aromatic carboxylic acids and their esters in reversed-phase HPLC is proportional to the sum of their partition coefficients in octanol-water system and retention increments. This equation can be used for the identification of various side-products formed in monomer production. PMID:12831183

Grechishkina, Olga

2002-03-01

150

Toward Molecular Nanowires Self-Assembled on an Insulating Substrate: Heptahelicene-2-carboxylic acid on Calcite (101j4)  

E-print Network

acid on Calcite (101j4) Philipp Rahe,,§ Markus Nimmrich,,§ Andreas Greuling, Jens Schu¨tte, Irena G) cleavage plane of calcite. The molecule used is racemic heptahelicene-2-carboxylic acid, which forms

Kühnle, Angelika

151

Determination of polyfluoroalkyl phosphoric acid diesters, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, perfluoroalkyl carboxylic acids, and perfluoroalkane sulfonic acids in lake trout from the Great Lakes region.  

PubMed

A comprehensive method to extract perfluoroalkyl carboxylic acids, perfluoroalkane sulfonic acids, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, and polyfluoroalkyl phosphoric acid diesters simultaneously from fish samples has been developed. The recoveries of target compounds ranged from 78 % to 121 %. The new method was used to analyze lake trout (Salvelinus namaycush) from the Great Lakes region. The results showed that the total perfluoroalkane sulfonate concentrations ranged from 0.1 to 145 ng/g (wet weight) with perfluorooctane sulfonate (PFOS) as the dominant contaminant. Concentrations in fish between lakes were in the order of Lakes Ontario ? Erie > Huron > Superior ? Nipigon. The total perfluoroalkyl carboxylic acid concentrations ranged from 0.2 to 18.2 ng/g wet weight. The aggregate mean perfluorooctanoic acid (PFOA) concentration in fish across all lakes was 0.045 ± 0.023 ng/g. Mean concentrations of PFOA were not significantly different (p > 0.1) among the five lakes. Perfluoroalkyl phosphinic acids were detected in lake trout from Lake Ontario, Lake Erie, and Lake Huron with concentration ranging from non-detect (ND) to 0.032 ng/g. Polyfluoroalkyl phosphoric acid diesters were detected only in lake trout from Lake Huron, at levels similar to perfluorooctanoic acid. PMID:22722738

Guo, Rui; Reiner, Eric J; Bhavsar, Satyendra P; Helm, Paul A; Mabury, Scott A; Braekevelt, Eric; Tittlemier, Sheryl A

2012-11-01

152

Preferential Interaction of Na+ over K+ to Carboxylate-functionalized Silver Nanoparticles  

EPA Science Inventory

Elucidating mechanistic interactions between specific ions (Na+/ K+) and nanoparticle surfaces to alter particle stability in polar media has received little attention. We investigated relative preferential binding of Na+ and K+ to carboxylate-functionalized silver nanoparticles ...

153

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)  

EPA Science Inventory

The complex photochemical transformations of biogenic hydrocarbons such as isoprene and of anthropogenic hydrocarbons such as aromatics are an important source of carboxylic acids in the troposphere. The identification of unknown carboxylic acids can be difficul...

154

Dehydrative C-H/N-OH Functionalizations in H2O by Ruthenium(II) Catalysis: Subtle Effect of Carboxylate Ligands and Mechanistic Insight.  

PubMed

A ruthenium(II) complex derived from the electron-deficient aromatic carboxylic acid 3-(F3C)C6H4CO2H proved to be a highly efficient catalyst for dehydrative alkyne annulation by NH-free hydroxamic acids in water. The C-H/N-OH functionalization occurred with excellent positional selectivity as well as ample substrate scope, setting the stage for effective intermolecular alkenylations of hydroxamic acids. Detailed mechanistic studies were suggestive of a kinetically relevant C-H metalation by carboxylate assistance along with subsequent migratory alkyne insertion, reductive elimination, and intramolecular oxidative addition. PMID:25335189

Yang, Fanzhi; Ackermann, Lutz

2014-12-19

155

Profiling of chiral and achiral carboxylic acid metabolomics: synthesis and evaluation of triazine-type chiral derivatization reagents for carboxylic acids by LC-ESI-MS/MS and the application to saliva of healthy volunteers and diabetic patients.  

PubMed

Novel triazine-type chiral derivatization reagents, i.e., (S)-1-(4,6-dimethoxy-1,3,5-triazin-2-yl)pyrrolidin-3-amine (DMT-3(S)-Apy) and (S)-4,6-dimethoxy-N-(pyrrolidin-3-yl)-1,3,5-triazin-2-amine (DMT-1(S)-Apy), were developed for the highly sensitive and selective detection of chiral carboxylic acids by UPLC-MS/MS analysis. Among the synthesized reagents, DMT-3(S)-Apy was a more efficient chiral reagent for the enantiomeric separation of chiral carboxylic acids in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. The DMT-3(S)-Apy was used for the determination of 13 carboxylic acids in human saliva of healthy volunteers and diabetic patients. Various biological carboxylic acids including chiral carboxylic acids, and mono- and di-carboxylic acids were clearly identified in the saliva of healthy persons and diabetic patients. The concentrations of carboxylic acids detected in the saliva of diabetic patients were relatively higher than those in the healthy persons. Furthermore, the concentration of D-lactic acid (LA) and the ratio of D/L-LA in the diabetic patients were significantly higher than those in the healthy persons. The low ratio of D/L-LA in healthy persons was also identified to be independent of age and sex. These results suggest that the determination of the D/L-LA ratio in saliva might be applicable for the diagnosis of diabetes. Based on these observations, DMT-3(S)-Apy seems to be a useful chiral derivatization reagent for the determination not only of chiral carboxylic acids but also achiral ones. In conclusion, the proposed method using DMT-3(S)-Apy is useful for the carboxylic acid metabolomics study of various specimens. PMID:25366977

Takayama, Takahiro; Kuwabara, Tomohiro; Maeda, Toshio; Noge, Ichiro; Kitagawa, Yutaka; Inoue, Koichi; Todoroki, Kenichiro; Min, Jun Zhe; Toyo'oka, Toshimasa

2015-01-01

156

Robust carboxylic acid-terminated organic thin films and nanoparticle protectants generated from bidentate alkanethiols.  

PubMed

A new carboxylic acid-terminated alkanethiol having bidentate character, 16-(3,5-bis(mercaptomethyl)phenoxy)hexadecanoic acid (BMPHA), was designed as an absorbate and protectant to form thermally stable carboxylic acid-terminated organic thin films on flat gold and nanoparticles, respectively. The structural features of the organic thin films derived from BMPHA were characterized by ellipsometry, X-ray photoelectron spectroscopy (XPS), and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and compared to those derived from mercaptohexadecanoic acid (MHA) and 16-(4-(mercaptomethyl)phenoxy)hexadecanoic acid (MMPHA). This study demonstrates that films derived from BMPHA are less densely packed than films derived from MHA and MMPHA. However, the results of solution-phase thermal desorption tests revealed that the carboxylic acid-terminated films generated from BMPHA exhibit an enhanced thermal stability compared to those generated from MHA and MMPHA. Furthermore, as a nanoparticle protectant, BMPHA can be used to stabilize large gold nanoparticles (~45 nm diameter) in solution, and BMPHA-protected gold nanoparticles exhibited a high thermal stability in solution thermolysis studies. PMID:23855957

Lee, Han Ju; Jamison, Andrew C; Yuan, Yuehua; Li, Chien-Hung; Rittikulsittichai, Supachai; Rusakova, Irene; Lee, T Randall

2013-08-20

157

Mechanism of SmI2/Amine/H2O-Promoted Chemoselective Reductions of Carboxylic Acid Derivatives (Esters, Acids, and Amides) to Alcohols.  

PubMed

Samarium(II) iodide-water-amine reagents have emerged as some of the most powerful reagents (E° = -2.8 V) for the reduction of unactivated carboxylic acid derivatives to primary alcohols under single electron transfer conditions, a transformation that had been considered to lie outside the scope of the classic SmI2 reductant for more than 30 years. In this article, we present a detailed mechanistic investigation of the reduction of unactivated esters, carboxylic acids, and amides using SmI2-water-amine reagents, in which we compare the reactivity of three functional groups. The mechanism has been studied using the following: (i) kinetic, (ii) reactivity, (iii) radical clock, and (iv) isotopic labeling experiments. The kinetic data indicate that for the three functional groups all reaction components (SmI2, amine, water) are involved in the rate equation and that the rate of electron transfer is facilitated by base assisted deprotonation of water. Notably, the mechanistic details presented herein indicate that complexation between SmI2, water, and amines can result in a new class of structurally diverse, thermodynamically powerful reductants for efficient electron transfer to a variety of carboxylic acid derivatives. These observations will have important implications for the design and optimization of new processes involving Sm(II)-reduction of ketyl radicals. PMID:25232891

Szostak, Michal; Spain, Malcolm; Eberhart, Andrew J; Procter, David J

2014-12-19

158

Dual effects of aliphatic carboxylic acids on cresolase and catecholase reactions of mushroom tyrosinase.  

PubMed

Catecholase and cresolase activities of mushroom tyrosinase (MT) were studied in presence of some n-alkyl carboxylic acid derivatives. Catecholase activity of MT achieved its optimal activity in presence of 1.0, 1.25, 2.0, 2.2 and 3.2 mM of pyruvic acid, acrylic acid, propanoic acid, 2-oxo-butanoic acid, and 2-oxo-octanoic acid, respectively. Contrarily, the cresolase activity of MT was inhibited by all type of the above acids. Propanoic acid caused an uncompetitive mode of inhibition (K(i)=0.14 mM), however, the pyruvic, acrylic, 2-oxo-butanoic and 2-oxo-octanoic acids showed a competitive manner of inhibition with the inhibition constants (K(i)) of 0.36, 0.6, 3.6 and 4.5 mM, respectively. So, it seems that, there is a physical difference in the docking of mono- and o-diphenols to the tyrosinase active site. This difference could be an essential determinant for the course of the catalytic cycle. Monophenols are proposed to bind only the oxyform of the tyrosinase. It is likely that the binding of acids occurs through their carboxylate group with one copper ion of the binuclear site. Thus, they could completely block the cresolase reaction, by preventing monophenol binding to the enzyme. From an allosteric point of view, n-alkyl acids may be involved in activation of MT catecholase reactions. PMID:19555185

Gheibi, N; Saboury, A A; Haghbeen, K; Rajaei, F; Pahlevan, A A

2009-10-01

159

1-aminocyclopropane-1-carboxylic acid (ACC) in plants: more than just the precursor of ethylene!  

PubMed Central

Ethylene is a simple two carbon atom molecule with profound effects on plants. There are quite a few review papers covering all aspects of ethylene biology in plants, including its biosynthesis, signaling and physiology. This is merely a logical consequence of the fascinating and pleiotropic nature of this gaseous plant hormone. Its biochemical precursor, 1-aminocyclopropane-1-carboxylic acid (ACC) is also a fairly simple molecule, but perhaps its role in plant biology is seriously underestimated. This triangularly shaped amino acid has many more features than just being the precursor of the lead-role player ethylene. For example, ACC can be conjugated to three different derivatives, but their biological role remains vague. ACC can also be metabolized by bacteria using ACC-deaminase, favoring plant growth and lowering stress susceptibility. ACC is also subjected to a sophisticated transport mechanism to ensure local and long-distance ethylene responses. Last but not least, there are now a few exciting studies where ACC has been reported to function as a signal itself, independently from ethylene. This review puts ACC in the spotlight, not to give it the lead-role, but to create a picture of the stunning co-production of the hormone and its precursor. PMID:25426135

Van de Poel, Bram; Van Der Straeten, Dominique

2014-01-01

160

Antioxidant activity of brocchlin carboxylic acid and its methyl ester from Chrozophora brocchiana.  

PubMed

The analogue of brevifolin carboxylic acid and its methyl ester were isolated and identified from the aqueous ethanolic extract of the leaves of Chrzophora brocchiana in addition to eight known compounds identified as gallic acid, methyl and ethyl gallate, ellagic acid, monomethoxy and methylenedioxy ellagic acid, apigenin 7-O-glucoside and luteolin 7-O-glucoside. The structures were determined primarily by ESI-MS and NMR spectroscopy. The assignment of NMR signals was preformed by means of 1H-H COSY, HMQC and HMBC experiments. The antioxidant activity of the new compounds was determined by checking the scavenging activity against DPPH free radical. PMID:17613821

Hawas, Usama W

2007-06-01

161

Design of co-crystals/salts of some Nitrogenous bases and some derivatives of thiophene carboxylic acids through a combination of hydrogen and halogen bonds  

PubMed Central

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 formed in the presence of pyrimidines and carboxylic acids. Results Fourteen crystals involving various substituted thiophene carboxylic acid derivatives and nitrogenous bases were prepared and characterized by using single crystal X-ray diffraction. The 14 crystals can further be divided into two groups [1a-7a], [8b-14b] based on the nature of the nitrogenous base. Carboxylic acid to pyridine proton transfer has occurred in 3 compounds of each group. In addition to the commonly occurring hydrogen bond based pyridine/carboxylic acid and pyrimidine/carboxylic acid synthons which is the reason for assembly of primary motifs, various other interactions like Cl…Cl, Cl…O, C–H…Cl, C-H…S add additional support in organizing these supermolecules into extended architectures. It is also interesting to note that in all the compounds ?-? stacking occurs between the pyrimidine-pyrimidine or pyridine-pyridine or acid-acid moieties rather than acid-pyrimidine/pyridine. Conclusions In all the compounds (1a-14b) either neutral O–H…Npyridyl/pyrimidine or charge-assisted Npyridinium-H…Ocarboxylate hydrogen bonds are present. The HT (hetero trimers) and LHT (linear heterotetramers) are dominant in the crystal structures of the adducts containing N-heterocyclic bases with two proton acceptors (1a-7a). Similar type supramolecular ladders are observed in 5TPC44BIPY (8b), TPC44BIPY (9b), TPC44TMBP (11b). Among the seven compounds [8b-14b] the extended ligands are linear in all except for the TMBP (10b, 11b, 12b). The structure of each compound depends on the dihedral angle between the carboxyl group and the nitrogenous base. All these compounds indicate three main synthons that regularly occur, namely linear heterodimer (HD), heterotrimer (HT) and heterotetramer (LHT). PMID:24655545

2014-01-01

162

Water chemical ionization mass spectrometry of aldehydes, ketones esters, and carboxylic acids  

SciTech Connect

Chemical ionization mass spectrometry (CI) of aliphatic and aromatic carbonyl compounds using water as the reagent gas provides intense pseudomolecular ions and class-specific fragmentation patterns that can be used to identify aliphatic aldehydes, ketones, carboxylic acids, and esters. The length of ester acyl and alkyl groups can easily be determined on the basis of loss of alcohols from the protonated parent. Water CI provides for an approximately 200:1 selectivity of carbonyl species over alkanes. No reagent ions are detected above 55 amu, allowing species as small as acetone, propanal, acetic acid, and methyl formate to be identified. When deuterate water was used as the reagent, only the carboxylic acids and ..beta..-diketones showed significant H/D exchange. The use of water CI to identify carbonyl compounds in a wastewater from the supercritical water extraction of lignite coal, in lemon oil, and in whiskey volatiles is discussed.

Hawthorne, S.B.; Miller, D.J.

1986-11-01

163

Partial Hydrothermal Oxidation of High Molecular Weight Unsaturated Carboxylic Acids for Upgrading of Biodiesel Fuel  

NASA Astrophysics Data System (ADS)

With increasing environmental awareness and crude oil price, biodiesel fuel (BDF) is gaining recognition as a renewable fuel which may be used as an alternative diesel fuel without any modification to the engine. The cold flow and viscosity of BDF, however, is a major drawback that limited its use in cold area. In this study, therefore, we investigated that partial oxidation of high molecular weight unsaturated carboxylic acids in subcritical water, which major compositions in BDF, to upgrade biodiesel fuel. Oleic acid, (HOOC(CH2)7CH=CH(CH2)7CH3), was selected as a model compound of high molecular weight unsaturated carboxylic acids. All experiments were performed with a batch reactor made of SUS 316 with an internal volume of 5.7 cm3. Oleic acid was oxidized at 300 °C with oxygen supply varying from 1-10 %. Results showed that a large amount of carboxylic acids and aldehydes having 8-9 carbon atoms were formed. These experimental results suggest that the hydrothermal oxidative cleavage may mainly occur at double bonds and the cleavage of double bonds could improve the cold flow and viscosity of BDF.

Kawasaki, K.; Jin, F.; Kishita, A.; Tohji, K.; Enomoto, H.

2007-03-01

164

DETERMINATION OF CARBOXYLIC ACIDS BY ION-EXCLUSION CHROMATOGRAPHY WITH NON-SUPPRESSED CONDUCTIVITY AND OPTICAL DETECTORS  

EPA Science Inventory

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...

165

DETERMINATION OF CARBOXYLIC ACIDS BY ION-EXCLUSION CHROMATOGRAPHY WITH NON-SUPPRESSED CONDUCTIVITY AND OPTICAL DETECTORS  

EPA Science Inventory

Determination of carboxylic acids using non-suppressed conductivity and UV detections is described. he background conductance of I-octanesulfonic acid, hexane sulfonic acid and sulfuric acid at varying concentrations was determined. sing 0.2 MM I-octanesulfonic acid as a mobile p...

166

Ground measurements of carboxylic acids during the ChArMEx field campaign using PTR-ToFMS  

NASA Astrophysics Data System (ADS)

Carboxylic acids are long-lived and persistent species that have been shown to be important for ambient acidity and secondary organic aerosol formation. Formic, acetic, and propionic acids are among the most abundant carboxylic acids in the troposphere. However, their atmospheric sources are poorly characterized due to limited measurement data. Techniques usually used to measure gas-phase concentrations of carboxylic acids suffer from low time resolution and the use of fast instruments would be of prime interest to apportion the contribution of anthropogenic and biogenic emissions, as well as photochemical processes to the carboxylic acid budget. A Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToFMS) was characterized for field measurements of n-carboxylic acids (C1-C4). Laboratory experiments were carried out to get insights into fragmentation patterns of parent (RCOOHH+) and acylium (RCO+) ions, sensitivities, and detection limits under various operating conditions. Carefully designed experiments were conducted to assess the impact of relative humidity on the sensitivity. Detection limits of 500, 90, 50 and 40 ppt were achieved for 10-min measurements of formic, acetic, propionic and butyric acids, respectively. This instrument was deployed for the first time during the 2013 ChArMEx intensive field campaign at a ground site in Cap Corsica and successfully measured concentrations of carboxylic acids from July 15th to August 5th. Elevated mixing ratios in the range 500-4000 ppt, 260-2500 ppt, and 50-500 ppt were observed for formic, acetic, and propionic acids, respectively. Mixing ratios of butyric acids were close to the detection limit. In this presentation, we will discuss the potential of carboxylic acid measurements by PTR-ToFMS in remote areas and we will provide a preliminary analysis of carboxylic acid sources in an area impacted by local biogenic emissions as well as aged anthropogenic air masses.

Dusanter, Sébastien; Sauvage, Stéphane; Locoge, Nadine; Michoud, Vincent; Touati, Nabil; Zhang, Shouwen; Riffault, Véronique

2014-05-01

167

Comparison Of Asymmetric Hydrogenations Of Unsaturated- Carboxylic Acids And -Esters  

PubMed Central

As methodology development matures it can be difficult to discern the most effective ways of performing certain transformations from the rest. This review summarizes the most important contributions leading to asymmetric hydrogenations of simple unsaturated-acid and ester substrates, with the objective of highlighting at least the best types of catalysts for each. Achievements in the area are described and these reveal situations where further efforts should be worthwhile, and ones where more research is only likely to give diminishing returns. In general, our conclusions are that the most useful types of catalysts for unsaturated-acids and -esters tend to be somewhat different, simple substrates have been studied extensively, and the field is poised to address more complex reactions. These could be ones involving alternative, particularly cyclic, structures, chemoselectivity issues, and more complex substrate stereochemistries. PMID:24729943

Khumsubdee, Sakunchai; Burgess, Kevin

2013-01-01

168

A Phosphetane Catalyzes Deoxygenative Condensation of ?-Keto Esters and Carboxylic Acids via P(III)/P(V)?O Redox Cycling.  

PubMed

A small-ring phosphacycle is found to catalyze the deoxygenative condensation of ?-keto esters and carboxylic acids. The reaction provides a chemoselective catalytic synthesis of ?-acyloxy ester products with good functional group compatibility. Based on both stoichiometric and catalytic mechanistic experiments, the reaction is proposed to proceed via catalytic P(III)/P(V)?O cycling. The importance of ring strain in the phosphacyclic catalyst is substantiated by an observed temperature-dependent product selectivity effect. The results point to an inherent distinction in design criteria for organophosphorus-based catalysts operating via P(III)/P(V)?O redox cycling as opposed to Lewis base (nucleophilic) catalysis. PMID:25564133

Zhao, Wei; Yan, Patrick K; Radosevich, Alexander T

2015-01-21

169

Effect of carboxylic acid of periodic mesoporous organosilicas on the fructose-to-5-hydroxymethylfurfural conversion in dimethylsulfoxide systems  

SciTech Connect

This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid (–COOH) group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl) benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and {sup 13}C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion of fructose to 5-hydroxymethylfurfural (HMF) in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed.

Dutta, Saikat; Wu, Kevin C.-W., E-mail: hmkao@cc.ncu.edu.tw, E-mail: kevinwu@ntu.edu.tw [Department of Chemical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan (China); Kao, Hsien-Ming, E-mail: hmkao@cc.ncu.edu.tw, E-mail: kevinwu@ntu.edu.tw [Department of Chemistry, National Central University, Chung-Li 32054, Taiwan (China)

2014-11-01

170

Effect of carboxylic acid of periodic mesoporous organosilicas on the fructose-to-5-hydroxymethylfurfural conversion in dimethylsulfoxide systems  

NASA Astrophysics Data System (ADS)

This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid (-COOH) group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl) benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and 13C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion of fructose to 5-hydroxymethylfurfural (HMF) in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed.

Dutta, Saikat; Kao, Hsien-Ming; Wu, Kevin C.-W.

2014-11-01

171

Formation routes of interstellar glycine involving carboxylic acids: possible favoritism between gas and solid phase.  

PubMed

Despite the extensive search for glycine (NH?CH?COOH) and other amino acids in molecular clouds associated with star-forming regions, only upper limits have been derived from radio observations. Nevertheless, two of glycine's precursors, formic acid and acetic acid, have been abundantly detected. Although both precursors may lead to glycine formation, the efficiency of reaction depends on their abundance and survival in the presence of a radiation field. These facts could promote some favoritism in the reaction pathways in the gas phase and solid phase (ice). Glycine and these two simplest carboxylic acids are found in many meteorites. Recently, glycine was also observed in cometary samples returned by the Stardust space probe. The goal of this work was to perform theoretical calculations for several interstellar reactions involving the simplest carboxylic acids as well as the carboxyl radical (COOH) in both gas and solid (ice) phase to understand which reactions could be the most favorable to produce glycine in interstellar regions fully illuminated by soft X-rays and UV, such as star-forming regions. The calculations were performed at four different levels for the gas phase (B3LYP/6-31G*, B3LYP/6-31++G**, MP2/6-31G*, and MP2/6-31++G**) and at MP2/6-31++G** level for the solid phase (ice). The current two-body reactions (thermochemical calculation) were combined with previous experimental data on the photodissociation of carboxylic acids to promote possible favoritism for glycine formation in the scenario involving formic and acetic acid in both gas and solid phase. Given that formic acid is destroyed more in the gas phase by soft X-rays than acetic acid is, we suggest that in the gas phase the most favorable reactions are acetic acid with NH or NH?OH. Another possible reaction involves NH?CH? and COOH, one of the most-produced radicals from the photodissociation of acetic acid. In the solid phase, we suggest that the reactions of formic acid with NH?CH or NH?CH?OH are the most favorable from the thermochemical point of view. PMID:22066498

Pilling, Sergio; Baptista, Leonardo; Boechat-Roberty, Heloisa M; Andrade, Diana P P

2011-11-01

172

The interaction of carboxylic acids with aluminium oxides: journeying from a basic understanding of alumina nanoparticles to water treatment for industrial and humanitarian applications.  

PubMed

Carboxylic acids are found to react with aluminium oxides via a topotactic reaction such that the carboxylate acts as a bridging ligand. This reaction allows for carboxylate-functionalized alumina nanoparticles to be prepared directly from boehmite (AlOOH). Understanding the structural relationship between molecular and surface species allows for the rationalization/prediction of suitable alternative ligands as well as alternative oxide surfaces. The identity of the carboxylate substituent controls the pH stability of a nanoparticle as well as the porosity and processability of ceramics prepared by thermolysis. Through the choice of functional groups on the carboxylic acid the properties of the alumina surface or alumina nanoparticle can be tailored. For example, the solubility/miscibility of nanoparticles can be tuned to the solvent/matrix, and the wettability to be varied from hydrophobic to super hydrophilic. The choice Zwitter ionic substituents on alumina micro-/ultra-filtration membranes are found to enhance the flux and limit fouling while allowing for the facile separation of organic compounds from water. Examples are presented of purification of frac and flow-back water from oil well production as well as providing drinking water from contaminated sources in underdeveloped regions. PMID:24728503

Barron, Andrew R

2014-06-14

173

Complexation of carboxylate anions with the arginine gas-phase amino acid: Effects of chain length on the geometry of extended ion binding  

NASA Astrophysics Data System (ADS)

Complexation of deprotonated carboxylic acids with arginine was investigated using collision-induced dissociation to probe the nature of isolated carboxylate-amino acid interactions as a function of anion size. Monocarboxylic CH3(CH2)nCOO-·Arg (n = 3-7, 9, 10) and dicarboxylic acid COOH(CH2)nCOO-·Arg (n = 3-5, 7-10) complexes were investigated. For the dicarboxylic acid clusters, chain length has a significant effect on the %fragmentation energies with the n = 9, 10 systems fragmenting at significantly lower energies than the corresponding shorter chain systems. Molecular mechanics calculations suggest that this fragmentation energy shift is associated with the longer-chain dicarboxylic acid-Arg clusters switching to ring structures.

Luxford, Thomas F. M.; Milner, Edward M.; Yoshikawa, Naruo; Bullivant, Chad; Dessent, Caroline E. H.

2013-07-01

174

6-Mercaptomethylpyridine-3-carboxylic acid (MEMNIC): a new reagent for peptide labeling with Tc99m  

Microsoft Academic Search

As part of our ongoing research into the development of peptide based radiopharmaceuticals, we have explored 2-mercaptopyridines and 2-mercapto-pyrimidines (2MPs) as coligands to control the radiochemical speciation of 99mTc-labeled hydrazinonicotinamide (HYNIC) derivatized chemotactic peptides. In an attempt to develop an aminothiol ligand with greater stability, we synthesized 6-mercaptomethylpyridine–3-carboxylic acid (MEMNIC), assuming a five-member chelate ring complex would be more stable

John W Babich; Wendy Graham; Frank J Femia; Qing Dong; Marlene Barzana; Kevin Ferrill; Alan J Fischman; Jon Zubieta

2001-01-01

175

Conversion of municipal solid waste into carboxylic acids by anaerobic countercurrent fermentation  

Microsoft Academic Search

Municipal solid waste (MSW) and sewage sludge (SS) were combined and anaerobically converted into carboxylate salts by using\\u000a a mixed culture of acid-forming microorganisms. MSW is an energy source and SS is a source of nutrients. In this study, MSW\\u000a and SS were combined, so they complemented each other. Four fermentors were arranged in series for a countercurrent fermentation\\u000a process.

Cateryna Aiello-Mazzarri; Guillermo Coward-Kelly; Frank K. Agbogbo; Mark T. Holtzapple

2005-01-01

176

Process for the generation of .alpha., .beta.-unsaturated carboxylic acids and esters using niobium catalyst  

DOEpatents

A process using a niobium catalyst includes the step of reacting an ester or carboxylic acid with oxygen and an alcohol in the presence a niobium catalyst to respectively produce an .alpha.,.beta.-unsaturated ester or carboxylic acid. Methanol may be used as the alcohol, and the ester or carboxylic acid may be passed over the niobium catalyst in a vapor stream containing oxygen and methanol. Alternatively, the process using a niobium catalyst may involve the step of reacting an ester and oxygen in the presence the niobium catalyst to produce an .alpha.,.beta.-unsaturated carboxylic acid. In this case the ester may be a methyl ester. In either case, niobium oxide may be used as the niobium catalyst with the niobium oxide being present on a support. The support may be an oxide selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide and mixtures thereof. The catalyst may be formed by reacting niobium fluoride with the oxide serving as the support. The niobium catalyst may contain elemental niobium within the range of 1 wt % to 70 wt %, and more preferably within the range of 10 wt % to 30 wt %. The process may be operated at a temperature from 150 to 450.degree. C. and preferably from 250 to 350.degree. C. The process may be operated at a pressure from 0.1 to 15 atm. absolute and preferably from 0.5-5 atm. absolute. The flow rate of reactants may be from 10 to 10,000 L/kg.sub.(cat) /h, and preferably from 100 to 1,000 L/kg.sub.(cat) /h.

Gogate, Makarand Ratnakav (Durham, NC); Spivey, James Jerome (Cary, NC); Zoeller, Joseph Robert (Kingsport, TN)

1999-01-01

177

Synthesis of all four enantiomers of 1-aminoindane-2-carboxylic acid, a new cispentacin benzologue  

Microsoft Academic Search

Racemic cis- and trans-1-aminoindane-2-carboxylic acids (3 and 5) were prepared from indene by chlorosulphonyl isocyanate addition followed by ring opening and isomerisation. The intermediate racemic hydroxymethylated ?-lactam 6 was resolved through the lipase-catalysed asymmetric acylation of the primary hydroxy group at the (R)-stereogenic centre. High enantioselectivities (E>200) were observed when the enzymatic reactions were performed with lipase AK or lipase

Ferenc Fülöp; Márta Palkó; Judit Kámán; László Lázár; Reijo Sillanpää

2000-01-01

178

Quinolizidinone Carboxylic Acids as CNS Penetrant, Selective M1 Allosteric Muscarinic Receptor Modulators  

PubMed Central

Positive allosteric modulation of the M1 muscarinic receptor represents an approach to treat the cognitive decline in patients with Alzheimer’s disease. Replacement of a quinolone ring system in a quinolone carboxylic acid series of M1 modulators with a quinolizidinone bearing a basic amine linkage led to a series of compounds with higher free fraction, enhanced CNS exposure, and improved efficacy in rodent in vivo models of cognition. PMID:24900206

2010-01-01

179

1-Aminocyclopropane-1-carboxylic acid as a signalling molecule in plants  

PubMed Central

Ethylene influences many aspects of plant growth and development including germination, leaf and floral senescence and abscission, fruit ripening, and the response to abiotic and biotic stress. The pathways involved in the biosynthesis of and response to ethylene have been elucidated. The first committed and generally rate-limiting step in ethylene biosynthesis is the conversion of S-adenosyl-methionine to 1-aminocyclopropane-1-carboxylic acid (ACC) by ACC synthase (ACS). This enzyme is encoded by a gene family in most plants and is subject to both transcriptional and post-transcriptional control in response to numerous endogenous and environmental cues. In addition to its well-described function as the immediate precursor of ethylene, recent studies suggest an alternative, non-canonical role for ACC. These studies found that in some contexts, chemical inhibitors of ethylene biosynthesis caused effects on root cell expansion that were not observed when ethylene perception or signalling was disrupted, suggesting that ACC, but not ethylene, played a role in these specific processes. Furthermore, mutation of all eight ACS genes in Arabidopsis was found to result in embryo lethality, in contrast to the relatively modest developmental effects of null mutants in the ethylene signalling components. This divergence suggests that ACC may play a role as a signalling molecule in plants. Here, we first review the ethylene biosynthesis pathway and then discuss these studies suggesting an independent role of ACC as a signalling molecule.

Yoon, Gyeong Mee; Kieber, Joseph J.

2013-01-01

180

Investigation of Pyridine Carboxylic Acids in CM2 Carbonaceous Chondrites: Potential Precursor Molecules for Ancient Coenzymes  

NASA Technical Reports Server (NTRS)

The distribution and abundances of pyridine carboxylic acids (including nicotinic acid) in eight CM2 carbonaceous chondrites (ALH 85013, DOM 03183, DOM 08003, EET 96016, LAP 02333, LAP 02336, LEW 85311, and WIS 91600) were investigated by liquid chromatography coupled to UV detection and high resolution Orbitrap mass spectrometry. We find that pyridine monocarboxylic acids are prevalent in CM2-type chondrites and their abundance negatively correlates with the degree of pre-terrestrial aqueous alteration that the meteorite parent body experienced. We lso report the first detection of pyridine dicarboxylic acids in carbonaceous chondrites. Additionally, we carried out laboratory studies of proton-irradiated pyridine in carbon dioxide-rich ices (a 1:1 mixture) to serve as a model of the interstellar ice chemistry that may have led to the synthesis of pyridine carboxylic acids. Analysis of the irradiated ice residue shows that a comparable suite of pyridine mono- and dicarboxylic acids was produced, although aqueous alteration may still play a role in the synthesis (and ultimate yield) of these compounds in carbonaceous meteorites. Nicotinic acid is a precursor to nicotinamide adenine dinucleotide, a likely ancient molecule used in cellular metabolism in all of life, and its common occurrence in CM2 chondrites may indicate that meteorites may have been a source of molecules for the emergence of more complex coenzymes on the early Earth.

Smith, Karen E.; Callahan, Michael P.; Gerakines, Perry A.; Dworkin, Jason P.; House, Christopher H.

2014-01-01

181

Evaluation of toxic effects of several carboxylic acids on bacterial growth by toxicodynamic modelling  

PubMed Central

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 (?) 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,?) 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. PMID:22118421

2011-01-01

182

Discovery of pyrazole carboxylic acids as potent inhibitors of rat long chain L-2-hydroxy acid oxidase.  

PubMed

Long chain L-2-hydroxy acid oxidase 2 (Hao2) is a peroxisomal enzyme expressed in the kidney and the liver. Hao2 was identified as a candidate gene for blood pressure (BP) quantitative trait locus (QTL) but the identity of its physiological substrate and its role in vivo remains largely unknown. To define a pharmacological role of this gene product, we report the development of selective inhibitors of Hao2. We identified pyrazole carboxylic acid hits 1 and 2 from screening of a compound library. Lead optimization of these hits led to the discovery of 15-XV and 15-XXXII as potent and selective inhibitors of rat Hao2. This report details the structure activity relationship of the pyrazole carboxylic acids as specific inhibitors of Hao2. PMID:22658862

Barawkar, Dinesh A; Bandyopadhyay, Anish; Deshpande, Anil; Koul, Summon; Kandalkar, Sachin; Patil, Pradeep; Khose, Goraksha; Vyas, Samir; Mone, Mahesh; Bhosale, Shubhangi; Singh, Umesh; De, Siddhartha; Meru, Ashwin; Gundu, Jayasagar; Chugh, Anita; Palle, Venkata P; Mookhtiar, Kasim A; Vacca, Joseph P; Chakravarty, Prasun K; Nargund, Ravi P; Wright, Samuel D; Roy, Sophie; Graziano, Michael P; Cully, Doris; Cai, Tian-Quan; Singh, Sheo B

2012-07-01

183

Acid monolayer functionalized iron oxide nanoparticle catalysts  

NASA Astrophysics Data System (ADS)

Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide nanoparticle syntheses and functionalizations for biomedical and catalytic applications, affecting understandings of surface charge and other material properties.

Ikenberry, Myles

184

Can an amine be a stronger acid than a carboxylic acid? The surprisingly high acidity of amine-borane complexes.  

PubMed

The gas-phase acidity of a series of amine-borane complexes has been investigated through the use of electrospray mass spectrometry (ESI-MS), with the application of the extended Cooks kinetic method, and high-level G4 ab initio calculations. The most significant finding is that typical nitrogen bases, such as aniline, react with BH(3) to give amine-borane complexes, which, in the gas phase, have acidities as high as those of either phosphoric, oxalic, or salicylic acid; their acidity is higher than many carboxylic acids, such as formic, acetic, and propanoic acid. Indeed the complexation of different amines with BH(3) leads to a substantial increase (from 167 to 195 kJ mol(-1)) in the intrinsic acidity of the system; in terms of ionization constants, this increase implies an increase as large as fifteen orders of magnitude. Interestingly, this increase in acidity is almost twice as large as that observed for the corresponding phosphine-borane analogues. The agreement between the experimental and the G4-based calculated values is excellent. The analysis of the electron-density rearrangements of the amine and the borane moieties indicates that the dative bond is significantly stronger in the N-deprotonated anion than in the corresponding neutral amine-borane complex, because the deprotonated amine is a much better electron donor than the neutral amine. On the top of that, the newly created lone pair on the nitrogen atom in the deprotonated species, conjugates with the BN bonding pair. The dispersion of the extra electron density into the BH(3) group also contributes to the increased stability of the deprotonated species. PMID:23060273

Martín-Sómer, Ana; Lamsabhi, Al Mokhtar; Yáñez, Manuel; Dávalos, Juan Z; González, Javier; Ramos, Rocío; Guillemin, Jean-Claude

2012-12-01

185

A Novel Aromatic Carboxylic Acid Inactivates Luciferase by Acylation of an Enzymatically Active Regulatory Lysine Residue  

PubMed Central

Firefly luciferase (Luc) is widely used as a reporter enzyme in cell-based assays for gene expression. A novel aromatic carboxylic acid, F-53, reported here for the first time, substantially inhibited the enzymatic activity of Luc in a Luc reporter screening. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and tandem mass spectrometry (MS/MS) analyses showed that F-53 modifies Luc at lysine-529 via amidation of the F-53 carboxyl group. The lysine-529 residue of Luc, which plays a regulatory catalytic role, can be acetylated. Luc also has a long-chain fatty acyl-CoA synthase activity. An in vitro assay that involved both recombinant Luc and mouse liver microsomes identified F-53-CoA as the reactive form produced from F-53. However, whereas the inhibitory effect of F-53 is observed in Hela cells that transiently expressed Luc, it is not observed in an in vitro assay that involves recombinant Luc alone. Therefore, insights into the activities of certain mammalian transferases can be translated to better understand the acylation by F-53. The insights from this study about the novel inhibitory modification mechanism might help not only to avoid misinterpretation of the results of Luc-based reporter screening assays but also to explain the pharmacological and toxicological effects of carboxylic acid-containing drugs. PMID:24066181

Nakagomi, Madoka; Fujimaki, Nobuko; Ito, Ai; Toda, Takahiro; Fukasawa, Hiroshi; Shudo, Koichi; Tomita, Ryoichi

2013-01-01

186

Contributions of low molecular weight carboxylic acids to aerosols and wet deposition in a natural subtropical broad-leaved forest environment  

NASA Astrophysics Data System (ADS)

The carboxylic acid component of autumn aerosol and wet deposition (fog water and rainwater) in a broad-leaved forest in central Taiwan was investigated. High levels of low molecular weight carboxylic acids (LMWCAs) were noted in all deposition types. Acetic acid, oxalic acid and formic acid were the most prevalent carboxylic acids, together accounting for 72.2% (fog water), 86.7% (rain water), 77.2% (PM2.5) and 88.3% (PM2.5-10) of total carboxylic acid. The forest fog water contained 2453.9 ± 1030.5 ng mL-1 of carboxylic acid, 2.71 times more than was contained in forest rainwater. In PM, most carboxylic acid existed in the fine PM2.5 aerosol (576.6 ± 254.1 ng m-3 or 6.28 times more than was contained in PM2.5-10. Most carboxylic acids in PM had higher concentrations during the day. Pyruvic acid concentration was higher during the night (2.97 times), however, owing to its rapid photodegradation during the day. Citric acid accounted for 9.1% of the total carboxylic acid in fog water compared with just 1.8% in rainwater, confirming its origin from emissions from leaves. Raman spectroscopy was used to observe the photochemical conversion of citric acid into intermediate products and this observation confirmed that the carboxylic acids identified in the forest dry and wet depositions originated directly from biological emissions in the forest environment.

Tsai, Ying I.; Kuo, Su-Ching

2013-12-01

187

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

PubMed

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

Shahroosvand, Hashem; Nasouti, Fahimeh; Sousaraei, Ahmad

2014-04-01

188

Regulation of gene expression in Pseudomonas aeruginosa M18 by phenazine-1-carboxylic acid.  

PubMed

Phenazine-1-carboxylic acid (PCA), an environmentally compatible redox-active metabolite produced by Pseudomonas sp., has been found to effectively protect against various phytopathogens. The objective of this study was to discover whether PCA can also act as a signaling molecule that regulates gene expression in Pseudomonas aeruginosa M18. We constructed a series of PCA-producing mutant strains (high PCA, M18MSU1; low PCA, M18MS; and no PCA, M18MSP1P2) and analyzed their gene expression by using a custom microarray DNA chip. We found that the expression of PCA in both M18MSU1 and M18MS altered the expression of a total of 545 different genes; however, the higher level of PCA in M18MSU1 altered more genes (489) than did the lower level of PCA in M18MS (129). Of particular note, 73 of these genes were commonly regulated between the two mutants, indicating their importance in the downstream function of PCA. PCA molecules upregulated genes that function primarily in energy production, cell motility, secretion, and defense mechanisms and downregulated genes involved in transcription, translation, cell division, and gene expression in the prophage. We found that PCA worked to alter the expression of an efflux pump gene mexH through a SoxR-mediated mechanism; we further hypothesized that other pathways should also be affected by this interaction. Taken together, our results provide the first evidence of PCA-derived molecular responses at the transcriptional level. They also help to elucidate the future of genetically engineered P. aeruginosa strains for the production of PCA used in a number of applications. PMID:25304879

Du, Xilin; Li, Yaqian; Zhou, Quan; Xu, Yuquan

2015-01-01

189

Floral benzenoid carboxyl methyltransferases: From in vitro to in planta function  

PubMed Central

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 planta 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 might represent the ancestor for the presently existing floral genes which during evolution gained different expression profiles and encoded enzymes with the ability to accept structurally similar substrates. PMID:15946712

Effmert, Uta; Saschenbrecker, Sandra; Ross, Jeannine; Negre, Florence; Fraser, Chris M.; Noel, Joseph P.; Dudareva, Natalia; Piechulla, Birgit

2010-01-01

190

Bio-inspired amino acid oxidation by a non-heme iron catalyst modeling the action of 1-aminocyclopropane-1-carboxylic acid oxidase.  

PubMed

In this communication we describe the first example of a biomimetic mononuclear iron complex, [Fe(III)(Salen)Cl] (Salen = N,N'-bis(salicylidene)-ethylenediaminato), that highly selectively and efficiently catalyzes the oxidation of 1-aminocyclopropane-1-carboxylic acid (ACCH), ?-aminoisobutyric acid (AIBH), and alanine (ALAH) to ethylene or the corresponding carbonyl compounds, mimicking the action of the non-heme iron enzyme 1-aminocyclopropane-1-carboxylic acid oxidase (ACCO). PMID:20830340

Baráth, Gábor; Kaizer, József; Pap, József Sándor; Speier, Gábor; El Bakkali-Taheri, Nadia; Simaan, A Jalila

2010-10-21

191

Collision-induced dissociation of carboxylate anions from derivatized 5-lipoxygenase metabolites of arachidonic acid.  

PubMed

The low-energy collision-induced dissociations (CID) of carboxylate anions derived from pentafluorobenzyl ester, trimethylsilyl ether derivatives of four arachidonic acid metabolites of the 5-lipoxygenase pathway have been determined. These molecules include leukotriene B4 (LTB4), a potent chemotactic factor for the human neutrophil; 20-carboxy-LTB4, an inactive metabolite; 5-hydroxyeicosatetraenoic acid (5-HETE), a useful marker of 5-lipoxygenase activity within cells; and 5-hydroxyeicosanoic acid (5-HEA), which has been previously used for the quantitation of leukotriene E4. The carboxylate anion of 5-HEA (m/z 399) was found to decompose by the loss of trimethylsilanol as well as the loss of 146 u corresponding to the loss of trimethylsilanol followed by acrolein, a process specific for 5-hydroxy-containing saturated fatty acids. The loss of trimethylsilanol by a remote site mechanism is the major transition observed for the 5-HETE carboxylate anion (m/z 391). The ion formed (m/z 301) further decomposes by the loss of CO2 (m/z 257). The loss of trimethylsilanol is also seen at m/z 389 after collisional activation of the carboxylate anion of LTB4 (m/z 479) by a complex charge-driven mechanism, not the remote site fragmentation mechanism as expected. The loss of an olefinic proton possibly from carbon-7 is involved as well as an oxygen atom derived from the carboxylic acid moiety. The loss of two trimethylsilanol neutral molecules gives rise to ions seen at m/z 299. Isotopic labeling studies revealed that two isobaric ions are present at m/z 299. Both of these ions involve the loss of trimethylsilanol from the carbon-12 position according to remote site mechanisms, but only one has lost the olefinic proton at carbon-7 and, therefore, likely originates from the further decomposition of the ion (m/z 389) described above. An additional ion seen at m/z 317 is attributed to the loss of trimethylsilyl ether (TMS-O-TMS) following a charge-driven mechanism involving the oxygen atom at carbon-12. The 20-carboxy-LTB4 carboxylate anion (m/z 689) decomposes primarily through the loss of one and two trimethylsilanol moieties, but the base peak (m/z 491) is due to the loss of pentafluorobenzyl alcohol. This ion, likely a ketene, further gives rise to three ions by the sequential loss of one and two trimethylsilanols and TMS-O-TMS. All collision-induced decompositions of the carboxylate anions of these eicosanoids are characterized by losses of small neutral molecules from the derivatizing groups (TMS and pentafluorobenzyl) and little fragmentation of the carbon backbone. PMID:8381676

Fruteau de Laclos, B; Zirrolli, J A; Murphy, R C

1993-01-01

192

Online gas and aerosol measurement of water soluble carboxylic acids in Zurich  

NASA Astrophysics Data System (ADS)

We discuss the diurnal and seasonal variability of low molecular weight organic acids in Zurich city on the basis of online quasi-continuous measurement in the gas and aerosol phase using a wet effluent diffusion denuder/aerosol collector (WEDD/AC) coupled to ion chromatography. The measurements were performed during August-September 2002 and March 2003. Acetic acid exhibited the highest concentration in the gas phase during all the measurement periods, followed by formic acid. Oxalic acid was predominantly found in the aerosol phase and often below the detection limit in the gas phase. In addition, filter samples were analyzed using ion chromatography-mass spectrometry (IC-MS) to provide more information on organic acids in the aerosol phase. From the offline IC-MS measurements, 20 monocarboxylic, dicarboxylic, and tricarboxylic acids were determined. In addition, more than 20 different masses were detected with the MS; however, identification of the organic acids was not possible. The sum of the carboxylic acids contributed on average 2% to the water soluble organic carbon (WSOC). The fraction of dicarboxylic acids to the WSOC was higher in summer compared to winter suggesting that dicarboxylic acids are mainly a result of photochemical reactions in summer whereas in winter they mainly result from primary sources.

Fisseha, Rebeka; Dommen, Josef; Gaeggeler, Kathrin; Weingartner, Ernest; Samburova, Vera; Kalberer, Markus; Baltensperger, Urs

2006-06-01

193

Theoretical and experimental studies on the electronic, optical, and structural properties of poly-pyrrole-2-carboxylic acid films  

NASA Astrophysics Data System (ADS)

A theoretical approach is used here to explain experimental results obtained from the electrosynthesis of polypyrrole-2-carboxylic acid (PPY-2-COOH) films in nonaqueous medium. An analysis of the Fukui function (reactivity index) indicates that the monomer (pyrrole-2-carboxylic acid, PY-2-COOH), and dimers and trimers are oxidized in the C4 or C5 positions of the heterocyclic ring of the PY-2-COOH structure. After calculating the heat of formation using semiempirical Austin Model 1 post-Hartree-Fock parameterization for dimer species, both C4 and C5 positions adjacent to the aromatic rings of PPY-2-COOH were considered the most susceptible ones to oxidative coupling reactions. The ZINDO-S/CI semiempirical method was used to simulate the electronic transitions typically seen in the UV-VIS-NIR range in monomer and oligomers with different conjugation lengths. The use of an electrochemical quartz crystal microbalance provides sufficient information to propose a polymerization mechanism of PY-2-COOH based on molecular modeling and experimental results.

Foschini, Mauricio; Silva, Hugo Santos; Silva, Raigna A.; Marletta, Alexandre; Gonçalves, Débora

2013-11-01

194

Theoretical Study of the Thermal Decomposition of Carboxylic Acids at Pyrolysis Temperature  

SciTech Connect

Carboxylic acids are important in the processing of biomass into renewable fuels and chemicals. They are formed from the pretreatment and pyrolysis of hemicellulose biopolymers and are released from the decomposition of sugars. They result from the deconstruction of polyhydroxyalkanoates (bacterial carbon storage polymers) from fatty acids derived from algae, bacteria, and oil crops. The thermal deoxygenation of carboxylic acids is an important step in the conversion of biomass into aliphatic hydrocarbons suitable for use in renewable biofuels and as petrochemical replacements. Decarboxylation, a primary decomposition pathway under pyrolysis conditions, represents an ideal conversion process, because it eliminates two atoms of oxygen for every carbon atom removed. Problematically, additional deoxygenation processes exist (e.g. dehydration) that are in direct competition with decarboxylation and result in the formation of reactive and more fragmented end products. To better understand the competition between decarboxylation and other deoxygenation processes and to gain insight into possible catalysts that would favor decarboxylation, we have investigated the mechanisms and thermochemistry of the various unimolecular and bimolecular deoxygenation pathways for a family of C1-C4 organic acids using electronic structure calculations at the M06-2X/6-311++G(2df,p) level of theory.

Clark, J. M.; Robichaud, D. J.; Nimlos, M. R.

2013-01-01

195

Hydrogen bond strength and bond geometry in cyclic dimers of crystalline carboxylic acids.  

PubMed

In a study of 101 crystal structures of carboxylic acids we have observed a clear trend in the difference between the formally single and formally double C-O bond distances, as observed by X-ray diffraction, with a clear-cut distinction between aromatic acids, where the two distances are similar, and non-aromatic acids, where the two distances distinctly differ by 0.06-0.12 A. A tentative energy classification - within the limits of the many assumptions - and a correlation with the O...O separation over the hydrogen bond indicate that the stability of the carboxylic acid dimer increases as the difference between the two apparent C-O distances becomes smaller, owing to an increasing Coulombic contribution to the dimerization energy. No simple hypothesis is adequate for a complete explanation of the origin, of the details and of the variations of this phenomenon. As often happens in crystal chemistry problems, one is presumably confronted with a balance of several subtle intra- and intermolecular factors. PMID:18490831

Gavezzotti, Angelo

2008-06-01

196

Efficient synthesis of 2-aminoindane-2-carboxylic acid via dialkylation of nucleophilic glycine equivalent.  

PubMed

An efficient, easy to scale-up method for preparing 2-aminoindane-2-carboxylic acid via two-step alkylation of a Ni(II)-complex of glycine Schiff base with 2-[N-(alpha-picolyl)amino]benzophenone (PAAP) (2b) with o-dibromoxylylene (3) is reported. The first step, monoalkylation of 2b with 3, conducted under phase-transfer conditions, gave the corresponding complex 6 in excellent chemical yield (97.2%). Without any purification the intermediate 6 was cyclized under homogeneous conditions (DMF, NaO-t-Bu) to give the product 7 in high chemical yield (93.1%). Decomposition of prepared 7 afforded the target amino acid 2-aminoindane-2-carboxylic acid (1) in 97.9% yield, along with recovery of ligand 8, which was converted back to the starting glycine complex 2b. Operationally convenient experimental procedures, mild reaction conditions, as well as high chemical and volume yields render the method practical for preparing amino acid 1 and its analogues. PMID:12790614

Ellis, Trevor K; Hochla, Veronica M; Soloshonok, Vadim A

2003-06-13

197

Crystal structures of (2 R,4 R)-2-(polyhydroxyalkyl)-1,3-thiazolidine-4-carboxylic acids: condensation products of l-cysteine with d-hexoses  

Microsoft Academic Search

We report herein the first crystal structures of (4-carboxy-1,3-thiazolidin-2-yl)pentitols [2-(polyhydroxyalkyl)thiazolidine-4-carboxylic acids], condensation products of l-cysteine with d-galactose and d-mannose: 2-(d-galacto-pentahydroxypentyl)thiazolidine-4-carboxylic acid hydrate, Gal-Cys·H2O (1), and 2-(d-manno-pentahydroxypentyl)thiazolidine-4-carboxylic acid hydrate, Man-Cys·H2O (2). In 1 and 2 the compounds crystallize as zwitterions, with the carboxylic groups deprotonated and the thiazolidine N atoms protonated. The sugar moiety and carboxylate group are in a cis

Miros?aw Tarnawski; Katarzyna ?lepokura; Tadeusz Lis

2011-01-01

198

1-Aminocyclopropane-1-carboxylic acid oxidase reaction mechanism and putative post-translational activities of the ACCO protein  

PubMed Central

1-Aminocyclopropane-1-carboxylic acid (ACC) oxidase (ACCO) catalyses the final step in ethylene biosynthesis converting ACC to ethylene, cyanide, CO2, dehydroascorbate and water with inputs of Fe(II), ascorbate, bicarbonate (as activators) and oxygen. Cyanide activates ACCO. A ‘nest’ comprising several positively charged amino acid residues from the C-terminal ?-helix 11 along with Lys158 and Arg299 are proposed as binding sites for ascorbate and bicarbonate to coordinately activate the ACCO reaction. The binding sites for ACC, bicarbonate and ascorbic acid for Malus domestica ACCO1 include Arg175, Arg244, Ser246, Lys158, Lys292, Arg299 and Phe300. Glutamate 297, Phe300 and Glu301 in ?-helix 11 are also important for the ACCO reaction. Our proposed reaction pathway incorporates cyanide as an ACCO/Fe(II) ligand after reaction turnover. The cyanide ligand is likely displaced upon binding of ACC and ascorbate to provide a binding site for oxygen. We propose that ACCO may be involved in the ethylene signal transduction pathway not directly linked to the ACCO reaction. ACC oxidase has significant homology with Lycopersicon esculentum cysteine protease LeCp, which functions as a protease and as a regulator of 1-aminocyclopropane-1-carboxylic acid synthase (Acs2) gene expression. ACC oxidase may play a similar role in signal transduction after post-translational processing. ACC oxidase becomes inactivated by fragmentation and apparently has intrinsic protease and transpeptidase activity. ACC oxidase contains several amino acid sequence motifs for putative protein–protein interactions, phosphokinases and cysteine protease. ACC oxidase is subject to autophosphorylaton in vitro and promotes phosphorylation of some apple fruit proteins in a ripening-dependent manner. PMID:24244837

Dilley, David R.; Wang, Zhenyong; Kadirjan-Kalbach, Deena K.; Ververidis, Fillipos; Beaudry, Randolph; Padmanabhan, Kallaithe

2013-01-01

199

Synthesis of chromium(III) complex with 1-hydroxy-2-pyridinone-6-carboxylic acid as insulin-mimetic agent and its spectroscopic and computational studies  

NASA Astrophysics Data System (ADS)

The new complex of chromium(III) and 1-hydroxy-2-pyridinone-6-carboxylic acid was synthesized and its preparation routes were reported. Mass spectrometry and elemental analysis indicated the formation of chromium complex with the metal-to-ligand mole ratio of 1:3. Combination of spectroscopic measurement and spectral computations based on the density functional theory suggested that 1-hydroxy-2-pyridinone-6-carboxylic acid was a bidentate ligand using one oxygen atom at pyridinone carbonyl group and the other at N-oxide group as donor atoms upon chelation with chromium(III), forming the six-coordinate complex with five-membered chelate rings. Due to the enhanced stability of the chelate rings, such the pathway of chelation was theoretically predicted to be more favorable than the case where the carboxylate oxygen atom of ligand participated in the chelation. According to the preliminary tests, the chromium(III) complex with 1-hydroxy-2-pyridinone-6-carboxylic acid was found to be active in lowering plasma glucose levels in vivo.

Yasarawan, Nuttawisit; Thipyapong, Khajadpai; Sirichai, Somsak; Ruangpornvisuti, Vithaya

2013-01-01

200

Simultaneous and sensitive analysis of aliphatic carboxylic acids by ion-chromatography using on-line complexation with copper(II) ion.  

PubMed

A new approach to ion chromatography is proposed to improve the UV detection of aliphatic carboxylic acids separated by anion-exchange chromatography. When copper(II) ion added to the mobile phase, it forms complexes with carboxylic acids that can be detected at 240nm. The absorbance was found to increase with increasing copper(II) ion concentration. The retention times of ?-hydroxy acids were also found to depend on the copper(II) ion concentration. Addition of acetonitrile to the mobile phase improved the separation of aliphatic carboxylic acids. The detection limits of the examined carboxylic acids (formate, glycolate, acetate, lactate, propionate, 3-hydroxypropionate, n-butyrate, isobutyrate, n-valerate, isovalerate, n-caproate) calculated at S/N=3 ranged from 0.06 to 3?M. The detector signal was linear over three orders of magnitude of carboxylic acid concentration. The proposed method was successfully applied to analyze aliphatic carboxylic acids in rainwater and bread. PMID:25523885

Kemmei, Tomoko; Kodama, Shuji; Yamamoto, Atsushi; Inoue, Yoshinori; Hayakawa, Kazuichi

2015-01-01

201

Synthesis, Characterization, Semiempirical and Biological Activities of Organotin(IV) Carboxylates with 4-Piperidinecarboxylic Acid  

PubMed Central

Organotin (IV) carboxylates with the general formulae R2Sn(Cl)L [R?=?Me (1), n-Bu (2), Ph (3)] and R3SnL [R?=?Me (4), Ph (5)] have been synthesized by the reaction of 4-piperidinecarboxylic acid (HL) with KOH and R2SnCl2 (R?=?Me, n-Bu, Ph)/R3SnCl (R?=?Me, Ph) in methanol under stirring conditions. The metal ligand binding site, structure, and stability of complexes have been verified by FT-IR, (1H, 13C) NMR, EI-MS technique, and semiempirical study. The FT-IR data indicate the bidentate chelating mode of the carboxylate ligand which is also confirmed by semiempirical study. In solution state, five and four coordinated geometry around tin was confirmed by NMR spectroscopy. The EI-MS data agreed well with the molecular structure of the complexes. Thermodynamic parameters and molecular descriptors were calculated by using semiempirical PM3 method. HOMO-LUMO calculations show that chlorodiorganotin complexes are more susceptible to nucleophilic attack as compared to triorganotin complexes. Computed negative heat of formation indicates that complexes 1–4 are thermodynamically stable. The organotin(IV) carboxylates displayed powerful antimicrobial activities against various strains of bacteria and fungi and their minimal inhibitory concentration were also evaluated. The complexes exhibited comparatively higher hemolytic activity as compared to free ligand. PMID:25548551

Sharma, Saroj K.; Qanungo, Kushal; Shahid, Muhammad

2014-01-01

202

Malic acid production by Saccharomyces cerevisiae: engineering of pyruvate carboxylation, oxaloacetate reduction, and malate export.  

PubMed

Malic acid is a potential biomass-derivable "building block" for chemical synthesis. Since wild-type Saccharomyces cerevisiae strains produce only low levels of malate, metabolic engineering is required to achieve efficient malate production with this yeast. A promising pathway for malate production from glucose proceeds via carboxylation of pyruvate, followed by reduction of oxaloacetate to malate. This redox- and ATP-neutral, CO(2)-fixing pathway has a theoretical maximum yield of 2 mol malate (mol glucose)(-1). A previously engineered glucose-tolerant, C(2)-independent pyruvate decarboxylase-negative S. cerevisiae strain was used as the platform to evaluate the impact of individual and combined introduction of three genetic modifications: (i) overexpression of the native pyruvate carboxylase encoded by PYC2, (ii) high-level expression of an allele of the MDH3 gene, of which the encoded malate dehydrogenase was retargeted to the cytosol by deletion of the C-terminal peroxisomal targeting sequence, and (iii) functional expression of the Schizosaccharomyces pombe malate transporter gene SpMAE1. While single or double modifications improved malate production, the highest malate yields and titers were obtained with the simultaneous introduction of all three modifications. In glucose-grown batch cultures, the resulting engineered strain produced malate at titers of up to 59 g liter(-1) at a malate yield of 0.42 mol (mol glucose)(-1). Metabolic flux analysis showed that metabolite labeling patterns observed upon nuclear magnetic resonance analyses of cultures grown on (13)C-labeled glucose were consistent with the envisaged nonoxidative, fermentative pathway for malate production. The engineered strains still produced substantial amounts of pyruvate, indicating that the pathway efficiency can be further improved. PMID:18344340

Zelle, Rintze M; de Hulster, Erik; van Winden, Wouter A; de Waard, Pieter; Dijkema, Cor; Winkler, Aaron A; Geertman, Jan-Maarten A; van Dijken, Johannes P; Pronk, Jack T; van Maris, Antonius J A

2008-05-01

203

Malic Acid Production by Saccharomyces cerevisiae: Engineering of Pyruvate Carboxylation, Oxaloacetate Reduction, and Malate Export? †  

PubMed Central

Malic acid is a potential biomass-derivable “building block” for chemical synthesis. Since wild-type Saccharomyces cerevisiae strains produce only low levels of malate, metabolic engineering is required to achieve efficient malate production with this yeast. A promising pathway for malate production from glucose proceeds via carboxylation of pyruvate, followed by reduction of oxaloacetate to malate. This redox- and ATP-neutral, CO2-fixing pathway has a theoretical maximum yield of 2 mol malate (mol glucose)?1. A previously engineered glucose-tolerant, C2-independent pyruvate decarboxylase-negative S. cerevisiae strain was used as the platform to evaluate the impact of individual and combined introduction of three genetic modifications: (i) overexpression of the native pyruvate carboxylase encoded by PYC2, (ii) high-level expression of an allele of the MDH3 gene, of which the encoded malate dehydrogenase was retargeted to the cytosol by deletion of the C-terminal peroxisomal targeting sequence, and (iii) functional expression of the Schizosaccharomyces pombe malate transporter gene SpMAE1. While single or double modifications improved malate production, the highest malate yields and titers were obtained with the simultaneous introduction of all three modifications. In glucose-grown batch cultures, the resulting engineered strain produced malate at titers of up to 59 g liter?1 at a malate yield of 0.42 mol (mol glucose)?1. Metabolic flux analysis showed that metabolite labeling patterns observed upon nuclear magnetic resonance analyses of cultures grown on 13C-labeled glucose were consistent with the envisaged nonoxidative, fermentative pathway for malate production. The engineered strains still produced substantial amounts of pyruvate, indicating that the pathway efficiency can be further improved. PMID:18344340

Zelle, Rintze M.; de Hulster, Erik; van Winden, Wouter A.; de Waard, Pieter; Dijkema, Cor; Winkler, Aaron A.; Geertman, Jan-Maarten A.; van Dijken, Johannes P.; Pronk, Jack T.; van Maris, Antonius J. A.

2008-01-01

204

Accumulation of the Antibiotic Phenazine-1-Carboxylic Acid in the Rhizosphere of Dryland Cereals  

PubMed Central

Natural antibiotics are thought to function in the defense, fitness, competitiveness, biocontrol activity, communication, and gene regulation of microorganisms. However, the scale and quantitative aspects of antibiotic production in natural settings are poorly understood. We addressed these fundamental questions by assessing the geographic distribution of indigenous phenazine-producing (Phz+) Pseudomonas spp. and the accumulation of the broad-spectrum antibiotic phenazine-1-carboxylic acid (PCA) in the rhizosphere of wheat grown in the low-precipitation zone (<350 mm) of the Columbia Plateau and in adjacent, higher-precipitation areas. Plants were collected from 61 commercial wheat fields located within an area of about 22,000 km2. Phz+ Pseudomonas spp. were detected in all sampled fields, with mean population sizes ranging from log 3.2 to log 7.1 g?1 (fresh weight) of roots. Linear regression analysis demonstrated a significant inverse relationship between annual precipitation and the proportion of plants colonized by Phz+ Pseudomonas spp. (r2 = 0.36, P = 0.0001). PCA was detected at up to nanomolar concentrations in the rhizosphere of plants from 26 of 29 fields that were selected for antibiotic quantitation. There was a direct relationship between the amount of PCA extracted from the rhizosphere and the population density of Phz+ pseudomonads (r2 = 0.46, P = 0.0006). This is the first demonstration of accumulation of significant quantities of a natural antibiotic across a terrestrial ecosystem. Our results strongly suggest that natural antibiotics can transiently accumulate in the plant rhizosphere in amounts sufficient not only for inter- and intraspecies signaling but also for the direct inhibition of sensitive organisms. PMID:22138981

Mavrodi, Dmitri V.; Mavrodi, Olga V.; Parejko, James A.; Bonsall, Robert F.; Kwak, Youn-Sig; Paulitz, Timothy C.; Weller, David M.

2012-01-01

205

Evaluating the potential of long chain n-alkanes and n-carboxylic acids as biomarkers for past vegetation  

NASA Astrophysics Data System (ADS)

Leaf waxes, such as long chain n-alkanes and n-carboxylic acids, may have a great potential for the reconstruction of past environmental and climate conditions (e.g. (Zech R. et al., 2013). While n-C27 and n-C29 alkanes often predominantly occur in trees and shrubs, n-C31 and n-C33 are more abundant in grasses and herbs. However, little is known about chain-length distributions of n-carboxylic acids, and very few studies have systematically investigated leaf waxes in top soils. We analyzed n-alkanes and n-carboxylic acids in ~100 litter and topsoil samples from Southern Germany to Sweden. Our results show that sites under deciduous trees often contain a lot of C27 n-alkanes and C28 n-carboxylic acids. Coniferous sites are characterized by dominance in n-alkanes C29 and C31 and have relatively high concentrations of n-carboxylic acids C22 and C24. Grass sites show a Cmax at C31 for n-alkanes and at C24 or C26 for n-carboxylic acids. Differences in homologue patterns are most pronounced in the litter samples, but are well preserved also in the topsoils (0-3 cm depth, a little less in the lower topsoils from 3-10 cm). Our results illustrate the potential of combining n-alkane and n-carboxylic acid analyses for paleo-vegetation reconstructions, yet indicate that the degree of degradation may have to be taken into consideration (Zech M. et al., 2013). References: Zech, M. et al. (2013) Quat. Int. 296, 108-116. Zech, R. et al. (2013) Palaeo3, 387, 165-175.

Lanny, Verena; Zech, Roland; Eglinton, Timothy

2014-05-01

206

Hydrogen-bonding linkage of thymidine derivatives with carboxylic acid and pyridyl groups in a crystalline state.  

PubMed

Thymidine derivatives with carboxylic acid and pyridyl groups were synthesized for constructing one-dimensional network structure based on hydrogen bonding in crystalline state. The solid sate structures and hydrogen bonding networks of the thymidine derivatives were characterized by single X-ray diffraction analysis. The thymidine derivatives formed a zwitterion structure with a pyridinium proton and a carboxylate moiety in a crystalline state due to transfer of a proton from the carboxylic acid to the pyridyl moiety. Strong hydrogen bonds between the pyridinium proton and the carboxylate moiety connected the thymidine units, resulting in a one-dimensional polymeric structure with a uniform direction reminiscent of the structure of single-strand polythymidine. The chemical structure of the pyridyl group affects the hydrogen-bonding networks. The well-designed hydrogen-bonding interaction served as connecting parts for polythymidine mimics even in the presence of other hydrogen-bonding motifs such as nucleobases. PMID:23901479

Hoshino, Junichi; Kuwabara, Junpei; Kanbara, Takaki

2013-07-01

207

Preferential interaction of Na+ over K+ with carboxylate-functionalized silver nanoparticles.  

PubMed

Elucidating mechanistic interactions between monovalent cations (Na(+)/K(+)) and engineered nanoparticle surfaces to alter particle stability in polar media have received little attention. We investigated relative preferential interaction of Na(+) and K(+) with carboxylate-functionalized silver nanoparticles (carboxylate-AgNPs) to determine if interaction preference followed the Hofmeister series (Na(+)>K(+)). We hypothesized that Na(+) will show greater affinity than K(+) to pair with carboxylates on AgNP surfaces, thereby destabilizing the colloidal system. Destabilization upon Na(+) or K(+) interacting with carboxylate-AgNPs was evaluated probing changes in multiple physicochemical characteristics: surface plasmon resonance/optical absorbance, electrical conductivity, pH, hydrodynamic diameter, electrophoretic mobility, surface charge, amount of Na(+)/K(+) directly associated with AgNPs, and Ag(+) dissociation kinetics. We show that Na(+) and K(+) react differently, indicating local Na(+) pairing with carboxylates on AgNP surfaces is kinetically faster and remarkably favored over K(+), thus supporting Hofmeister ordering. Our results suggest that AgNPs may transform into micron-size aggregates upon release into aqueous environments and that the fate of such aggregates may need consideration when assessing environmental risk. PMID:24840275

Pokhrel, Lok R; Andersen, Christian P; Rygiewicz, Paul T; Johnson, Mark G

2014-08-15

208

Iridium Catalyzed Hydrocarboxylation of 1,1-Dimethylallene: Byproduct-Free Reverse Prenylation of Carboxylic Acids  

PubMed Central

Exposure of carboxylic acids 1a-12a to commercially available 1,1-dimethylallene in the presence of substoichiometric quantities of an iridium catalyst prepared in situ from [Ir(cod)Cl]2 and BIPHEP provides the corresponding 1,1-dimethylallyl (reverse prenyl) esters 1b-12b in 74–92% isolated yield. This protocol represents the first branch-regioselective allene hydrocarboxylation. Stoichiometric byproducts are not generated in this process and protecting groups are not required for alcohols, phenols and indolic amines. PMID:18181640

Kim, In Su

2010-01-01

209

Retention of heavy metals by carboxyl functional groups of biochars in small arms range soil  

Technology Transfer Automated Retrieval System (TEKTRAN)

Long-term effectiveness of biochar for heavy metal stabilization depends upon biochar’s sorptive property and recalcitrance in soil. To understand the role of carboxyl functional groups on heavy metal stabilization, cottonseed hull biochar and flax shive steam activated biochar having low O/C ratio...

210

Europium(III) complexes of polyfunctional carboxylic acids: Luminescence probes of possible binding sites in fulvic acid  

SciTech Connect

The {sup 7}F{sub 0} {r_arrow} {sup 5}D{sub 0} excitation spectra of Eu(III) complexed with polyfunctional dicarboxylic acid containing neutral O, N, and S donors were investigated using Eu(III) luminescence spectroscopy. Three distinct peaks are seen in the excitation spectra in the Eu(III)-diglycolic acid (ODA) and Eu(III)-iminodiacetic acid (IMDA) systems showing the formation of three species, where each tridentate ODA {sup 2{minus}} and IMDA{sup 2{minus}} displace approximately three coordinated water molecules; however, the central S donor of Eu(III)-thiodiglycolate and 2,5-thiophenedicarboxylate are shown to be poor chelators for free Eu{sup 3+} ions. The neutral O and N donors in combination with neighboring carboxylates may form strong metal chelation sites on fulvic acid.

Lee, B.H.; Chung, K.H.; Shin, H.S.; Moon, H. [Korea Advanced Inst. of Science and Technology, Taejon (Korea, Republic of). Dept. of Chemistry] [Korea Advanced Inst. of Science and Technology, Taejon (Korea, Republic of). Dept. of Chemistry; Park, Y.J. [Korea Atomic Energy Research Inst., Taejon (Korea, Republic of)] [Korea Atomic Energy Research Inst., Taejon (Korea, Republic of)

1997-04-15

211

Nickel-catalysed carboxylation of organoboronates.  

PubMed

A nickel/N-heterocyclic carbene (NHC) catalysed carboxylation of aryl-, heteroaryl- and alkenylboronates, affording the corresponding carboxylic acids, has been developed. This transformation proceeds under one atmosphere of CO2 with a broad range of substrates and exhibits good functional group compatibility. PMID:24915842

Makida, Yusuke; Marelli, Enrico; Slawin, Alexandra M Z; Nolan, Steven P

2014-07-28

212

Solubility of Small-Chain Carboxylic Acids in Supercritical Carbon Dioxide  

SciTech Connect

The solubility of heptanoic acid and octanoic acid in supercritical carbon dioxide has been determined at temperatures of (313.15, 323.15, and 333.15) K over a pressure range of (8.5 to 30.0) MPa, depending upon the solute. The solubility of heptanoic acid ranged from a solute concentration of (0.08 ± 0.03) kg�m -3 (T = 323.15 K, p = 8.5 MPa) to (147 ± 0.2) kg�m -3 (T = 323.15 K, p = 20.0 MPa). The lowest octanoic acid solubility obtained was a solute concentration of (0.40 ± 0.1) kg�m -3 (T = 333.15 K, p = 10.0 MPa), while the highest solute concentration was (151 ± 2) kg�m -3 (T = 333.15 K, p = 26.7 MPa). Additionally, solubility experiments were performed for nonanoic acid in supercritical carbon dioxide at 323.15 K and pressures of (10.0 to 30.0) MPa to add to the solubility data previously published by the authors. In general, carboxylic acid solubility increased with increasing solvent density. The results also showed that the solubility of the solutes decreased with increasing molar mass at constant supercritical-fluid density. Additionally, the efficacy of Chrastil's equation and other density-based models was evaluated for each fatty acid.

Sparks, Darrell L.; Estevez, L. Antonio; Hernandez, Rafael; McEwen, Jason; French, Todd

2010-07-08

213

Charge transport and structural dynamics in carboxylic-acid-based deep eutectic mixtures.  

PubMed

Charge transport and structural dynamics in the 1:2 mol ratio mixture of lidocaine and decanoic acid (LID-DA), a model deep eutectic mixture (DEM), have been characterized over a wide temperature range using broad-band dielectric spectroscopy and depolarized dynamic light scattering. Additionally, Fourier transform infrared spectroscopy measurements were performed to assess the degree of proton transfer between the neutral parent molecules. From our detailed analysis of the dielectric spectra, we have determined that this carboxylic-acid-based DEM is approximately 25% ionic at room temperature. Furthermore, we have found that the characteristic diffusion rate of mobile charge carriers is practically identical to the rate of structural relaxation at all measured temperatures, indicating that fast proton transport does not occur in LID-DA. Our results demonstrate that while LID-DA exhibits the thermal characteristics of a DEM, its charge transport properties resemble those of a protic ionic liquid. PMID:25025600

Griffin, Philip J; Cosby, Tyler; Holt, Adam P; Benson, Roberto S; Sangoro, Joshua R

2014-08-01

214

A supported polymeric liquid membrane process for removal of carboxylic acids from a waste stream  

SciTech Connect

The removal or elimination of organic residues from aqueous waste streams represents a major need in the chemical industry. The authors have developed a new class of membrane called supported polymeric liquid membranes that are capable of removing and concentrating low molecular weight organic compounds from dilute aqueous solutions, especially those that also contain high concentrations of inorganic salts. Attractive features of this membrane process include the ability to recover the contaminants in concentrated form for either recycle or more economical disposal, low pressure (ambient) operation, simple scale-up using commercial hollow fiber modules, and ease of in-situ regeneration of the polymeric liquid. The process has shown treatment feasibility for several types of aqueous waste streams. This paper describes the laboratory development activities for treating a waste stream containing a dilute mixture of C2-C6 carboxylic acids and nitric acid.

Ho, S.V.

1999-12-31

215

Synthesis, spectroscopic characterization and molecular modeling of a tetranuclear platinum(II) complex with thiazolidine-4-carboxylic acid  

NASA Astrophysics Data System (ADS)

The synthesis, spectroscopic characterization and molecular modeling of a novel tetranuclear platinum(II) complex with thiazolidine-4-carboxylic acid (THC) are described. Elemental analysis is consistent with the composition PtCl2C4H7NO2S·H2O. Infrared (IR) spectroscopic results and solid-state 13C and 15N nuclear magnetic resonance (NMR) data indicate coordination of the ligand to Pt(II) through the nitrogen and sulfur atoms. The square planar geometry of the platinum(II) complex is completed by chlorine atoms. Density functional theory (DFT) suggests the formation of a tetrameric cluster as the most probable structure, where each THC molecule bridges between two metal centers. The compound is insoluble in water.

Corbi, Pedro P.; Formiga, André L. B.; Bonk, Fábio A.; Quintão, Frederico A.; Ferraresi, Diego K. D.; Lustri, Wilton R.; Massabni, Antonio C.

2012-07-01

216

Ion-pair reversed-phase liquid chromatography for determination of polar underivatized amino acids using perfluorinated carboxylic acids as ion pairing agent  

Microsoft Academic Search

An isocratic liquid chromatography method using volatile ion pairing agent and evaporative light scattering detection was developed for the analysis of 10 underivatized amino acids (Asp, Asn, Ser, Gly, Gln, Cys, Glu, Thr, Ala, Pro) which are not sufficiently retained and resolved in the LC system commonly used. Five perfluorinated carboxylic acids (trifluoroacetic, heptafluorobutyric, nonafluoropentanoic, tridecafluoroheptanoic and pentadecafluorooctanoic acid) have

K. N Petritis; P Chaimbault; C Elfakir; M Dreux

1999-01-01

217

The use of fluorine-containing carboxylic acids for the large-scale isolation of highly polymerized deoxyribonucleic acids  

PubMed Central

1. The precipitation of the proteins of calf-thymus nucleohistone and herringsperm nucleoprotamine with the salts of fluorine-containing carboxylic acids has been studied. Pentadecafluoro-octanoate gave a precipitate that could be sedimented almost completely by centrifuging at 2350g for 20min. ?-H-Hexadecafluorononanoate, ?-H-eicosafluoro-undecanoate and dodecyl sulphate gave precipitates that could only be partly sedimented under these conditions. 2. A method has been developed for the isolation of highly polymerized DNA on a large scale from calf thymus and herring sperm by the use of pentadecafluorooctanoate. This is more convenient and less tedious than existing methods. PMID:6007456

Jones, A. S.; Walker, R. T.

1966-01-01

218

Sulfonated poly(ether ether ketone) membranes containing pendent carboxylic acid groups and their application in vanadium flow battery  

NASA Astrophysics Data System (ADS)

Sulfonated poly(ether ether ketone) (C-SPEEK) membranes with pendent carboxylic acid groups are prepared and first investigated for vanadium flow battery (VFB) application. The introduction of carboxylic acid groups can effectively improve the ion conductivities of C-SPEEK membranes, while, keep their ion selectivities. The prepared C-SPEEK membranes exhibit excellent performance under VFB operating condition. VFB single cell assembled with C-SPEEK-50 membranes shows much higher energy efficiency (85% Vs 82%) and columbic efficiency (97.3% Vs 94.6%) than that assembled with Nafion 115. The membrane keeps a stable performance after more than 180 cycles charge-discharge test, showing good stability.

Chen, Dongju; Li, Xianfeng

2014-02-01

219

Addition of carboxylic acids modifies phosphate sorption on soil and boehmite surfaces: a solution chemistry and XANES spectroscopy study.  

PubMed

Soil acidification is a globally significant agricultural issue, as the plant availability of phosphorus (P) is decreased through increased P sorption onto aluminium (Al) hydroxides and other solid phase binding sites. X-ray absorption near edge structure (XANES) spectroscopy generated new information on the speciation of Al and P in the presence of carboxylic acids on soil and boehmite (gamma-AlOOH) surfaces. XANES spectra were acquired in the soft X-ray regime at the P and Al L(2,3)-edges, and the Al K-edge, respectively. Adding oxalic acid to soil enhanced Al dissolution and exposed previously occluded soil P, while hydroxybenzoic and coumaric acids did not compete with P for surface binding sites. Boehmite strongly adsorbed carboxylic acids in the absence of applied phosphorus. However, when P was applied with carboxylic acids, the carboxylics were unable to compete with P for binding, especially hydroxybenzoic and coumaric acids. Using XANES in both total electron yield and fluorescence yield modes provided valuable information on both surface and near-surface processes of P and Al due to different information depths. The Al K-edge XANES provided baseline information on the solid-phase matrix. XANES in total electron yield mode and at the P L-edge shows promise for speciation of elements on soil surfaces due to enhanced sensitivity for speciation of surface-adsorbed species compared to the commonly used P K-edge XANES. PMID:18990400

Schefe, C R; Kappen, P; Zuin, L; Pigram, P J; Christensen, C

2009-02-01

220

Abiotic Formation of Carboxylic Acids (RCOOH) in Interstellar and Solar System Model Ices  

NASA Astrophysics Data System (ADS)

The present laboratory study simulated the abiotic formation of carboxylic acids (RCOOH) in interstellar and solar system model ices of carbon dioxide (CO2)-hydrocarbon mix C n H2n+2 (n = 1-6). The pristine model ices were irradiated at 10 K under contamination-free, ultrahigh vacuum conditions with energetic electrons generated in the track of galactic cosmic-ray particles. The chemical processing of the ices was monitored by a Fourier transform infrared spectrometer and a quadrupole mass spectrometer during the irradiation phase and subsequent warm-up phases on line and in situ in order to extract qualitative (carriers) and quantitative (rate constants and yields) information on the newly synthesized species. Carboxylic acids were identified to be the main carrier, together with carbon monoxide (CO) and a trace of formyl (HCO) and hydroxycarbonyl (HOCO) radicals at 10 K. The upper limit of acid column density at 10 K was estimated as much as (1.2 ± 0.1) × 1017 molecules cm-2 at doses of 17 ± 2 eV molecule-1, or the yield of 39% ± 4% from the initial column density of carbon dioxide. The temporal column density profiles of the products were then numerically fit using two independent kinetic schemes of reaction mechanisms. Finally, we transfer this laboratory simulation to star-forming regions of the interstellar medium, wherein cosmic-ray-induced processing of icy grains at temperatures as low as 10 K could contribute to the current level of chemical complexity as evidenced in astronomical observations and in extracts of carbonaceous meteorites.

Kim, Y. S.; Kaiser, R. I.

2010-12-01

221

A fluorimetric study of terbium, europium and dysprosium in aqueous solution using pyridine carboxylic acids as ligands  

Microsoft Academic Search

Fluorescence enhancement of Tb3+, Eu3+ and Dy3+ was studied in aqueous solution using pyridine carboxylic acids (nicotinic, picolinic and dipicolinic acids) as ligands. The fluorescence intensity of Tb3+, Eu3+ and Dy3+ could be enhanced, contrary to an earlier report by more than two to three orders of magnitude using these acids as ligands. To further enhance the lanthanide fluorescence, a

B. S Panigrahi

2002-01-01

222

A practical two-step procedure for the preparation of enantiopure pyridines: Multicomponent reactions of alkoxyallenes, nitriles and carboxylic acids followed by a cyclocondensation reaction  

PubMed Central

Summary A practical approach to highly functionalized 4-hydroxypyridine derivatives with stereogenic side chains in the 2- and 6-positions is described. The presented two-step process utilizes a multicomponent reaction of alkoxyallenes, nitriles and carboxylic acids to provide ?-methoxy-?-ketoenamides which are transformed into 4-hydroxypyridines in a subsequent cyclocondensation. The process shows broad substrate scope and leads to differentially substituted enantiopure pyridines in good to moderate yields. The preparation of diverse substituted lactic acid derived pyrid-4-yl nonaflates is described. Additional evidence for the postulated mechanism of the multicomponent reaction is presented. PMID:21915195

Eidamshaus, Christian; Kumar, Roopender; Bera, Mrinal K

2011-01-01

223

Understanding potential exposure sources of perfluorinated carboxylic acids in the workplace.  

PubMed

This paper integrates perspectives from analytical chemistry, environmental engineering, and industrial hygiene to better understand how workers may be exposed to perfluorinated carboxylic acids when handling them in the workplace in order to identify appropriate exposure controls. Due to the dramatic difference in physical properties of the protonated acid form and the anionic form, this family of chemicals provides unique industrial hygiene challenges. Workplace monitoring, experimental data, and modeling results were used to ascertain the most probable workplace exposure sources and transport mechanisms for perfluorooctanoic acid (PFOA) and its ammonium salt (APFO). PFOA is biopersistent and its measurement in the blood has been used to assess human exposure since it integrates exposure from all routes of entry. Monitoring suggests that inhalation of airborne material may be an important exposure route. Transport studies indicated that, under low pH conditions, PFOA, the undissociated (acid) species, actively partitions from water into air. In addition, solid-phase PFOA and APFO may also sublime into the air. Modeling studies determined that contributions from surface sublimation and loss from low pH aqueous solutions can be significant potential sources of workplace exposure. These findings suggest that keeping surfaces clean, preventing accumulation of material in unventilated areas, removing solids from waste trenches and sumps, and maintaining neutral pH in sumps can lower workplace exposures. PMID:20974675

Kaiser, Mary A; Dawson, Barbara J; Barton, Catherine A; Botelho, Miguel A

2010-11-01

224

Effects of carboxylic acids on the rheological properties of crumb rubber modified asphalt  

SciTech Connect

The Federal mandate of 1991-1995 on the use of scrap tires in Federal roadway construction sparked a major interest in gaining a fundamental understanding of the behavior of rubber in asphalt. This study is a systematic elucidation of what chemistry controls the final crumb rubber modified asphalt (CRMA) product quality. We discovered that the type and total acid content in the asphalt are the most influential chemical factors that determine the changes in the important roadway properties of shear modulus (G*) and loss angle ({delta}) of CRMA. Low acid (<0.005 m/L) asphalts were modified with three types of carboxylic acid and each made into CRMA using typical field mixing conditions of 1 hour at 175{degrees}C. Rheological measurements were then made at various storage times up to 192 hours following storage at both 156 and 200{degrees}C. We found the changes in CRMA theological properties correspond to the acid type spiked into the asphalt.

Tauer, J.E.; Robertson, R.E. [Western Research Institute, Laramie, WY (United States)

1996-12-31

225

Understanding Potential Exposure Sources of Perfluorinated Carboxylic Acids in the Workplace  

PubMed Central

This paper integrates perspectives from analytical chemistry, environmental engineering, and industrial hygiene to better understand how workers may be exposed to perfluorinated carboxylic acids when handling them in the workplace in order to identify appropriate exposure controls. Due to the dramatic difference in physical properties of the protonated acid form and the anionic form, this family of chemicals provides unique industrial hygiene challenges. Workplace monitoring, experimental data, and modeling results were used to ascertain the most probable workplace exposure sources and transport mechanisms for perfluorooctanoic acid (PFOA) and its ammonium salt (APFO). PFOA is biopersistent and its measurement in the blood has been used to assess human exposure since it integrates exposure from all routes of entry. Monitoring suggests that inhalation of airborne material may be an important exposure route. Transport studies indicated that, under low pH conditions, PFOA, the undissociated (acid) species, actively partitions from water into air. In addition, solid-phase PFOA and APFO may also sublime into the air. Modeling studies determined that contributions from surface sublimation and loss from low pH aqueous solutions can be significant potential sources of workplace exposure. These findings suggest that keeping surfaces clean, preventing accumulation of material in unventilated areas, removing solids from waste trenches and sumps, and maintaining neutral pH in sumps can lower workplace exposures. PMID:20974675

Kaiser, Mary A.; Dawson, Barbara J.; Barton, Catherine A.; Botelho, Miguel A.

2010-01-01

226

Dielectric, electric and thermal properties of carboxylic functionalized multiwalled carbon nanotubes impregnated polydimethylsiloxane nanocomposite  

NASA Astrophysics Data System (ADS)

The dielectric, electric and thermal properties of carboxylic functionalized multiwalled carbon nanotubes (F-MWCNT) incorporated into the polydimethylsiloxane (PDMS) were evaluated to determine their potential in the field of electronic materials. Carboxylic functionalization of the pristine multi walled carbon tubes (Ps-MWCNT) was confirmed through Fourier transform infrared spectroscopy, X-ray diffraction patterns for both Ps-MWCNTs and F-MWCNTs elaborated that crystalline behavior did not change with carboxylic moieties. Thermogravimetric and differential thermal analyses were performed to elucidate the thermal stability with increasing weight % addition of F-MWCNTs in the polymer matrix. Crystallization/glass transition / melting temperatures were evaluated using differential scanning calorimeter and it was observed that glass transition and crystallization temperatures were diminished while temperatures of first and second melting transitions were progressed with increasing F-MWCNT concentration in the PDMS matrix. Scanning electron microscopy and energy dispersive x-ray spectroscopy were carried out to confirm the morphology, functionalization, and uniform dispersion of F-MWCNTs in the polymer matrix. Electrical resistivity at temperature range (100-300°C), dielectric loss (tan?) and dielectric parameters (epsilon/ epsilon//) were measured in the frequency range (1MHz-3GHz). The measured data simulate that the aforementioned properties were influenced by increasing filler contents in the polymer matrix because of the high polarization of conductive F-MWCNTs at the reinforcement/polymer interface.

Sagar, Sadia; Iqbal, Nadeem; Maqsood, Asghari

2013-06-01

227

Challenges in the Synthesis of a Unique Mono-Carboxylic Acid Antibiotic (+)-Zincophorin  

PubMed Central

(+)-Zincophorin, also referred to as M144255 or griseochellin, is a polyoxygenated ionophoric antibiotic that was isolated from Streptomyces griseus in 1984. It possesses strong in vivo activity against Gram-positive bacteria and Clostridium coelchii. Its methyl ester was reported in a patent as having strong inhibitory properties against influenza WSN/virus with reduced toxicity for the host cell. Its ability to strongly bind with Zn2+, which is also present in its X-ray structure, is the basis for its name. Over the last two decades, (+)-zincophorin h as attracted an impressive array of synthetic efforts including Danishefsky's first total synthesis along with two recent elegant total syntheses reported by Cossy and Miyashita as well as our own formal total synthesis. This Account provides a comparison of the different synthetic efforts on this novel mono-carboxylic acid antibiotic and documents its interesting isolation, structure determination, and biological activities. PMID:19642422

Song, Zhenlei; Lohse, Andrew G.; Hsung, Richard P.

2009-01-01

228

Azetidine-2-carboxylic acid resistant mutants of Arabidopsis thaliana with increased salt tolerance  

SciTech Connect

Nineteen mutant Arabidopsis families resistant to the proline analog azetidine-2-carboxylic acid (ACA) were characterized in terms of NaCl tolerance and proline content. Mutants were selected from about 64,000 progeny of about 16,000 self-pollinated Columbia parents which had been mutated with ethyl methane sulfonate during seed imbibition. Selections were performed during seed germination on aseptic agar medium containing 0.2 to 0.25 mM ACA. Nineteen mutant families, 12 clearly independent, retained resistance to ACA in the M{sub 4} generation. Based on germination on 150 mM NaCl, 13 of the mutant families were more tolerant than the wild type. Two mutants of intermediate resistance to ACA were markedly more salt tolerant than the others. Four mutant families appeared to overproduce proline. Of these, only 3 showed slight increases in salt tolerance.

Lehle, F.R.; Murphy, M.A.; Khan, R.A. (Univ. of Arizona, Tuscon (USA))

1989-04-01

229

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

PubMed Central

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. PMID:22837666

Lu, Chao; Wei, Yinying; Zhu, Erkuang; Reutt-Robey, Janice E.; Xu, Bo

2012-01-01

230

Yeast fermentation of carboxylic acids obtained from pyrolytic aqueous phases for lipid production.  

PubMed

The presence of very reactive C1-C4 molecules adversely affects the quality bio-oils produced from the pyrolysis of lignocellulosic materials. In this paper a scheme to produce lipids with Cryptococcus curvatus from the carboxylic acids in the pyrolytic aqueous phase collected in fractional condensers is proposed. The capacities of three oleaginous yeasts C. curvatus, Rhodotorula glutinis, Lipomyces starkeyi to ferment acetate, formate, hydroxylacat-aldehyde, phenol and acetol were investigated. While acetate could be a good carbon source for lipid production, formate provides additional energy and contributes to yeast growth and lipid production as auxiliary energy resource. Acetol could slightly support yeast growth, but it inhibits lipid accumulation. Hydroxyacetaldehyde and phenols showed high yeast growth and lipid accumulation inhibition. A pyrolytic aqueous phase with 20 g/L acetate was fermented with C. curvatus, after neutralization and detoxification to produce 6.9 g/L dry biomass and 2.2 g/L lipid. PMID:22705522

Lian, Jieni; Garcia-Perez, Manuel; Coates, Ralph; Wu, Hongwei; Chen, Shulin

2012-08-01

231

Short-chain carboxylic acids from gray catbird (Dumetella carolinensis) uropygial secretions vary with testosterone levels and photoperiod.  

PubMed

The uropygial gland of birds produces secretions that are important in maintaining the health and structural integrity of feathers. Non-volatile components of uropygial secretions are believed to serve a number of functions including waterproofing and conditioning the feathers. Volatile components have been characterized in fewer species, but are particularly interesting because of their potential importance in olfactory interactions within and across species. We used solid-phase microextraction headspace sampling with gas chromatography-mass spectrometry to detect and identify volatiles in uropygial secretions of gray catbirds (Dumetella carolinensis), a North American migratory bird. We consistently detected the following carboxylic acids: acetic, propanoic, 2-methylpropanoic, butanoic, and 3-methylbutanoic. We tested for the effect of lengthened photoperiod and/or exogenous testosterone on volatile signal strength and found a negative effect of lengthened photoperiod on the signal strength of propanoic, 2-methylpropanoic, and butanoic acids, suggesting a trade-off between their production and heightened night-time activity associated with lengthened photoperiod. Signal strength of propanoic and 2-methylpropanoic acids was lower in birds treated with exogenous testosterone than in birds treated with placebos. Sex did not affect signal strength of any of the volatile compounds. PMID:20346408

Whelan, Rebecca J; Levin, Tera C; Owen, Jennifer C; Garvin, Mary C

2010-07-01

232

Enantioselective synthesis of ( R)- and ( S)- N-Boc-morpholine-2-carboxylic acids by enzyme-catalyzed kinetic resolution: application to the synthesis of reboxetine analogs  

Microsoft Academic Search

The (R)- and (S)-N-Boc-morpholine-2-carboxylic acids 9 and 10 were prepared using an enantioselective synthesis employing a highly selective enzyme-catalyzed kinetic resolution of racemic n-butyl 4-benzylmorpholine-2-carboxylate (11) as the key step. Acids 9 and 10 were then converted efficiently and stereoselectively to reboxetine analogs 3 and 4.

Paul V. Fish; Malcolm Mackenny; Gerwyn Bish; Timothy Buxton; Russell Cave; David Drouard; David Hoople; Alan Jessiman; Duncan Miller; Christelle Pasquinet; Bhairavi Patel; Keith Reeves; Thomas Ryckmans; Melanie Skerten; Florian Wakenhut

2009-01-01

233

Direct ester condensation from a 1:1 mixture of carboxylic acids and alcohols catalyzed by hafnium(IV) or zirconium(IV) salts  

Microsoft Academic Search

To promote atom efficiency in synthesis and to avoid the generation of environmental waste, the use of stoichiometric amounts of condensing reagents or excess substrates should be avoided. In esterification, excess amounts of either carboxylic acids or alcohols are normally needed. We found that the direct condensation of equimolar amounts of carboxylic acids and alcohols could be achieved using hafnium(IV)

Kazuaki Ishihara; Masaya Nakayama; Suguru Ohara; Hisashi Yamamoto

2002-01-01

234

Analysis of protein back-extraction processes in alcohol- and carboxylic acid-mediated AOT reverse micellar systems based on structural changes of proteins and reverse micelles  

Microsoft Academic Search

The effects of the addition of alcohol and carboxylic acid on the back-extraction of several small globular proteins such as ?-lactoglobulin (?-LG), bovine carbonic anhydrase (CAB), and lipase have been studied using reverse micellar systems (RVMS). The protein back-extraction induced by the addition of alcohol and carboxylic acid was markedly influenced by the structural changes of reverse micelles (?t) and

Bong-Kuk Lee; Dong-Pyo Hong; Sung-Sik Lee; Ryoichi Kuboi

2004-01-01

235

Dissociative Binding of Carboxylic Acid Ligand on Nanoceria Surface in Aqueous Solution: A Joint in Situ Spectroscopic Characterization and First-Principles Study  

SciTech Connect

Carboxylic acid is a common ligand anchoring group to functionalize nanoparticle surfaces. Its binding structures and mechanisms as a function of the oxidation states of metal oxide nanoparticle surfaces are not well characterized experimentally. We present an in situ sum frequency generation vibrational spectroscopy (SFG-VS) study on the binding of deuterated acetic acid on ceria nanoparticles in the aqueous solution. In the SFG experiment, ceria nanoparticles were deposited on the flat surface of a CaF2 hemisphere in contact with acetic acid solutions. While the ceria nanoparticle deprotonated the acetic acid, the CaF2 surface could not. Thus, the binding of the deprotonated acetic acid on ceria can be selectively probed. SFG spectra revealed that the binding modes of the carboxylate group depend on the oxidation states of the ceria surfaces. SFG polarization analysis suggested that the bidentate chelating and bridging binding modes co-exist on the reduced ceria surfaces, while the oxidized ceria surfaces are dominated by the bidentate bridging mode. The direct spectroscopic evidence helps to clarify the binding structures and mechanisms on the ceria nanoparticles. Furthermore, the middle-infrared (IR) transparent CaF2 and its chemical inertness make CaF2 and similar substrate materials good candidates for direct SFG-VS measurement of nanoparticle surface reactions and binding chem-istry.

Lu, Zhou; Karakoti, Ajay S.; Velarde Ruiz Esparza, Luis A.; Wang, Weina; Yang, Ping; Thevuthasan, Suntharampillai; Wang, Hongfei

2013-11-21

236

Novel Antiphytopathogenic Compound 2-Heptyl-5-Hexylfuran-3-Carboxylic Acid, Produced by Newly Isolated Pseudomonas sp. Strain SJT25 ?†  

PubMed Central

Pseudomonas sp. strain SJT25, which strongly antagonizes plant pathogens, was isolated from rice rhizosphere soil by a bioactivity-guided approach. A novel antiphytopathogenic compound was isolated from the fermentation broth of Pseudomonas sp. SJT25 and identified as 2-heptyl-5-hexylfuran-3-carboxylic acid. This compound showed antimicrobial activities both in vitro and in vivo. PMID:21742907

Wang, Xiao-Ying; Xu, Yu-Quan; Lin, Shuang-Jun; Liu, Zhen-Zhen; Zhong, Jian-Jiang

2011-01-01

237

Selective Nickel- and Manganese-Catalyzed Decarboxylative Cross Coupling of Some ?,?-Unsaturated Carboxylic Acids with Cyclic Ethers  

NASA Astrophysics Data System (ADS)

A nickel- and manganese-catalyzed decarboxylative cross coupling of ?, ?-unsaturated carboxylic acids with cyclic ethers such as tetrahydrofuran and 1, 4-dioxane was developed. Oxyalkylation was achieved when nickel acetate was used as catalyst, while manganese acetate promoted the reaction of alkenylation.

Zhang, Jia-Xiang; Wang, Yan-Jing; Zhang, Wei; Wang, Nai-Xing; Bai, Cui-Bing; Xing, Ya-Lan; Li, Yi-He; Wen, Jia-Long

2014-12-01

238

Alkaline battery containing a separator of a cross-linked copolymer of vinyl alcohol and unsaturated carboxylic acid  

SciTech Connect

A battery separator for an alkaline battery separator comprises a crosslinked copolymer of vinyl alcohol units and unsaturated carboxylic acid units. The crosslinked copolymer is insoluble in water, has excellent zincate diffusion and oxygen gas barrier properties and a low electrical resistivity. A polyaldehyde crosslinking agent is preferred.

Hsu, L.C.; Philipp, W.H.; Sheibley, D.W.; Gonzalez-Sanabria, O.D.

1981-07-01

239

Alkaline battery containing a separator of a cross-linked copolymer of vinyl alcohol and unsaturated carboxylic acid  

NASA Technical Reports Server (NTRS)

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.

Hsu, L. C.; Philipp, W. H.; Sheibley, D. W.; Gonzalez-Sanabria, O. D. (inventors)

1985-01-01

240

Selective Nickel- and Manganese-Catalyzed Decarboxylative Cross Coupling of Some ?,?-Unsaturated Carboxylic Acids with Cyclic Ethers  

PubMed Central

A nickel- and manganese-catalyzed decarboxylative cross coupling of ?, ?-unsaturated carboxylic acids with cyclic ethers such as tetrahydrofuran and 1, 4-dioxane was developed. Oxyalkylation was achieved when nickel acetate was used as catalyst, while manganese acetate promoted the reaction of alkenylation. PMID:25502282

Zhang, Jia-Xiang; Wang, Yan-Jing; Zhang, Wei; Wang, Nai-Xing; Bai, Cui-Bing; Xing, Ya-Lan; Li, Yi-He; Wen, Jia-Long

2014-01-01

241

EFFECTS OF CARBOXYLIC ACIDS ON LIQUID-PHASE ADSORPTION OF ETHANOL AND WATER BY HIGH-SILICA ZSM-5  

EPA Science Inventory

Adsorption isotherms were measured for each compound adsorbed on commercially available ZSM-5 (Si/Al = 140) powder from binary and ternary liquid mixtures of ethanol, carboxylic acids, and water at room temperature. The amounts adsorbed were measured using a recently developed t...

242

Diamond nanowires modified with poly[3-(pyrrolyl)carboxylic acid] for the immobilization of histidine-tagged peptides.  

PubMed

Coating boron-doped diamond nanowires (BDD NWs) with a conducting polymer, poly[3-(pyrrolyl)carboxylic acid], has been reported. Polymer coating was achieved through electropolymerization of 3-(pyrrolyl)carboxylic acid at the electrode interface by amperometrically biasing the BDD NWs interface until a predefined charge has passed. The poly[3-(pyrrolyl)carboxylic acid] modified BDD NWs (PPA-BDD NWs) were characterized by scanning electron microscopy (SEM) and cyclic voltammetry (CV). Using a deposition charge of 11 mC cm(-2) resulted in a thin polymer film deposition. The availability of the carboxylic groups of the polymer coated BDD NWs electrode was demonstrated through copper ion (Cu(2+)) chelation. The resulting complex was successfully used for the site-specific immobilization of histidine-tagged peptides. The binding process was followed by electrochemical impedance spectroscopy (EIS). The Cu(2+)-chelated PPA-BDD NWs interface showed peptide loading capability comparable to those of commercially available interfaces and can be easily regenerated several times using ethylenediaminetetraacetic acid (EDTA). PMID:25009833

Subramanian, Palaniappan; Mazurenko, Ievgen; Zaitsev, Vladimir; Coffinier, Yannick; Boukherroub, Rabah; Szunerits, Sabine

2014-09-01

243

The direct electrocatalysis of phenazine-1-carboxylic acid excreted by Pseudomonas alcaliphila under alkaline condition in microbial fuel cells  

Microsoft Academic Search

In this paper, we reported a kind of exoelectrogens, Pseudomonas alcaliphila (P. alcaliphila) strain MBR, which could excrete phenazine-1-carboxylic acid (PCA) to transfer electron under alkaline condition in microbial fuel cells (MFCs). The electrochemical activity of strain MBR and the extracellular electron transfer mechanism in MFCs were evaluated by cyclic voltammetry (CV) and electricity generation curve measurement. The results indicated

Tingtao Zhang; Lixia Zhang; Wentao Su; Ping Gao; Daping Li; Xiaohong He; Yashu Zhang

2011-01-01

244

Gold(I)-Catalyzed Intermolecular Addition of Phenols and Carboxylic Acids to Cai-Guang Yang and Chuan He*  

E-print Network

Gold(I)-Catalyzed Intermolecular Addition of Phenols and Carboxylic Acids to Olefins Cai-Guang Yang 60637 Received January 20, 2005; E-mail: chuanhe@uchicago.edu Gold-catalyzed reactions have emerged as important synthetic methods.1 Cationic gold(I) and gold(III) show exceptional activities to activate alkynes

He, Chuan

245

Investigation of supramolecular synthons and structural characterisation of aminopyridine-carboxylic acid derivatives  

PubMed Central

Background Co-crystal is a structurally homogeneous crystalline material that contains two or more neutral building blocks that are present in definite stoichiometric amounts. The main advantage of co-crystals is their ability to generate a variety of solid forms of a drug that have distinct physicochemical properties from the solid co-crystal components. In the present investigation, five co-crystals containing 2-amino-6-chloropyridine (AMPY) moiety were synthesized and characterized. Results The crystal structure of 2-amino-6-chloropyridine (AMPY) (I), and the robustness of pyridine-acid supramolecular synthon were discussed in four stoichiometry co-crystals of AMPY…BA (II), AMPY…2ABA (III), AMPY…3CLBA (IV) and AMPY…4NBA (V). The abbreviated designations used are benzoic acid (BA), 2-aminobenzoic acid (2ABA), 3-chlorobenzoic acid (3CLBA) and 4-nitrobenzoic acid (4NBA). All the crystalline materials have been characterized by 1HNMR, 13CNMR, IR, photoluminescence, TEM analysis and X-ray diffraction. The supramolecular assembly of each co-crystal is analyzed and discussed. Conclusions Extensive N---H?·?·?·?N/N---H?·?·?·?O/O---H?·?·?·?N hydrogen bonds are found in (I-V), featuring different supramolecular synthons. In the crystal structure, for compound (I), the 2-amino-6-chloropyridine molecules are linked together into centrosymmetric dimers by hydrogen bonds to form homosynthon, whereas for compounds (II-V), the carboxylic group of the respective acids (benzoic acid, 2-aminobenzoic acid, 3-chlorobenzoic acid and 4-nitrobenzoic acid) interacts with pyridine molecule in a linear fashion through a pair of N---H?·?·?·?O and O---H?·?·?·?N hydrogen bonds, generating cyclic hydrogen-bonded motifs with the graph-set notation R 2 2 8 , to form heterosynthon. In compound (II), another intermolecular N---H?·?·?·?O hydrogen bonds further link these heterosynthons into zig-zag chains. Whereas in compounds (IV) and (V), these heterosynthons are centrosymmetrically paired via N---H?·?·?·?O hydrogen bonds and each forms a complementary DADA [D?=?donor and A?=?acceptor] array of quadruple hydrogen bonds, with graph-set notation R238, R228 and R238. PMID:24887234

2014-01-01

246

Highly stereoselective biosynthesis of (R)-?-hydroxy carboxylic acids through rationally re-designed mutation of d-lactate dehydrogenase  

PubMed Central

An NAD-dependent d-lactate dehydrogenase (d-nLDH) of Lactobacillus bulgaricus ATCC 11842 was rationally re-designed for asymmetric reduction of a homologous series of ?-keto carboxylic acids such as phenylpyruvic acid (PPA), ?-ketobutyric acid, ?-ketovaleric acid, ?-hydroxypyruvate. Compared with wild-type d-nLDH, the Y52L mutant d-nLDH showed elevated activities toward unnatural substrates especially with large substitutes at C-3. By the biocatalysis combined with a formate dehydrogenase for in situ generation of NADH, the corresponding (R)-?-hydroxy carboxylic acids could be produced at high yields and highly optical purities. Taking the production of chiral (R)-phenyllactic acid (PLA) from PPA for example, 50?mM PPA was completely reduced to (R)-PLA in 90?min with a high yield of 99.0% and a highly optical purity (>99.9% e.e.) by the coupling system. The results presented in this work suggest a promising alternative for the production of chiral ?-hydroxy carboxylic acids. PMID:24292439

Zheng, Zhaojuan; Sheng, Binbin; Gao, Chao; Zhang, Haiwei; Qin, Tong; Ma, Cuiqing; Xu, Ping

2013-01-01

247

Highly stereoselective biosynthesis of (R)-?-hydroxy carboxylic acids through rationally re-designed mutation of D-lactate dehydrogenase.  

PubMed

An NAD-dependent D-lactate dehydrogenase (D-nLDH) of Lactobacillus bulgaricus ATCC 11842 was rationally re-designed for asymmetric reduction of a homologous series of ?-keto carboxylic acids such as phenylpyruvic acid (PPA), ?-ketobutyric acid, ?-ketovaleric acid, ?-hydroxypyruvate. Compared with wild-type D-nLDH, the Y52L mutant D-nLDH showed elevated activities toward unnatural substrates especially with large substitutes at C-3. By the biocatalysis combined with a formate dehydrogenase for in situ generation of NADH, the corresponding (R)-?-hydroxy carboxylic acids could be produced at high yields and highly optical purities. Taking the production of chiral (R)-phenyllactic acid (PLA) from PPA for example, 50?mM PPA was completely reduced to (R)-PLA in 90?min with a high yield of 99.0% and a highly optical purity (>99.9% e.e.) by the coupling system. The results presented in this work suggest a promising alternative for the production of chiral ?-hydroxy carboxylic acids. PMID:24292439

Zheng, Zhaojuan; Sheng, Binbin; Gao, Chao; Zhang, Haiwei; Qin, Tong; Ma, Cuiqing; Xu, Ping

2013-01-01

248

Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite  

NASA Technical Reports Server (NTRS)

The isotopic composition of hydrogen, nitrogen, and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite has been determined. The unusually high D/H and N-15/N-14 ratios in the amino acid fraction are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound and provide the first evidence suggesting a direct relationship between the massive organosynthesis occurring in interstellar clouds and the presence of prebiotic compounds in primitive planetary bodies.

Epstein, S.; Krishnamurthy, R. V.; Cronin, J. R.; Pizzarello, S.; Yuen, G. U.

1987-01-01

249

Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction  

NASA Astrophysics Data System (ADS)

A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD) analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, ?-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H)-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

Gomes, Ruth; Dutta, Saikat; Bhaumik, Asim

2014-11-01

250

Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction  

SciTech Connect

A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state {sup 13}C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N{sub 2} sorption, HR-TEM, and NH{sub 3} temperature programmed desorption-thermal conductivity detector (TPD-TCD) analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, ?-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H)-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

Gomes, Ruth; Bhaumik, Asim [Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India); Dutta, Saikat [Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan (China)

2014-11-01

251

Metabolomic Analysis of Key Central Carbon Metabolism Carboxylic Acids as Their 3-Nitrophenylhydrazones by UPLC/ESI-MS  

PubMed Central

Multiple hydroxy-, keto-, di-, and tri-carboxylic acids are among the cellular metabolites of central carbon metabolism (CCM). Sensitive and reliable analysis of these carboxylates is important for many biological and cell engineering studies. In this work, we examined 3-nitrophenylhydrazine as a derivatizing reagent and optimized the reaction conditions for the measurement of ten CCM related carboxylic compounds, including glycolate, lactate, malate, fumarate, succinate, citrate, isocitrate, pyruvate, oxaloacetate, and ?-ketoglutarate as their 3-nitrophenylhydrazones using LC/MS with electrospray ionization. With the derivatization protocol which we have developed, and using negative-ion multiple reaction monitoring on a triple-quadrupole instrument, all of the carboxylates showed good linearity within a dynamic range of ca. 200 to more than 2000. The on-column limits of detection and quantitation were from high femtomoles to low picomoles. The analytical accuracies for eight of the ten analytes were determined to be between 89.5 to 114.8% (CV?7.4%, n=6). Using a quadrupole time-of-flight instrument, the isotopic distribution patterns of these carboxylates, extracted from a 13C-labeled mouse heart, were successfully determined by UPLC/MS with full-mass detection, indicating the possible utility of this analytical method for metabolic flux analysis. In summary, this work demonstrates an efficient chemical derivatization LC/MS method for metabolomic analysis of these key CCM intermediates in a biological matrix. PMID:23580203

Han, Jun; Gagnon, Susannah; Eckle, Tobias; Borchers, Christoph H.

2014-01-01

252

Design and synthesis of novel dihydroxyindole-2-carboxylic acids as HIV-1 integrase inhibitors.  

PubMed

In a search for new HIV-1 integrase (IN) inhibitors, we synthesized and evaluated the biological activity of 5,6-dihydroxyindole-2-carboxylic acid (DHICA) and a series of its derivatives. These compounds were designed as conformationally constrained analogues of the acrylate moiety of caffeic acid phenethyl ester (CAPE). DHICA, an intermediate in the biosynthesis of melanins, was prepared as a monomeric unit by a novel synthetic route. In order to perform coherent SAR studies, two series of DHICA amides were synthesized. First, to validate the utility of a previously identified three-point pharmacophore based on CAPE in inhibitor design, we prepared a series of benzyl- or phenylethylamine substituted derivatives lacking and containing hydroxyl groups. Second, dimers of DHICA containing various aminoalkylamine linkers were also prepared with a goal to increase potency. All compounds were tested against purified IN and the C65S mutant in enzyme-based assays. They were also tested for cytotoxicity in an ovarian carcinoma cell line and antiviral activity in HIV-1-infected CEM cells. Seven compounds inhibited catalytic activities of purified IN with IC50 values below 10 microM. Further computational docking studies were performed to determine the title compounds' mode of interaction with the IN active site. The residues K156, K159 and D64 were the most important for potency against purified IN. PMID:15185725

Sechi, Mario; Angotzi, Gianfranco; Dallocchio, Roberto; Dessì, Alessandro; Carta, Fabrizio; Sannia, Luciano; Mariani, Alberto; Fiori, Stefano; Sanchez, Tino; Movsessian, Leah; Plasencia, Carmen; Neamati, Nouri

2004-03-01

253

A novel metal coordination enabled in carboxylated alginic acid for effective fluoride removal.  

PubMed

This article enlightens the synthesis of carboxylated alginic acid (CAA) and metal ions coordinated CAA (M-CAA) for defluoridation studies in batch mode. The oxidation of alginic acid (AA) with KMnO4 gives CAA and the metal coordination was enabled in CAA by using high valence metal ions viz., La(3+) (La-CAA) and Zr(4+) (Zr-CAA). The synthesized materials Zr-CAA, La-CAA and CAA possess the defluoridation capacities (DCs) of 4064, 3137 and 880 mgF(-)/kg respectively. An enhanced DC was observed for metal-coordinated CAA (M-CAA) than CAA. The defluoridation experiments were carried with numerous influencing parameters like contact time, pH and competitor anions for optimization. The characterization of materials was carried out using FTIR, EDAX and SEM analysis. The sorption data was fitted with various isotherms and kinetic models. The values of thermodynamic parameters indicate the nature of fluoride removal is spontaneous and endothermic. At field conditions, M-CAA reduce the fluoride concentration below the tolerance limit. PMID:25542130

Pandi, Kalimuthu; Viswanathan, Natrayasamy

2015-03-15

254

Lipid peroxidation forms ethylene from 1-aminocyclopropane-1-carboxylic acid and may operate in leaf senescence  

PubMed Central

An enzyme system is described which oxidizes 1-aminocyclopropane-1-carboxylic acid (ACC) to ethylene under physiological conditions. It comprises linoleic acid, pyridoxal phosphate, manganese, and lipoxygenase (linoleate:oxygen oxidoreductase, EC 1.13.11.12). It requires oxygen and is specific for manganese; it can operate but only with greatly reduced yield in the absence of pyridoxal phosphate. An enzyme with the same properties was prepared from microsomal membranes of the seedling shoots of peas. Both have similar reactions to a variety of inhibitors and other reagents. The properties also resemble those of at least two of the in vivo systems recorded in the literature. Intact green oat leaves also contain a similar system. Because there is a growing body of evidence that ethylene formation is associated with cell membranes and because the yields of ethylene from the complete system are much higher than those recorded for other enzymes, it may be identical with the in vivo system acting in senescent leaves. PMID:16593436

Bousquet, Jean-Francois; Thimann, Kenneth V.

1984-01-01

255

2-substituted thiazolidine-4(R)-carboxylic acids as prodrugs of L-cysteine. Protection of mice against acetaminophen hepatotoxicity  

SciTech Connect

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.

Nagasawa, H.T.; Goon, D.J.; Muldoon, W.P.; Zera, R.T.

1984-05-01

256

Discrimination of fresh fruit juices by a fluorescent sensor array for carboxylic acids based on molecularly imprinted titania.  

PubMed

Design of chemical sensor arrays that can discriminate real-world samples has been highly attractive in recent years. Herein a fluorescent indicator-displacement sensor array for discrimination of fresh fruit juices was developed. By coupling the unique high affinity of titania to electron-donating anions and the cross-reactivity of molecularly imprinted materials to structurally similar species, a small array was fabricated using only one rhodamine-based fluorescent dye and three synthesized materials. Citric, malic, succinic and tartaric acids were chosen as indices. The recognition mechanism was investigated by spectrofluorimetric titration using a non-linear Langmuir-type adsorption model. The proposed method was applied to discriminate thirteen fruit juices through their carboxylic acid contents. Principal component analysis of the data clearly grouped the thirteen juices with the first principal component owning 98.2% of the total variation. The comparison of the sensor array with HPLC determination of the carboxylic acids was finally made. PMID:25038646

Tan, Jin; Li, Rong; Jiang, Zi-Tao

2014-12-15

257

Carboxylic acid reductase is a versatile enzyme for the conversion of fatty acids into fuels and chemical commodities  

PubMed Central

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 Mycobacterium marinum was found to convert a wide range of aliphatic fatty acids (C6–C18) into corresponding aldehydes. Together with the broad-substrate specificity of an aldehyde reductase or an aldehyde decarbonylase, the catalytic conversion of fatty acids to fatty alcohols (C8–C16) or fatty alkanes (C7–C15) was reconstituted in vitro. This concept was applied in vivo, in combination with a chain-length-specific thioesterase, to engineer Escherichia coli BL21(DE3) strains that were capable of synthesizing fatty alcohols and alkanes. A fatty alcohol titer exceeding 350 mg·L?1 was obtained in minimal media supplemented with glucose. Moreover, by combining the CAR-dependent pathway with an exogenous fatty acid-generating lipase, natural oils (coconut oil, palm oil, and algal oil bodies) were enzymatically converted into fatty alcohols across a broad chain-length range (C8–C18). Together with complementing enzymes, the broad substrate specificity and kinetic characteristics of CAR opens the road for direct and tailored enzyme-catalyzed conversion of lipids into user-ready chemical commodities. PMID:23248280

Akhtar, M. Kalim; Turner, Nicholas J.; Jones, Patrik R.

2013-01-01

258

Carboxylic Acid Ionophores as Probes of the Role of Calcium in Biological Systems  

NASA Technical Reports Server (NTRS)

The biological effects of calcium ionophores are described, focusing on arachidonic acid oxygenation, and the formation of a number of oxygenated metabolites of arachidonic acid. These metabolites are involved in a number of bodily functions, and their production may be regulated by calcium.

Reed, P. W.

1983-01-01

259

Synthesis, characterization and crystal structures of the organotin(IV) compounds with the Schiff base ligands of pyruvic acid thiophene-2-carboxylic hydrazone and salicylaldehyde thiophene-2-carboxylic hydrazone  

Microsoft Academic Search

A series of organotin (IV) compounds of the type [R3SnL]2, R is Me (1), Bu (2), [R2SnL]2, R is Ph (3), Me (4), Bu (5), L is pyruvic acid thiophene-2-carboxylic hydrazone, and R2SnL, R is Me (6), Bu (7), Ph (8), L is salicylaldehyde thiophene-2-carboxylic hydrazone have been synthesized in 1:1 molar ratio. All compounds were characterized by elemental analysis,

Han Dong Yin; Shao Wen Chen; Lin Wei Li; Da Qi Wang

2007-01-01

260

FT-IR, Laser-Raman spectra and computational analysis of 5-Methyl-3-phenylisoxazole-4-carboxylic acid.  

PubMed

In this study the experimental and theoretical vibrational frequencies of a newly synthesized anti-tumor, antiviral, hypoglycemic, antifungal and anti-HIV agent namely, 5-Methyl-3-phenylisoxazole-4-carboxylic acid has been investigated. The experimental FT-IR (4000-400cm(-1)) and Laser-Raman spectra (4000-100cm(-1)) of the molecule in solid phase have been recorded. The theoretical vibrational frequencies and optimized geometric parameters (bond lengths, bond angles and torsion angles) have been calculated by using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr and DFT/M06-2X: highly parametrized, empirical exchange correlation function) with 6-311++G(d,p) basis set by Gaussian 09W software, for the first time. The assignments of the vibrational frequencies have been done by potential energy distribution (PED) analysis by using VEDA 4 software. The theoretical optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data and results in the literature. In addition, the highest occupied molecular orbital (HOMO) energy, the lowest unoccupied molecular orbital (LUMO) energy and the other related molecular energy values of the compound have been investigated by using the same theoretical calculations. PMID:25554964

Sert, Yusuf; Mahendra, M; Keskino?lu, S; Chandra; Srikantamurthy, N; Umesha, K B; Ç?rak, Ç

2015-03-15

261

Cell wall integrity controls root elongation via a general 1-aminocyclopropane-1-carboxylic acid-dependent, ethylene-independent pathway.  

PubMed

Cell expansion in plants requires cell wall biosynthesis and rearrangement. During periods of rapid elongation, such as during the growth of etiolated hypocotyls and primary root tips, cells respond dramatically to perturbation of either of these processes. There is growing evidence that this response is initiated by a cell wall integrity-sensing mechanism and dedicated signaling pathway rather than being an inevitable consequence of lost structural integrity. However, the existence of such a pathway in root tissue and its function in a broader developmental context have remained largely unknown. Here, we show that various types of cell wall stress rapidly reduce primary root elongation in Arabidopsis (Arabidopsis thaliana). This response depended on the biosynthesis of 1-aminocyclopropane-1-carboxylic acid (ACC). In agreement with the established ethylene signaling pathway in roots, auxin signaling and superoxide production are required downstream of ACC to reduce elongation. However, this cell wall stress response unexpectedly does not depend on the perception of ethylene. We show that the short-term effect of ACC on roots is partially independent of its conversion to ethylene or ethylene signaling and that this ACC-dependent pathway is also responsible for the rapid reduction of root elongation in response to pathogen-associated molecular patterns. This acute response to internal and external stress thus represents a novel, noncanonical signaling function of ACC. PMID:21508182

Tsang, Dat L; Edmond, Clare; Harrington, Jennifer L; Nühse, Thomas S

2011-06-01

262

Identification of indole-3-carboxylic acid as mediator of priming against Plectosphaerella cucumerina.  

PubMed

Plant resistance against the necrotrophic pathogen Plectosphaerella cucumerina is mediated by a combination of several hormonal-controlled signalling pathways. The priming agent ?-aminobutyric acid (BABA) is able to induce effective resistance against this pathogen by stimulating callose-rich cell wall depositions. In the present research it is demonstrated that BABA-Induced Resistance (BABA-IR) against P. cucumerina in Arabidopsis has additional components such as the induction of defences mediated by indolic derivatives. Chromatographic approach for the detection and characterization of metabolites enhanced by BABA compared with water-treated plants only when the challenge is present has been developed. The metabolites matching this criteria are considered to be primed by BABA. The analytic procedure is based on the combination of liquid chromatography (LC) with a triple quadrupole (TQD) detector in a precursor ion scanning mode. Using this analytical system a signal in negative electro-spray mode of 160 m/z is primed by BABA in infected plants. A subsequent exact mass analysis in a quadrupole time-of-flight mass spectrometer demonstrated that this ion was the indole-derivative metabolite indole-3-carboxylic acid (I3CA). The identity of indole-3-carboxilic acid was definitively confirmed by comparing its retention time and fragmentation spectra with a commercial standard. Quantification of I3CA in primed plants showed that this indolic metabolite is specifically primed by BABA upon P. cucumerina infection, while other indolic compounds such as IAA and camalexin are not. Taking together these observations with the known role of callose in priming against this pathogen, suggests that priming is not a single mechanism but rather a multicomponent defence. PMID:23116603

Gamir, J; Pastor, V; Cerezo, M; Flors, V

2012-12-01

263

(±)-2,2-Dimethyl-5-oxotetrahydrofuran-3-carboxylic acid (terebic acid): a racemic layered structure.  

PubMed

A racemic crystalline form of terebic acid, C(7)H(10)O(4), which is an important industrial chemical compound, is reported for the first time. The crystal structure is stabilized by O-H···O and C-H···O hydrogen bonds which form racemic double layers parallel to (001). PMID:22850854

Santos, L M; Legendre, A O; Villis, P C M; Viegas, C; Doriguetto, A C

2012-08-01

264

Solubility and spectroscopic studies of the interaction of palladium with simple carboxylic acids and fulvic acid at low temperature  

NASA Astrophysics Data System (ADS)

The interaction of Pd with some O-donor organic acid anions has been investigated using solubility measurements and a variety of spectroscopic techniques (UV-visible, Raman, FTIR, 13C NMR). Some of the ligands investigated (acetate, oxalate and fulvic acid) occur naturally in relatively high concentrations, whereas others (phthalate and salicylate) serve as models of potential binding sites on humic and fulvic acids. Solubility measurements show that the presence of acetate, phthalate, salicylate and fulvic acid (oxalate was not studied via solubility methods) can increase the mobility of Pd over various pH ranges, depending on the organic ligand. In the case of acetate, UV-visible and Raman spectroscopy ( 13C NMR results were inconclusive) provide strong evidence for the formation of electrostatically bound, possibly outer-sphere palladium acetate complexes. Oxalate was confirmed by UV-visible and FTIR spectroscopy to compete favorably with chloride (0.56 M NaCl) for Pd even at oxalate concentrations as low as 1 mM at pH = 6-7. Available data from the literature suggest that oxalate may have an influence on Pd mobility at free oxalate concentrations as low as 10 -8-10 -9 M. UV-visible spectroscopy provides evidence of an initially rapid, followed by a slower, reaction between PdCl 42- and o-phthalate ion. Our findings lend support to the idea that similar binding sites on fulvic acid may be capable of complexing and solubilizing Pd in the natural environment. Although thermodynamic data are required to fully quantify the extent, it is concluded that simple carboxylic acid anions and/or fulvic and humic acids should be capable of significantly enhancing Pd transport in the surficial environment by forming truly dissolved complexes. On the other hand, flocculation of fulvic/humic acids, owing to changing ionic strengths or pH, or adsorption of these acids onto mineral surfaces, may also provide effective means of immobilizing Pd. These results have applications in exploration geochemistry and disposal of radioactive waste containing 107Pd.

Wood, Scott A.; Tait, C. Drew; Vlassopoulos, Dimitri; Janecky, D. R.

1994-01-01

265

Solubility and spectroscopic studies of the interaction of palladium with simple carboxylic acids and fulvic acid at low temperature  

SciTech Connect

The interaction of Pd with some O-donor organic acid anions has been investigated using solubility measurements and a variety of spectroscopic techniques (UV-visible, Raman, FTIR, [sup 13]C NMR). Some of the ligands investigated (acetate, oxalate, and fulvic acid) occur naturally in relatively high concentrations, whereas others (phthalate and salicylate) serve as models of potential binding sites on humic and fulvic acids. Solubility measurements show that the presence of acetate, phthalate, salicylate, and fulvic acid (oxalate was not studied via solubility methods) can increase the mobility of Pd over various pH ranges, depending on the organic ligand. In the case of acetate, UV-visible and Raman spectroscopy provide strong evidence for the formation of electrostatically bound, possibly outer-sphere palladium acetate complexes. Oxalate was confirmed by UV-visible and FTIR spectroscopy to compete favorably with chloride (0.56 M NaCl) for Pd even at oxalate concentrations as low as 1 mM at pH = 6-7. Available data from the literature suggest that oxalate may have an influence on Pd mobility at free oxalate concentrations as low as 10[sup [minus]8]=10[sup [minus]9] M. UV-visible spectroscopy provides evidence of an initially rapid, followed by a slower, reaction between PdCl[sup 2-][sub 4] and o-phthalate ion. These findings lend support to the idea that similar bindings sites on fulvic acid may be capable of complexing and solubilizing Pd in the natural environment. Although thermodynamic data are required to fully quantify the extent, it is concluded that simple carboxylic acid anions and/or fulvic and humic acids should be capable of significantly enhancing Pd transport in the surficial environment by forming truly dissolved complexes. On the other hand, flocculation of fulvic/humic acids, owing to changing ionic strengths or pH, or adsorption of these acids onto mineral surfaces, may also provide effective means of immobilizing Pd.

Wood, S.A. (Univ. of Idaho, Moscow, ID (United States)); Tait, C.D.; Janecky, D.R. (Los Alamos National Laboratory, NM (United States)); Vlassopoulos, D. (California Institute of Technology, Pasadena, CA (United States))

1994-01-01

266

Crystal structure of 5-formyl-3-hydroxy-2-methylpyridine 4-carboxylic acid 5-dehydrogenase, an NAD(+)-dependent dismutase from Mesorhizobium loti.  

PubMed

5-Formyl-3-hydroxy-2-methylpyridine 4-carboxylic acid 5-dehydrogenase (FHMPCDH) from Mesorhizobium loti is the fifth enzyme in degradation pathway I for pyridoxine. The enzyme catalyzes a dismutation reaction: the oxidation of 5-formyl-3-hydroxy-2-methylpyridine 4-carboxylic acid (FHMPC) to 3-hydroxy-2-methylpyridine 4,5-dicarboxylic acid with NAD(+) and reduction of FHMPC to 4-pyridoxic acid with NADH. FHMPCDH belongs to the l-3-hydroxyacyl-CoA dehydrogenase (HAD) family. The crystal structure was determined by molecular replacement and refined to a resolution of 1.55Å (R-factor of 16.4%, Rfree=19.4%). There were two monomers in the asymmetric unit. The overall structure of the monomer consisted of N- and C-terminal domains connected by a short linker loop. The monomer was similar to members of the HAD family (RMSD=1.9Å). The active site was located between the domains and highly conserved to that of human heart l-3-hydroxyacyl-CoA dehydrogenase (HhHAD). His-Glu catalytic dyad, a serine and two asparagine residues of HhHAD were conserved. Ser116, His137 and Glu149 in FHMPCDH are connected by a hydrogen bonding network forming a catalytic triad. The functions of the active site residues in the reaction mechanism are discussed. PMID:25446130

Mugo, Andrew Njagi; Kobayashi, Jun; Mikami, Bunzo; Yoshikane, Yu; Yagi, Toshiharu; Ohnishi, Kouhei

2015-01-01

267

A physiologically based pharmacokinetic model for quinoxaline-2-carboxylic acid in rats, extrapolation to pigs.  

PubMed

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. PMID:25378053

Yang, X; Zhou, Y-F; Yu, Y; Zhao, D-H; Shi, W; Fang, B-H; Liu, Y-H

2015-02-01

268

Carboxylic acid-doped SBA-15 silica as a host for metallo-supramolecular coordination polymers.  

PubMed

The adsorption of a metallo-supramolecular coordination polymer (Fe-MEPE) in the cylindrical pores of SBA-15 silica with pure and carboxylic acid (CA) carrying pore walls has been studied. Fe-MEPE is an intrinsically stiff polycation formed by complexation of Fe(II)-acetate with an uncharged ditopic bis-terpyridine ligand. The adsorption affinity and kinetics of the Fe-MEPE chains is strongly enhanced when the pore walls are doped with CA, and when the pH of the aqueous medium or temperature is increased. The initial fast uptake is connected with a decrease of pH of the aqueous solution, indicating an ion-exchange mechanism. It is followed by a slower (presumably diffusion-controlled) further uptake. The maximum adsorbed amount of Fe-MEPE in the CA-doped material corresponds to a monolayer of Fe-MEPE chains disposed side-by-side along the pore walls. The stoichiometry of Fe-MEPE in the pores (determined by XPS) was found to be independent of the loading and similar to that of the starting material. The mean chain length of Fe-MEPE before and after embedding in the CA-doped matrix was studied by solid-state 15N NMR using partially 15N-labeled Fe-MEPE. It is shown that the average chain length of Fe-MEPE is reduced when the complex is incorporated in the pores. PMID:18839983

Akcakayiran, D; Mauder, D; Hess, C; Sievers, T K; Kurth, D G; Shenderovich, I; Limbach, H-H; Findenegg, G H

2008-11-20

269

Oxidation of benzene with hydrogen peroxide catalyzed with ferrocene in the presence of pyrazine carboxylic acid  

NASA Astrophysics Data System (ADS)

It is found that ferrocene in the presence of small amounts of pyrazine carboxylic acid (PCA) effectively catalyzes the oxidation of benzene to phenol with hydrogen peroxide. Two main differences upon the oxidation of two different substrates, i.e., cyclohexane and benzene, with the same H2O2-ferrocene-PCA catalytic system are revealed: the rates of benzene oxidation and hydrogen peroxide decomposition are several times lower than the rate of cyclohexane oxidation at close concentrations of both substrates, and the rate constant ratios for the reactions of oxidizing particles with benzene and acetonitrile are significantly lower than would be expected for reactions involving free hydroxyl radicals. The overall rate of hydrogen peroxide decomposition, including both the catalase and oxidase routes, is lower in the presence of benzene than in the presence of cyclohexane. It is suggested on the grounds of these data that a catalytically active particle different from the one generated in the absence of benzene is formed in the presence of benzene. This particle catalyzes hydrogen peroxide decomposition less efficiently than the initial complex and generates a dissimilar oxidizing particle that exhibits higher selectivity. It is shown that reactivity of the system at higher concentrations of benzene differs from that of an initial system not containing an aromatic component with the capability of ?-coordination with metal ions.

Shul'pina, L. S.; Durova, E. L.; Kozlov, Yu. N.; Kudinov, A. R.; Strelkova, T. V.; Shul'pin, G. B.

2013-12-01

270

Generation and characterization of isolates of Peronophythora litchii resistant to carboxylic acid amide fungicides.  

PubMed

Four isolates of Peronophythora litchii with resistance to carboxylic acid amide (CAA) fungicides were selected on fungicide-amended agar. These isolates had various levels of resistance, as evidenced by their resistance factor (RF), which is the 50% effective concentration (EC(50)) value of a particular isolate divided by that of the wild-type parent. RF values to dimethomorph for the four isolates were 15, 24, 141, and >1,500. Resistance was stable for two isolates, while the EC(50) values decreased for the other two after repeated subculturing on fungicide-free medium. Cross-resistance occurred with all CAAs tested here (dimethomorph, mandipropamid, flumorph, and pyrimorph), but not with strobilurins (azoxystrobin and famoxadone) or other fungicides (metalaxyl, cymoxanil, and mancozeb). Studies on fitness parameters (mycelial growth, sporulation, spore germination, zoospore formation, aggressiveness, and temperature tolerance) in the parent wild-type and resistant isolates demonstrated that penalties in different parameters may be associated with CAA resistance, depending on the isolate. These studies show that Peronophythora litchii is able to express CAA resistance under laboratory conditions but it is not known if resistant strains could become established in the field and sensitivity monitoring studies are recommended. PMID:20373974

Wang, Hancheng; Sun, Haiyan; Stammler, Gerd; Ma, Jianxia; Zhou, Mingguo

2010-05-01

271

A mechanical strain-induced 1-aminocyclopropane-1-carboxylic acid synthase gene.  

PubMed Central

Ethylene production is observed in all higher plants, where it is involved in numerous aspects of growth, development, and senescence. 1-Aminocyclopropane-1-carboxylic acid synthase (ACC synthase; S-adenosyl-L-methionine methylthioadenosine-lyase, EC 4.4.1.14) is the key regulatory enzyme in the ethylene biosynthetic pathway. We are reporting an ACC synthase gene in Vigna radiata (mung bean) that is inducible by mechanical strain. The ACC synthase cDNA AIM-1 was induced by mechanical strain within 10 min, reaching a maximum at 30 min, showing a dramatic reduction after 60 min, and showing no detectable message by 3 hr. The kinetics of induction for AIM-1 was similar to a mechanical strain-induced calmodulin (MBCaM-1) in V. radiata, whereas the kinetics of its decline from maximum was different. When plants were subjected to calcium-deficient conditions, supplemental calcium, calcium chelators, calcium storage releasers, calcium ionophore, or calmodulin antagonists, there was no effect on AIM-1, indicating that the mechanical strain-induced AIM-1 expression is a calcium-independent process. Induction of MBCaM-1 in all cases behaved in the same way as AIM-1, suggesting that they share similar mechanically activated cis- and/or trans-acting elements in their promoter. Images Fig. 1 Fig. 2 Fig. 3 PMID:7878024

Botella, J R; Arteca, R N; Frangos, J A

1995-01-01

272

Stimulation of H+ Efflux and Inhibition of Photosynthesis by Esters of Carboxylic Acids 1  

PubMed Central

Suspensions of mechanically isolated Asparagus sprengeri Regel mesophyll cells were used to investigate the influence of various carboxyester compounds on rates of net H+ efflux in the dark or light and photosynthetic O2 production. Addition of 0.15 to 1.5 millimolar malathion, ?-naphthyl acetate, phenyl acetate, or p-nitrophenyl acetate stimulated H+ efflux and inhibited photosynthesis within 1 minute. In contrast, the more polar esters methyl acetoacetate or ethyl p-aminobenzoate had little or no effect on either of these two processes. A 0.15 millimolar concentration of ?-naphthylacetate stimulated the normal rate of H+ efflux, 0.77 nanomoles H+ per 106 cells per minute by 750% and inhibited photosynthesis by 100%. The four active carboxyester compounds also stimulated H+ efflux after the normal rate of H+ efflux was eliminated with 0.01 milligrams per milliliter oligomycin or 100% N2. Oligomycin reduced the ATP level by 70%. Incubation of cells with malathion, ?-naphthyl acetate, or p-nitrophenyl acetate resulted in the generation of the respective hydrolysis products ethanol, ?-naphthol, and p-nitrophenol. It is proposed that inhibition of photosynthesis and stimulation of H+ efflux result when nonpolar carboxyester compounds enter the cell and generate acidic carboxyl groups when hydrolyzed by esterase enzymes. PMID:16663308

Duhaime, Donna E.; Bown, Alan W.

1983-01-01

273

An efficient transformation of cyclic ene-carbamates into omega-(N-formylamino)carboxylic acids by ruthenium tetroxide oxidation.  

PubMed

The ruthenium tetroxide (RuO(4)) oxidation of cyclic ene-carbamates resulted in the endo-cyclic carbon-carbon double bond cleavage to afford the corresponding omega-(N-formylamino)carboxylic acids in good yields. Substituted cyclic ene-carbamates derived from (3R)-3-hydroxypiperidine hydrochloride were converted into the N-Boc 4-aminobutyric acids by utilization of the RuO(4) oxidation as the key step, which were further transformed into (3R)-4-amino-3-hydroxybutyric acid, an important key intermediate for the synthesis of L-carnitine. PMID:18758107

Kaname, Mamoru; Yoshifuji, Shigeyuki; Sashida, Haruki

2008-09-01

274

Carboxylic and Dicarboxylic Acids Extracted from Crushed Magnesium Oxide Single Crystals  

NASA Technical Reports Server (NTRS)

Carboxylic and dicarboxylic acids (glycolic, oxalic, malonic and succinic) have been extracted with tetrahydrofuran (THE) and H2O from large synthetic MgO crystals, crushed to a medium fine powder. The extracts were characterized by infrared spectroscopy and (sup 1)H-NMR (Nuclear Magnetic Resonance). The THF extracts were derivatized with tert-butyldimethylsilyl (t-BDMS) for GC-MS (Gas Chromatography - Mass Spectroscopy) analysis. A single crystal separated from the extract was used for an x-ray structure analysis, giving the monoclinic unit cell, space group P2(sub 1)/c with a(sub o) = 5.543 A, b(sub o) = 8.845 A, c(sub o) = 5.086 A, and beta = 91.9 degrees, consistent with beta-succinic acid, HOOC(CH2)COOH. The amount of extracted acids is estimated to be of the order of 0.1 to 0.5 mg/g MgO. The MgO crystals from which these organic acids were extracted grew from the 2360 C hot melt, saturated with CO/CO2 and H2O, thereby incorporating small amounts of the gaseous components to form a solid solution (ss) with MgO. Upon cooling, the ss becomes supersaturated, causing solute carbon and other solute species to segregate not only to the surface but also internally, to dislocations and subgrain boundaries. The organic acids extracted from the MgO crystals after crushing appear to derive from these segregated solutes that formed C-C, C-H, and C-O bonds along dislocations and other defects in the MgO structure, leading to entities that can generically be described as (HxCyOz)(sup n-). The processes underlying the formation of these precursors are fundamental in nature and expected to be operational in any minerals, preferentially those with dense structures, that crystallized in H2O-CO2-laden environments. This opens the possibility that common magmatic and metamorphic rocks when weathering at the surface of a tectonically active planet like Earth may be an important source of abiogenically formed complex organic compounds.

Freund, Friedemann; Gupta, Alka D.; Kumar, Devendra; DeVincenzi, Donald (Technical Monitor)

1998-01-01

275

Carboxylic and dicarboxylic acids extracted from crushed magnesium oxide single crystals  

NASA Technical Reports Server (NTRS)

Carboxylic and dicarboxylic acids (glycolic, oxalic, malonic and succinic) have been extracted with tetrahydrofuran (THF) and H2O from large synthetic MgO crystals, crushed to a medium fine powder. The extracts were characterized by infrared spectroscopy and 1H-NMR. The THF extracts were derivatized with tert-butyldimethylsilyl (t-BDMS) for GC-MS analysis. A single crystal separated from the extract was used for an x-ray structure analysis, giving the monoclinic unit cell, space group P21/c with ao = 5.543 A, bo = 8.845 A, co = 5.086 A, and beta = 91.9 degrees, consistent with beta-succinic acid, HOOC(CH2)COOH. The amount of extracted acids is estimated to be of the order of 0.1 to 0.5 mg g-1 MgO. The MgO crystals from which these organic acids were extracted grew from the 2860 degrees C hot melt, saturated with CO/CO2 and H2O, thereby incorporating small amounts of the gaseous components to form a solid solution (ss) with MgO. Upon cooling, the ss becomes supersaturated, causing solute carbon and other solute species to segregate not only to the surface but also internally, to dislocations and subgrain boundaries. The organic acids extracted from the MgO crystals after crushing appear to derive from these segregated solutes that formed C-C, C-H and C-O bonds along dislocations and other defects in the MgO structure, leading to entities that can generically be described as (HxCyOz)n-. The processes underlying the formation of these precursors are fundamental in nature and expected to be operational in any minerals, preferentially those with dense structures, that crystallized in H2O-CO2-laden environments. This opens the possibility that common magmatic and metamorphic rocks when weathering at the surface of a tectonically active planet like Earth may be an important source of abiogenically formed complex organic compounds.

Freund, F.; Gupta, A. D.; Kumar, D.

1999-01-01

276

An Improved Method for ?-Carboxylation of ?-Diketones. Synthesis of 4Alkyl3,5-Dioxohexanoic Acids and 5Alkyl Derivatives of Triacetic Acid Lactone  

Microsoft Academic Search

?-Carboxylation of ?-diketones, 1, can be improved using samples containing 100% of ketoenol tautomers, 3, prepared by mild hydrolysis of the corresponding copper(II) complexes 2. Cyclization of the so formed 4-alkyl-3,5-dioxohexanoic acids, 4, affords 5-alkyl-4-hydroxy-6-methyl-2-pyrones, 5.

Jordi Cervelló; Jorge Marquet; Marcial Moreno-mañas

1990-01-01

277

Spectrofluorimetric determination of 3-methylflavone-8-carboxylic acid, the main active metabolite of flavoxate hydrochloride in human urine  

NASA Astrophysics Data System (ADS)

A simple, sensitive and selective spectrofluorimetric method has been developed for the determination of 3-methylflavone-8-carboxylic acid as the main active metabolite of flavoxate hydrochloride in human urine. The proposed method was based on the measurement of the native fluorescence of the metabolite in methanol at an emission wavelength 390 nm, upon excitation at 338 nm. Moreover, the urinary excretion pattern has been calculated using the proposed method. Taking the advantage that 3-methylflavone-8-carboxylic acid is also the alkaline degradate, the proposed method was applied to in vitro determination of flavoxate hydrochloride in tablets dosage form via the measurement of its corresponding degradate. The method was validated in accordance with the ICH requirements and statistically compared to the official method with no significant difference in performance.

Zaazaa, Hala E.; Mohamed, Afaf O.; Hawwam, Maha A.; Abdelkawy, Mohamed

2015-01-01

278

Spectrofluorimetric determination of 3-methylflavone-8-carboxylic acid, the main active metabolite of flavoxate hydrochloride in human urine.  

PubMed

A simple, sensitive and selective spectrofluorimetric method has been developed for the determination of 3-methylflavone-8-carboxylic acid as the main active metabolite of flavoxate hydrochloride in human urine. The proposed method was based on the measurement of the native fluorescence of the metabolite in methanol at an emission wavelength 390 nm, upon excitation at 338 nm. Moreover, the urinary excretion pattern has been calculated using the proposed method. Taking the advantage that 3-methylflavone-8-carboxylic acid is also the alkaline degradate, the proposed method was applied to in vitro determination of flavoxate hydrochloride in tablets dosage form via the measurement of its corresponding degradate. The method was validated in accordance with the ICH requirements and statistically compared to the official method with no significant difference in performance. PMID:25004902

Zaazaa, Hala E; Mohamed, Afaf O; Hawwam, Maha A; Abdelkawy, Mohamed

2015-01-01

279

Isotachophoresis on a chip with indirect fluorescence detection as a field deployable system for analysis of carboxylic acids.  

PubMed

ITP with indirect fluorescence detection (IFD) was introduced three decades ago. Despite this fact, the method has never become widely adopted. The main aim of this work was to utilize the ITP-IFD for the separation of carboxylic acids by using a commercially available, portable, microfluidic chip electrophoresis system. On the 16.8-mm effective length separation channel, a maximum of eight carboxylic acids could be separated, with LOD values in a range from 0.12 to 0.4 mM. The commercial chips used for all experiments have multichannel structures important for analysis of more than one sample per a chip in case of standard use. This multichannel structure was used to investigate the possibility of multiple sample loading for ITP separation. Application of ITP-IFD was investigated for analysis of benzoate in diet soft drinks and the results were in good agreement with results of a CE method. PMID:23065658

Smejkal, Petr; Breadmore, Michael C; Guijt, Rosanne M; Foret, František; Bek, Fritz; Macka, Mirek

2012-11-01

280

Short-chain carboxylic acids, a new class of teratogens: studies of potential biochemical mechanisms  

SciTech Connect

Certain short-chain carboxylic acids (SCCA) appear to share a common teratogenic potential, although the structural requirements for activity remain obscure. By using a whole rat embryo culture model system, several biochemical processes have been examined, either as potential initial sites of teratogenic action or as early steps in the pathway to malformation. Valproate, methoxyacetate, and butyrate were the prototype SCCA examined. Measurement of (/sup 14/C)glucose utilization and lactate production confirmed that energy production by the early organogenesis embryo is predominantly from glycolysis. While the positive control agent, iodoacetate, caused a significant inhibition of lactate production, none of the SCCA affected this process or glucose utilization at teratogenic concentrations. Pinocytosis by the visceral yolk sac (VYS) was measured by the uptake of (/sup 125/I)polyvinylpyrrolidone. This process ultimately supplies the embryo with amino-acids and is essential for normal development. SCCA induce morphological abnormalities of the VYS in embryo culture. Pinocytosis was slightly reduced by valproate, but not the other SCCA. However, comparison with the action of an antiserum, for which inhibition of pinocytosis is the initial teratogenic insult, suggests that this is not the mechanism for valproate. Incorporation of (/sup 3/H)thymidine into embryo or yolk sac was not affected after 3 hr of SCCA exposure, but there was a marked effect of the positive control, hydroxyurea. This suggests that DNA synthesis is not directly influenced by SCCA. It can be concluded that SCCA do not exert their teratogenic effects by actions on glycolysis; maintenance of cellular acetyl CoA; pinocytosis or DNA synthesis. These observations contrast with preliminary results which suggest significant effects of SCCA on embryonic and yolk sac lipid metabolic pathways.

Coakley, M.E.; Rawlings, S.J.; Brown, N.A.

1986-12-01

281

Toxicokinetics of perfluoroalkyl carboxylic acids with different carbon chain lengths in mice and humans.  

PubMed

Objectives: Perfluoroalkyl carboxylic acids (PFCAs) consist of analogs with various carbon chain lengths. Their toxicokinetics have remained unexplored except in the case of perfluorooctanoic acid (8 carbon chemicals). This study aimed to investigate the toxicokinetics of PFCAs with six to fourteen carbon atoms (C6 to C14) in mice and humans. Methods: We applied a two-compartment model to mice administered PFCAs intravenously or by gavage. The time courses of the serum concentration and tissue distribution and elimination were evaluated for 24 h after treatment. For human samples, urine from healthy volunteers, bile from patients who underwent biliary drainage, and cerebral spinal fluid (CSF) from brain drainage were collected. Results: The mouse experiment showed that short-chained PFCAs (C6 and C7) were rapidly eliminated in the urine, whereas long-chain PFCAs (C8 to C14) accumulated in the liver and were excreted slowly in feces. Urinary clearance of PFCAs in humans also decreased with increasing alkyl chain lengths, while biliary clearances increased. C9 to C10 had the smallest total clearance for both mice and humans. However, disparities existed in the magnitude of the total clearance between mice and humans. A slightly higher partition ratio (brain/serum) was observed for long-chained PFCAs in mice, but this was not observed in the corresponding partition ratio in humans (CSF/serum). Conclusions: The large sequestration volumes of PFCAs in the liver seem to be attributable to the liver's large binding capacity in both species. This will be useful in evaluating PFCA bioaccumulation in other species. PMID:25422127

Fujii, Yukiko; Niisoe, Tamon; Harada, Kouji H; Uemoto, Shinji; Ogura, Yasuhiro; Takenaka, Katsunobu; Koizumi, Akio

2014-11-21

282

The hydrogen bond environments of 1H-tetrazole and tetrazolate rings: the structural basis for tetrazole-carboxylic acid bioisosterism.  

PubMed

Bioisosterism involving replacement of a carboxylic acid substituent by 1H-tetrazole, yielding deprotonated carboxylate and tetrazolate under physiological conditions, is a well-known synthetic strategy in medicinal chemistry. To improve our overall understanding of bioisosterism, we have used this example to study the geometrical and energetic aspects of the functional group replacement. Specifically, we use crystal structure informatics and high-level ab initio calculations to study the hydrogen bond (H-bond) energy landscapes of the protonated and deprotonated bioisosteric pairs. Each pair exhibits very similar H-bond environments in crystal structures retrieved from the CSD, and the attractive energies of these H-bonds are also very similar. However, by comparison with -COOH and -COO(-), the H-bond environments around 1H-tetrazole and tetrazolate substituents extend further, by about 1.2 Å, from the core of the connected molecule. Analysis of pairs of PDB structures containing ligands which differ only in having a tetrazole or a carboxyl substituent and which are bound to the same protein indicates that the protein binding site must flex sufficiently to form strong H-bonds to either substituent. A survey of DrugBank shows a rather small number of tetrazole-containing drugs in the 'approved' and 'experimental' drug sections of that database. PMID:22303876

Allen, Frank H; Groom, Colin R; Liebeschuetz, John W; Bardwell, David A; Olsson, Tjelvar S G; Wood, Peter A

2012-03-26

283

Selective aerobic oxidation of alcohols to aldehydes, carboxylic acids, and imines catalyzed by a Ag-NHC complex.  

PubMed

Silver NHC catalysts have been developed for the selective oxidation of alcohols to aldehydes or carboxylic acids in the presence of BnMe3NOH or KOH under dry air. The aerobic oxidation conditions are mild, and the yield is excellent. Further tandem catalysis enables the one-pot synthesis of imines in excellent yield. Only 0.1 mol % of the catalyst is required. PMID:24937233

Han, Lei; Xing, Ping; Jiang, Biao

2014-07-01

284

Anaerobic degradation of trans -cinnamate and ?-phenylalkane carboxylic acids by the photosynthetic bacterium Rhodopseudomonas palustris : evidence for a ?-oxidation mechanism  

Microsoft Academic Search

The mechanism responsible for the initial steps in the anaerobic degradation of trans-cinnamate and ?-phenylalkane carboxylates by the purple non-sulphur photosynthetic bacterium Rhodopseudomonas palustris was investigated. Phenylacetate did not support growth and there was a marked CO2 dependence for growth on acids with greater side-chain lengths. Here, CO2 was presumably acting as a redox sink for the disposal of excess

Douglas J. E. Elder; Philip Morgan; David J. Kelly

1992-01-01

285

Copper-catalyzed regioselective synthesis of furan via tandem cycloaddition of ketone with an unsaturated carboxylic acid under air.  

PubMed

A catalytic decarboxylative annulation has been developed for the regioselective synthesis of trisubstituted furans by the cycloaddition of ketones with ?,?-unsaturated carboxylic acids under ambient air. A library of furan derivatives were obtained in good yields from the readily available substrates in the combination of a catalytic amount of Cu-salt and a stoichiometric amount of water. Water plays a crucial role in this catalytic transformation. PMID:25370303

Ghosh, Monoranjan; Mishra, Subhajit; Monir, Kamarul; Hajra, Alakananda

2015-01-01

286

Rapid adsorption of 2,4-dichlorophenoxyacetic acid by iron oxide nanoparticles-doped carboxylic ordered mesoporous carbon.  

PubMed

The ordered mesoporous carbon composite functionalized with carboxylate groups and iron oxide nanoparticles (Fe/OMC) was successfully prepared and used to adsorb 2,4-dichlorophenoxyacetic acid (2,4-D) from wastewater. The resultant adsorbent possessed high degree of order, large specific surface area and pore volume, and good magnetic properties. The increase in initial pollutant concentration and contact time would make the adsorption capacity increase, but the pH and temperature are inversely proportional to 2,4-D uptake. The equilibrium of adsorption was reached within 120min, and the equilibrated adsorption capacity increased from 99.38 to 310.78mg/g with the increase of initial concentration of 2,4-D from 100 to 500mg/L. Notablely, the adsorption capacity reached 97% of the maximum within the first 5min. The kinetics and isotherm study showed that the pseudo-second-order kinetic and Langmuir isotherm models could well fit the adsorption data. These results indicate that Fe/OMC has a good potential for the rapid adsorption of 2,4-D and prevention of its further diffusion. PMID:25594883

Tang, Lin; Zhang, Sheng; Zeng, Guang-Ming; Zhang, Yi; Yang, Gui-De; Chen, Jun; Wang, Jing-Jing; Wang, Jia-Jia; Zhou, Yao-Yu; Deng, Yao-Cheng

2015-05-01

287

Amino acid ester prodrugs conjugated to the ?-carboxylic acid group do not display affinity for the L-type amino acid transporter 1 (LAT1).  

PubMed

L-type amino acid transporter (LAT1) is an intriguing target for carrier-mediated transport of drugs as it is highly expressed in the blood-brain barrier and also in various types of cancer. Several studies have proposed that in order for compounds to act as LAT1 substrates they should possess both negatively charged ?-carboxyl and positively charged ?-amino groups. However, in some reports, such as in two recent publications describing an isoleucine-quinidine ester prodrug (1), compounds having no free ?-carboxyl group have been reported to exhibit high affinity for LAT1 in vitro. In the present study, 1 was synthesized and its affinity for LAT1 was evaluated both with an in situ rat brain perfusion technique and in the human breast cancer cell line MCF-7 in vitro. 1 showed no affinity for LAT1 in either model nor did it show any affinity for LAT2 in an in vitro study. Our results confirm the earlier reported requirements for LAT1 substrates. Thus drugs or prodrugs with substituted ?-carboxyl group cannot bind to LAT with high affinity. PMID:25305508

Rautio, Jarkko; Kärkkäinen, Jussi; Huttunen, Kristiina; Gynther, Mikko

2014-10-01

288

Structure of six anhydrous molecular salts assembled from noncovalent associations between carboxylic acids and bis-N-imidazoles  

NASA Astrophysics Data System (ADS)

Six crystalline organic acid-base adducts derived from bis(N-imidazolyl) and carboxylic acids (3,5-dinitrobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, and phthalic acid) were prepared and characterized by X-ray diffraction analysis, IR, mp, and elemental analysis. The six compounds are all organic salts. In salts 1, 2, 4, 5, and 6 the corresponding bis(imidazole) derivatives are diprotonated, while in 3, the corresponding bis(imidazole) derivative is only monoprotonated. All supramolecular architectures of the salts 1-6 involve extensive Nsbnd H⋯O, Osbnd H⋯O, CH⋯O, and CH2⋯O hydrogen bonds as well as other noncovalent interactions. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. All the salts displayed 3D framework structures under the cooperation of these weak interactions. The results presented herein indicate that the strength and directionality of the N+sbnd H⋯O-, Osbnd H⋯O, and Nsbnd H⋯N hydrogen bonds between carboxylic acids and ditopic imidazoles are sufficient to bring about the formation of binary organic salts.

Jin, Shouwen; Guo, Ming; Wang, Daqi

2012-08-01

289

Synthesis, tautomeric forms, specific intermolecular interactions, and lipophilicity of methylated 6-hydroxypyridazine-3-carboxylic acid and its 4,5-dihydro analogs  

NASA Astrophysics Data System (ADS)

Effects of methylation for intermolecular interactions and lipophilicity have been studied for a series of methylated 4,5-dihydro-6-hydroxypyridazine-3-carboxylic and 6-hydroxypyridazine-3-carboxylic acids ( 1 and 2). In solution they exist in equilibrium of the lactam and lactim tautomers, with the reverse preferences for analogs 1 and 2, which affect the syntheses of their methylated derivatives. Carboxylic acid 2 preferably crystallizes as a hydrate, built of carboxylate anions and hydronium cations 2- rad H 3O +, hydrogen bonded into catemeric patterns involving both ions. In methyl 4,5-dihydro-6-oxopyridazine-3-carboxylate ( 4A) the molecules are NH⋯O hydrogen bonded into chains. In both structures 2- rad H 3O + and 4A, there are relatively strong CH⋯O hydrogen bonds, arranging the molecules into sheets. The increased lipophilicity of the methylated derivatives has been correlated with the formation of CH⋯O bonds.

Katrusiak, Anna; Piechowiak, Pawe?; Katrusiak, Andrzej

2011-07-01

290

ESTIMATION OF HYDROLYSIS RATE CONSTANTS OF CARBOXYLIC ACID ESTER AND PHOSPHATE ESTER COMPOUNDS IN AQUEOUS SYSTEMS FROM MOLECULAR STRUCTURE BY SPARC  

EPA Science Inventory

SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid ester and phosphate ester compounds in aqueous non- aqueous and systems strictly from molecular structure. The energy diffe...

291

40 CFR 180.426 - 2-[4,5-Dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinoline carboxylic acid...  

Code of Federal Regulations, 2013 CFR

...imidazol-2-yl]-3-quinoline carboxylic acid; tolerance for residues. A tolerance is established for residues of the herbicide 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H -imidazol-2-yl]-3-quinoline...

2013-07-01

292

40 CFR 180.426 - 2-[4,5-Dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinoline carboxylic acid...  

Code of Federal Regulations, 2011 CFR

...imidazol-2-yl]-3-quinoline carboxylic acid; tolerance for residues. A tolerance is established for residues of the herbicide 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H -imidazol-2-yl]-3-quinoline...

2011-07-01

293

Separation of the isomers of benzene poly(carboxylic acid)s by quaternary ammonium salt via formation of deep eutectic solvents.  

PubMed

Because of similar properties and very low volatility, isomers of benzene poly(carboxylic acid)s (BPCAs) are very difficult to separate. In this work, we found that isomers of BPCAs could be separated efficiently by quaternary ammonium salts (QASs) via formation of deep eutectic solvents (DESs). Three kinds of QASs were used to separate the isomers of BPCAs, including the isomers of benzene tricarboxylic acids (trimellitic acid, trimesic acid, and hemimellitic acid) and the isomers of benzene dicarboxylic acids (phthalic acid and isophthalic acid). Among the QASs, tetraethylammonium chloride was found to have the best performance, which could completely separate BPCA isomers in methyl ethyl ketone solutions. It was found that the hydrogen bond forming between QAS and BPCA results in the selective separation of BPCA isomers. QAS in DES was regenerated effectively by the antisolvent method, and the regenerated QAS was reused four times with the same high efficiency. PMID:25351281

Hou, Yucui; Li, Jian; Ren, Shuhang; Niu, Muge; Wu, Weize

2014-11-26

294

Parahydrogen-induced polarization of carboxylic acids: a pilot study of valproic acid and related structures.  

PubMed

Parahydrogen-induced polarization (PHIP) is a promising new tool for medical applications of MR, including MRI. The PHIP technique can be used to transfer high non-Boltzmann polarization, derived from parahydrogen, to isotopes with a low natural abundance or low gyromagnetic ratio (e.g. (13)C), thus improving the signal-to-noise ratio by several orders of magnitude. A few molecules acting as metabolic sensors have already been hyperpolarized with PHIP, but the direct hyperpolarization of drugs used to treat neurological disorders has not been accomplished until now. Here, we report on the first successful hyperpolarization of valproate (valproic acid, VPA), an important and commonly used antiepileptic drug. Hyperpolarization was confirmed by detecting the corresponding signal patterns in the (1)H NMR spectrum. To identify the optimal experimental conditions for the conversion of an appropriate VPA precursor, structurally related molecules with different side chains were analyzed in different solvents using various catalytic systems. The presented results include hyperpolarized (13)C NMR spectra and proton images of related systems, confirming their applicability for MR studies. PHIP-based polarization enhancement may provide a new MR technique to monitor the spatial distribution of valproate in brain tissue and to analyze metabolic pathways after valproate administration. PMID:24812006

Lego, Denise; Plaumann, Markus; Trantzschel, Thomas; Bargon, Joachim; Scheich, Henning; Buntkowsky, Gerd; Gutmann, Torsten; Sauer, Grit; Bernarding, Johannes; Bommerich, Ute

2014-07-01

295

Polystyrene-bound Mn(T4PyP): A highly efficient and reusable catalyst for biomimetic oxidative decarboxylation of carboxylic acids with sodium periodate  

Microsoft Academic Search

In this report, highly efficient oxidative decarboxylation of carboxylic acids with sodium periodate catalyzed by a supported manganese(III) porphyrin is described. In the presence of manganese(III) tetra(4-pyridyl)porphyrin supported on cross-linked chloromethylated polystyrene, [Mn(T4PyP)-CMP], as catalyst, carboxylic acids were converted to their corresponding carbonyl compounds via oxidative decarboxylation with sodium periodate using imidazole as axial ligand. The oxidation of anti-inflammatory drugs

Majid Moghadam; Shahram Tangestaninejad; Valiollah Mirkhani; Iraj Mohammadpoor-baltork; Narges Sirjanian; Somayeh Parand

2009-01-01

296

A comparison of the conversion of 1-amino-2-ethylcyclopropane-1-carboxylic acid stereoisomers to 1-butene by pea epicotyls and by a cell-free system  

Microsoft Academic Search

The characteristics of the conversion of 1-aminocyclopropane-1-carboxylic acid (ACC) to ethylene by pea (Pisum sativum L.) epicotyls and by pea epicotyl enzyme are compared. Of the four stereoisomers of 1-amino-2-ethylcyclopropane-1-carboxylic acid (AEC), only (1R,2S)-AEC is preferentially converted to 1-butene in pea epicotyls. This conversion is inhibited by ACC, indicating that butene production from (1R,2S)-AEC and ethylene production from ACC are

Thomas A. McKeon; Shang Fa Yang

1984-01-01

297

Chemical analysis and transplacental transfer of oseltamivir and oseltamivir carboxylic acid in pregnant rats.  

PubMed

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 OSE and OCA in plasma, amniotic fluids, placenta, and fetus were measured by the validated LC-MS/MS after OSE administration (10 mg/kg, i.v.). The pharmacokinetic data of both analytes were examined by non-compartmental modeling. The area under the concentration-time curve (AUC) of OCA in maternal plasma was found to be 3.6 times larger than that of OSE. The AUCs of OCA in both amniotic fluid and fetus were significantly decreased, in comparison with that in maternal plasma (reduced by 76.7 and 98.1%, respectively). We found that both OSE and OCA can penetrate the placenta, amniotic fluids and fetus in rats during pregnancy; however, the penetration of OCA was much lower than that of OSE. The mother-to-fetus transfer ratio was defined as AUC(fetus)/AUC(mother). The data demonstrated that the mother-to-fetus transfer ratio of OSE and OCA were 1.64 and 0.019, respectively, suggesting that OSE, but not OCA, penetrated through the placenta. Moreover, OCA might not be easily metabolized in the fetus due to the lack of carboxylase in the fetus. PMID:23056234

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

2012-01-01

298

Differential Activity of Carboxylic Acid Amide Fungicides Against Various Developmental Stages of Phytophthora infestans.  

PubMed

ABSTRACT Three carboxylic acid amide (CAA) fungicides, mandipropamid (MPD), dimethomorph (DMM) and iprovalicarb (IPRO) were examined for their effects on various asexual developmental stages of Phytophthora infestans in vitro and in planta. Germination of cystospores and direct germination of sporangia were inhibited with nanomole concentrations of MPD (0.005 mug/ml) and micromole concentrations of DMM (0.05 mug/ml) or IPRO (0.5 mug/ml). A temporary exposure of 1 h to CAAs was not detrimental to germination and infectivity of sporangia or cystospores. CAAs applied to cystospores at 1 h after the onset of germination did not prevent the emergence of germ tubes, but inhibited their further growth and deformed their shape. None of the fungicides affected discharge of zoospores from sporangia or the encystment (cell wall formation/assembly) of the zoospores. Mycelium growth in solid or liquid media was inhibited with micromole concentrations. CAAs mixed with sporangia and drop inoculated onto detached leaves strongly suppressed infection. Curative application at 1 day postinoculation (dpi) required higher concentrations of CAAs than preventive application to inhibit infection and lost its effectiveness at 2 dpi. When sprayed on established late blight lesions 4 days after inoculation, CAAs reduced sporangial production in a dose-dependent manner. Trans-laminar protection of potato or tomato leaves, although achieved with higher doses, was more effective with MPD than with DMM or IPRO. Shade house studies demonstrated superior control of late blight epidemics by MPD compared with the other molecules. The data suggest that germ tube formation by cystospores or sporangia is the most sensitive stage in the life cycle of P. infestans to CAAs. Of the three CAAs, MPD had the highest intrinsic activity against spore germination. This property, together with its better trans-laminar activity, makes MPD more effective than DMM or IPRO in controlling epidemics caused by P. infestans. PMID:18943685

Cohen, Yigal; Gisi, Ulrich

2007-10-01

299

Electronically Rich N-Substituted Tetrahydroisoquinoline 3-Carboxylic Acid Esters: Concise Synthesis and Conformational Studies  

PubMed Central

Recent work in our laboratory has shown that the highly substituted, electronically rich 1,2,3,4–tetrahydroisoquinoline–3–carboxylic acid (THIQ3CA) scaffold is a key building block for a novel class of promising anticoagulants (Al-Horani et al. J. Med. Chem. 2011, 54, 6125–6138). The synthesis of THIQ3CA analogs, especially containing specific, electronically rich substituents, has been a challenge and essentially no efficient methods have been reported in the literature. We describe three complementary, glycine donor-based strategies for high yielding synthesis of highly substituted, electronically rich THIQ3CA esters. Three glycine donors studied herein include hydantoin 1, (±)-Boc-?-phosphonoglycine trimethyl ester 2 and (±)-Z-?-phosphonoglycine trimethyl ester 3. Although the synthesis of THIQ3CA analogs could be achieved using either of the three, an optimal, high yielding approach for the desired THIQ3CA esters was best achieved using 3 in three mild, efficient steps. Using this approach, a focused library of advanced N-arylacyl, N-arylalkyl, and bis-THIQ3CA analogs was synthesized. Variable temperature and solvent-dependent NMR chemical shift studies indicated the presence of two major conformational rotamers in 3:1 proportion for N–arylacyl–THIQ3CA analogs, which were separated by a high kinetic barrier of ~17 kcal/mol. In contrast, N–arylalkyl and bis–THIQ3CA variants displayed no rotamerism, which implicates restricted rotation around the amide bond as the origin for high-barrier conformational interconversion. This phenomenon is of major significance because structure-based drug design typically utilizes only one conformation. Overall, the work presents fundamental studies on the synthesis and conformational properties of highly substituted, electronically rich THIQ3CA analogs. PMID:22665943

Al-Horani, Rami A.; Desai, Umesh R.

2012-01-01

300

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

PubMed Central

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 OSE and OCA in plasma, amniotic fluids, placenta, and fetus were measured by the validated LC-MS/MS after OSE administration (10 mg/kg, iv). The pharmacokinetic data of both analytes were examined by non-compartmental modeling. The area under the concentration-time curve (AUC) of OCA in maternal plasma was found to be 3.6 times larger than that of OSE. The AUCs of OCA in both amniotic fluid and fetus were significantly decreased, in comparison with that in maternal plasma (reduced by 76.7 and 98.1%, respectively). We found that both OSE and OCA can penetrate the placenta, amniotic fluids and fetus in rats during pregnancy; however, the penetration of OCA was much lower than that of OSE. The mother-to-fetus transfer ratio was defined as AUCfetus/AUCmother. The data demonstrated that the mother-to-fetus transfer ratio of OSE and OCA were 1.64 and 0.019, respectively, suggesting that OSE, but not OCA, penetrated through the placenta. Moreover, OCA might not be easily metabolized in the fetus due to the lack of carboxylase in the fetus. PMID:23056234

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

2012-01-01

301

Extraction and metalation of porphyrins in fluorous liquids with carboxylic acids and metal salts.  

PubMed

Porphyrins have found application in a remarkable variety of areas such as sensors, ion selective electrodes, photodynamic therapy, and energy-transfer systems. Here, we demonstrate the extraction of 5,10,15,20-tetraphenylporphyrin (TPhP) and 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP) into a mixture of perfluorohexanes (FC-72) through noncovalent interactions with Krytox (1), a carboxylic acid terminated perfluoropolyether. We found that 1 transfers two protons to the TPhP tetrapyrrole ring to create the porphyrin dication (H2TPhP2+) in FC-72 while up to six protons are transferred to the TPyP pyridyl and tetrapyrrole nitrogens to create a hexavalent cation macrocycle in the fluorous phase. The total charge on TPyP is controlled by adjusting the concentration of 1 in the fluorous phase. In addition, we observed extraction of ZnTPyP from CDCl3 with 1/FC-72, while ZnTPhP is not extracted by 1/FC-72. We prepared the Zn salt of 1 and found that it extracts (from CDCl3) and metalates TPyP but not TPhP. Competitive binding between the porphyrins and an ethanol cosolvent hinders the extraction of both TPhP and TPyP and inhibits the formation of the TPyP hexacation in FC-72. By controlling the concentration of porphyrin, 1, and ethanol, it is possible to reversibly solubilize TPyP in the fluorous phase through noncovalent interactions between the pyridyl moieties and 1 while leaving the tetrapyrrole ring available to interact with metals or other substrates. In addition, both porphyrins and ZnTPyP are easily recovered from the fluorous phase using commercially available fluorous solid-phase extraction cartridges. Understanding noncovalent interactions in fluorous matrices should lead to development of more robust devices for sensing and energy transfer. PMID:19413352

O'Neal, Kristi L; Weber, Stephen G

2009-05-28

302

Laccase-mediator system for alcohol oxidation to carbonyls or carboxylic acids: toward a sustainable synthesis of profens.  

PubMed

By combining two green and efficient catalysts, such as the commercially available enzyme laccase from Trametes versicolor and the stable free radical 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), the oxidation in water of some primary alcohols to the corresponding carboxylic acids or aldehydes and of selected secondary alcohols to ketones can be accomplished. The range of applicability of bio-oxidation is widened by applying the optimized protocol to the oxidation of enantiomerically pure 2-arylpropanols (profenols) into the corresponding 2-arylpropionic acids (profens), in high yields and with complete retention of configuration. PMID:25044433

Galletti, Paola; Pori, Matteo; Funiciello, Federica; Soldati, Roberto; Ballardini, Alberto; Giacomini, Daria

2014-09-01

303

Anaerobic thermophilic fermentation for carboxylic acid production from in-storage air-lime-treated sugarcane bagasse.  

PubMed

Wet storage and in situ lime pretreatment (50 °C, 1-atm air, 56 days, excess lime loading of 0.3 g Ca(OH)(2)/g dry biomass) of sugarcane bagasse (4,000 g dry weight) was performed in a bench-scale pile pretreatment system. Under thermophilic conditions (55 °C, NH(4)HCO(3) buffer, methane inhibitors), air-lime-treated bagasse (80 wt.%) and chicken manure (20 wt.%) were anaerobically co-digested in 1-L rotary fermentors by a mixed culture of marine microorganisms (Galveston, TX). During four-stage countercurrent fermentation, the resulting carboxylic acids consisted of primarily acetate (average 87.7 wt.%) and butyrate (average 9.0 wt.%). The experimental fermentation trains had the highest yield (0.47 g total acids/g volatile solids (VS) fed) and highest selectivity (0.79 g total acids/g VS digested) at a total acid concentration of 28.3 g/L, which is equivalent to an ethanol yield of 105.2 gal/(tonne VS fed). Both high total acid concentrations (>44.7 g/L) and high substrate conversions (>77.5%) are predicted for countercurrent fermentations of bagasse at commercial scale, allowing for an efficient conversion of air-lime-treated biomass to liquid transportation fuels and chemicals via the carboxylate platform. PMID:21365471

Fu, Zhihong; Holtzapple, Mark T

2011-06-01

304

Biosynthesis of 1-aminocyclopropane-1-carboxylic acid and ethylene from delta-aminolevulinic acid in ripening tomato fruits  

SciTech Connect

A new pathway for ethylene (C/sub 2/H/sub 4/) biosynthesis, which utilizes delta-aminolevulinic acid (ALA) as a precursor of 1-aminocyclopropane-1-carboxylic acid (ACC), the immediate precursor of C/sub 2/H/sub 4/, is presented. ALA enhanced ACC accumulation to 410% and C/sub 2/H/sub 4/ production to 232% of the control. The C/sub 2/H/sub 4/ production rate varied with the ALA concentration and the stage of tomato fruit development. As the ALA concentration increased from zero to 40 mM, the C/sub 2/H/sub 4/ production rate increased. Both treated and untreated pericarp discs from fruits at the pink stage of development yielded the largest C/sub 2/H/sub 4/ production rate. Radioactivity from (2,3-/sup 3/H)ALA was detected in both ACC and C/sub 2/H/sub 4/, and radioactivity from (4-/sup 14/C)ALA was detected in ACC and CO/sub 2/ but not in C/sub 2/H/sub 4/. However, radioactivity from (5-/sup 14/C)ALA was detected in CO/sub 2/, and its amount was greater than that obtained from (4-/sup 14/C)ALA. Neither ACC nor C/sub 2/H/sub 4/ showed any radioactivity when (5-/sup 14/C)ALA was supplied to the fruit discs. In addition, when (2,3-/sup 3/H)ALA or (4-/sup 14/C)ALA was supplied to the fruit discs, radioactivity was detected in other metabolites such as fumarate, succinate, malate, glutamate, glutamine, ..cap alpha..-ketoglutarate, and methionine, but the amount of radioactivity was insignificant as compared with the amount of radioactivity found in C/sub 2/H/sub 4/ and ACC.

El-Rayes, D.E.D.A.

1987-01-01

305

Insights on the susceptibility of plant pathogenic fungi to phenazine-1-carboxylic acid and its chemical derivatives.  

PubMed

Pseudomonas chlororaphis subsp. aureofaciens strain M71 produced two phenazine compounds as main secondary metabolites. These metabolites were identified as phenazine-1-carboxylic acid (PCA) and 2-hydroxyphenazine (2-OH P). In this study, the spectrum of the activity of PCA and 2-OH P was evaluated against a group of crop and forestal plant pathogenic fungi by an agar plate bioassay. PCA was active against most of the tested plant pathogens, while 2-OH P slightly inhibited a few fungal species. Furthermore, four semisynthesised derivatives of PCA (phenazine-1-carboxymethyl, phenazine-1-carboxamide, phenazine-1-hydroxymethyl and phenazine-1-acetoxymethyl) were assayed for their antifungal activity against 11 phytopathogenic species. Results showed that the carboxyl group is a structural feature important for the antifungal activity of PCA. Since the activity of phenazine-1-carboxymethyl and phenazine-1-carboxamide, the two more lipophilic and reversible PCA derivatives remained substantially unaltered compared with PCA. PMID:22724439

Puopolo, Gerardo; Masi, Marco; Raio, Aida; Andolfi, Anna; Zoina, Astolfo; Cimmino, Alessio; Evidente, Antonio

2013-01-01

306

Equilibrium 2H/ 1H fractionations in organic molecules. II: Linear alkanes, alkenes, ketones, carboxylic acids, esters, alcohols and ethers  

NASA Astrophysics Data System (ADS)

Equilibrium 2H/ 1H fractionation factors (? eq) for various H positions in alkanes, alkenes, ketones, carboxylic acids, esters, alcohols, and ethers were calculated between 0 and 100 °C using vibrational frequencies from ab initio QM calculations (B3LYP/6-311G**). Results were then corrected using a temperature-dependent linear calibration curve based on experimental data for H ? in ketones ( Wang et al., 2009). The total uncertainty in reported ? eq values is estimated at 10-20‰. The effects of functional groups were found to increase the value of ? eq for H next to electron-donating groups, e.g. sbnd OR, sbnd OH or sbnd O(C dbnd O)R, and to decrease the value of ? eq for H next to electron-withdrawing groups, e.g. sbnd (C dbnd O)R or sbnd (C dbnd O)OR. Smaller but significant functional group effects are also observed for H ? and sometimes H ?. By summing over individual H positions, we estimate the equilibrium fractionation relative to water to be -90‰ to -70‰ for n-alkanes and around -100‰ for pristane and phytane. The temperature dependence of these fractionations is very weak between 0 and 100 °C. Our estimates of ? eq agree well with field data for thermally mature hydrocarbons (? 2H values between -80‰ and -110‰ relative to water). Therefore the observed ? 2H increase of individual hydrocarbons and the disappearance of the biosynthetic ? 2H offset between n-alkyl and linear isoprenoid lipids during maturation of organic matter can be confidently attributed to H exchange towards an equilibrium state. Our results also indicate that many n-alkyl lipids are biosynthesized with ? 2H values that are close to equilibrium with water. In these cases, constant down-core ? 2H values for n-alkyl lipids cannot be reliably used to infer a lack of isotopic exchange.

Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A., III

2009-12-01

307

Selective catalytic oxidative-dehydrogenation of carboxylic acids-acrylate and crotonate formation at the Au/TiO2 interface.  

PubMed

The oxidative-dehydrogenation of carboxylic acids to selectively produce unsaturated acids at the second and third carbons regardless of alkyl chain length was found to occur on a Au/TiO2 catalyst. Using transmission infrared spectroscopy (IR) and density functional theory (DFT), unsaturated acrylate (H2C?CHCOO) and crotonate (CH3CH?CHCOO) were observed to form from propionic acid (H3CCH2COOH) and butyric acid (H3CCH2CH2COOH), respectively, on a catalyst with ?3 nm diameter Au particles on TiO2 at 400 K. Desorption experiments also show gas phase acrylic acid is produced. Isotopically labeled (13)C and (12)C propionic acid experiments along with DFT calculated frequency shifts confirm the formation of acrylate and crotonate. Experiments on pure TiO2 confirmed that the unsaturated acids were not produced on the TiO2 support alone, providing evidence that the sites for catalytic activity are at the dual Au-Ti(4+) sites at the nanometer Au particles' perimeter. The DFT calculated energy barriers between 0.3 and 0.5 eV for the reaction pathway are consistent with the reaction occurring at 400 K on Au/TiO2. PMID:24597473

McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Yates, John T

2014-04-01

308

CLEAVAGE OF THE CARBOXYL-TERMINUS OF LEACS2, A TOMATO 1-AMINOCYCLOPROPANE-1-CARBOXYLIC ACID SYNTHASE ISOMER, BY A 64-KDA TOMATO METALLOPROTEASE PRODUCES A TRUNCATED BUT ACTIVE ENZYME  

Technology Transfer Automated Retrieval System (TEKTRAN)

1-Aminocyclopropane-1-carboxylic acid (ACC) synthase (ACS) is the principal enzyme in phytohormone ethylene biosynthesis. Previous studies have shown that the hypervariable C-terminus of ACS is proteolytically processed in vivo. However, the protease responsible for this has not yet been identified....

309

Determination of carboxylic acids in water by gas chromatography-mass spectrometry after continuous extraction and derivatisation.  

PubMed

This paper describes a new approach for the determination of monocarboxylic, dicarboxylic and tricarboxylic acids (35 compounds) in water. The analytes, in acid medium (pH ? 1.3), were sorbed on an 80 mg LiChrolut EN-Supelclean ENVI-18 (1:1) column and subsequently eluted with methanol. After evaporation of the extract to ? 10 ?L, the analytes were spiked with 60 ?L of the derivatising reagent and derivatised in a household microwave oven for 3 min. Among the reagents tested (BF(3)/1-butanol; acetyl chloride/1-butanol; isobutyl chloroformate/1-butanol; trimethylphenylammonium hydroxide, N,O-bis-(trimethylsilyl)acetamide, N,O-bis-(trimethylsilyl)trifluoroacetamide and trimethylchlorosilane), the best results in terms of reaction yield and stability of the derivatives were obtained with the mixture of 1% trimethylchlorosilane in N,O-bis-(trimethylsilyl)trifluoroacetamide. Microwave assisted derivatisation was used as an alternative heating approach for the rapid silylation of carboxylic acids. The proposed method proved to be a suitable analytical procedure for several types of carboxylic acids in water, with limits of detection within the range 0.6-15 ng L(-1), precision values from 4.0 to 6.0% (as within-day relative standard deviation) and recoveries from 93 to 101% for all the target analytes. PMID:22483903

Jurado-Sánchez, Beatriz; Ballesteros, Evaristo; Gallego, Mercedes

2012-05-15

310

Eight salts constructed from 4-phenylthiazol-2-amine and carboxylic acid derivatives through combination of strong hydrogen bonding and weak noncovalent interactions  

NASA Astrophysics Data System (ADS)

Eight crystalline organic salts derived from 4-phenylthiazol-2-amine and carboxylic acid derivatives (2-chloronicotinic acid, 3-hydroxy-2-naphthoic acid, p-nitrobenzoic acid, 2-hydroxy-5-(phenyldiazenyl)benzoic acid, 5-nitrosalicylic acid, 5-sulfosalicylic acid, oxalic acid, and L-malic acid) were prepared and characterized by X-ray diffraction analysis, IR, mp, and elemental analysis. In all of the salts except 6, 7, and 8, the 4-phenylthiazol-2-amine and carboxylic acid components are held together by two fused heterosynthons: a R22(7) heterosynthon and a R22(8) heterosynthon. All supramolecular architectures of the organic salts 1-8 involve extensive Nsbnd H⋯O hydrogen bonds as well as other noncovalent interactions. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. The salts displayed 2D/3D framework structure under these weak interactions.

Jin, Shouwen; Zhu, Qiaowang; Wei, ShuaiShuai; Wang, Daqi

2013-10-01

311

Efficient cluster-based catalysts for asymmetric hydrogenation of ?-unsaturated carboxylic acids.  

PubMed

The new clusters [H(4)Ru(4)(CO)(10)(?-1,2-P-P)], [H(4)Ru(4)(CO)(10) (1,1-P-P)] and [H(4)Ru(4)(CO)(11)(P-P)] (P-P=chiral diphosphine of the ferrocene-based Josiphos or Walphos ligand families) have been synthesised and characterised. The crystal and molecular structures of eleven clusters reveal that the coordination modes of the diphosphine in the [H(4)Ru(4)(CO)(10)(?-1,2-P-P)] clusters are different for the Josiphos and the Walphos ligands. The Josiphos ligands bridge a metal-metal bond of the ruthenium tetrahedron in the "conventional" manner, that is, with both phosphine moieties coordinated in equatorial positions relative to a triangular face of the tetrahedron, whereas the phosphine moieties of the Walphos ligands coordinate in one axial and one equatorial position. The differences in the ligand size and the coordination mode between the two types of ligands appear to be reflected in a relative propensity for isomerisation; in solution, the [H(4)Ru(4)(CO)(10)(1,1-Walphos)] clusters isomerise to the corresponding [H(4)Ru(4)(CO)(10)(?-1,2-Walphos)] clusters, whereas the Josiphos-containing clusters show no tendency to isomerisation in solution. The clusters have been tested as catalysts for asymmetric hydrogenation of four prochiral ?-unsaturated carboxylic acids and the prochiral methyl ester (E)-methyl 2-methylbut-2-enoate. High conversion rates (>94%) and selectivities of product formation were observed for almost all catalysts/catalyst precursors. The observed enantioselectivities were low or nonexistent for the Josiphos-containing clusters and catalyst (cluster) recovery was low, suggesting that cluster fragmentation takes place. On the other hand, excellent conversion rates (99-100%), product selectivities (99-100% in most cases) and good enantioselectivities, reaching 90% enantiomeric excess (ee) in certain cases, were observed for the Walphos-containing clusters, and the clusters could be recovered in good yield after completed catalysis. Results from high-pressure NMR and IR studies, catalyst poisoning tests and comparison of catalytic properties of two [H(4)Ru(4)(CO)(10)(?-1,2-P-P)] clusters (P-P=Walphos ligands) with the analogous mononuclear catalysts [Ru(P-P)(carboxylato)(2)] suggest that these clusters may be the active catalytic species, or direct precursors of an active catalytic cluster species. PMID:22890820

Moberg, Viktor; Duquesne, Robin; Contaldi, Simone; Röhrs, Oliver; Nachtigall, Jonny; Damoense, Llewellyn; Hutton, Alan T; Green, Michael; Monari, Magda; Santelia, Daniela; Haukka, Matti; Nordlander, Ebbe

2012-09-24

312

Molecular Models of Reactants and Products from an Asymmetric Synthesis of a Chiral Carboxylic Acid  

NSDL National Science Digital Library

Our JCE Featured Molecules for this month come from the paper by Thomas E. Smith, David P. Richardson, George A. Truran, Katherine Belecki, and Megumi Onishi (1). The authors describe the use of a chiral auxiliary, 4-benzyl-2-oxazolidinone, in the synthesis of a chiral carboxylic acid. The majority of the molecules used in the experiment, together with several of the pharmaceuticals mentioned in the paper, have been added to our molecule collection. In many instances multiple enantiomeric and diastereomeric forms of the molecules have been included. This experiment could easily be extended to incorporate various aspects of computation for use in an advanced organic or integrated laboratory. Here are some possible exercises using the R and S forms of the 4-benzyl-2-oxazolidinone as the authors point out that both forms are available commercially. Calculation of the optimized structures and energies of the enantiomers at the HF/631-G(d) level using Gaussian03 (2) produces the results shown in Table 1. Evaluation of the vibrational frequencies results in no imaginary frequencies and the 66 real frequencies are identical for the two forms. Examination of the computed IR spectra also shows them to be identical. Additionally, the Raman and NMR spectra can be calculated for the enantiomers and compared to experimental values and spectral patterns. A tool that is becoming increasingly important for assigning absolute configuration is vibrational circular dichroism (VCD). Although the vibrational spectra of an enantiomeric pair are identical, the VCD spectra show opposite signs, as shown in Figure 1. One can imagine a synthesis, using an unknown enantiomer of the chiral auxiliary, followed by calculations of the electronic and vibrational properties of all of the intermediates and the product, and determination of absolute configuration of reactants and products by comparison of experimental and computed VCD spectra. Using a viewer capable of displaying two molecules that can be moved independently, students could more easily visualize the origin of the enantiomeric preference in the reaction between the chelated enolate and allyl iodide.

313

Diverse models for the prediction of HIV integrase inhibitory activity of substituted quinolone carboxylic acids.  

PubMed

In the present study both classification and correlation techniques of diverse nature were successfully employed for the development of models for the prediction of human immunodeficiency virus (HIV) integrase inhibitory activity using a dataset comprising 50 analogs of quinolone carboxylic acid. The values of various molecular descriptors (MDs) for each analog in the dataset were computed using the MDS V-life science QSAR plus module. The values of other MDs which are not part of MDS V-life science were computed using an in-house computer program. A decision tree (DT) was constructed for the HIV integrase inhibitory activity to determine the importance of MDs. The DT learned the information from the input data with an accuracy of 98% and correctly predicted the cross-validated (10 fold) data with an accuracy of 96%. Three MDs, E-state contribution descriptor (SssOHE), molecular connectivity topochemical index ($\\chi {}^{{\\rm A}} $), and eccentric connectivity topochemical index ($\\xi _{{\\rm C}}^{{\\rm C}} $), were used to develop the models using moving average analysis (MAA). The accuracy of classification of single descriptor based models using MAA was found to vary from a minimum of 96% to a maximum of 98%. The statistical significance of the models was assessed through specificity, sensitivity, overall accuracy, Mathew's correlation coefficient, and intercorrelation analysis. The widely used methods like multiple linear regression, partial least squares, and principal component regression were employed for development of correlation models. The models were generated on a training set of 36 molecules. The models had a correlation coefficient (r(2) ) of 0.86 to 0.92, significant cross validated correlation coefficient (q(2) ) of 0.79 to 0.85, F-test from 63.2 to 93.06, r(2) for external test set (pred_r(2) ) from 0.69, coefficient of correlation of predicted dataset (pred_ r(2) Se) of 0.77, and degree of freedom from 27 to 30. Alignment independent descriptors, SsOHE-index, SaaCHE index, SssCH2, and x?log?P were found to be the most important descriptors for the development of correlation models for the prediction of HIV integrase inhibitory activity. PMID:22945879

Gupta, Monika; Madan, Anil Kumar

2012-12-01

314

L-2-oxothiazolidine-4-carboxylic acid attenuates oxidative stress and inflammation in retinal pigment epithelium  

PubMed Central

Purpose Oxidant- and inflammation-induced damage to retinal pigment epithelial (RPE) cells is central to the pathogenesis of age-related macular degeneration (AMD). Thus, developing novel strategies to protect these cells is important. We reported previously on the robust antioxidant and therefore cell-protective effects of the cysteine pro-drug L-2-oxothiazolidine-4-carboxylic acid (OTC) in cultured human RPE cells. New reports citing a novel anti-inflammatory role for OTC in addition to the known glutathione-stimulating and antioxidant properties emerged recently; however, this role has not been evaluated in RPE cells or in intact retina. Given the crucial causative roles of oxidative stress and inflammation in AMD pathogenesis, knowing whether OTC might exhibit a similar benefit in this cell and tissue type has high clinical relevance; thus, we evaluated OTC in the present study. Methods ARPE-19 and primary RPE cells isolated from wild-type, Gpr109a?/?, or Slc5a8?/? mouse eyes were exposed to TNF-? in the presence or absence of OTC, followed by analysis of IL-6 and Ccl2 expression with real-time quantitative polymerase chain reaction or enzyme-linked immunosorbent assay. Cellular and molecular markers of inflammation and oxidative stress (i.e., IL-1?, TGF-?, ABCG1, ABCA1, reduced glutathione, and dihydroethidium) were evaluated in Ccl2?/?/Cx3cr1?/? double knockout mice on rd8 background (DKO rd8) treated with OTC (10 mg/ml) in drinking water for a period of 5 months. Results OTC treatment significantly inhibited the expression and secretion of IL-6 and Ccl2 in TNF-?-stimulated ARPE-19 cells. Studies conducted using DKO rd8 animals treated with OTC in drinking water confirmed these findings. Cellular and molecular markers of inflammation were significantly suppressed in the retinas of the OTC-treated DKO rd8 animals. Subsequent in vitro and in vivo studies of the possible mechanism(s) to explain these actions revealed that although OTC is an agonist of the anti-inflammatory G-protein coupled receptor GPR109A and a transportable substrate of the sodium-coupled monocarboxylate transporter SMCT1 (SLC5A8), these properties may play a role but do not explain entirely the anti-inflammatory effects this compound elicits in cultured RPE cells and the intact mouse retina. Conclusions This study represents, to our knowledge, the first report of the suppressive effects of OTC on inflammation in cultured RPE cells and on inflammation and oxidative stress in the retina in vivo. PMID:24426777

Promsote, Wanwisa; Veeranan-Karmegam, Rajalakshmi; Ananth, Sudha; Shen, Defen; Chan, Chi-Chao; Lambert, Nevin A.; Ganapathy, Vadivel

2014-01-01

315

Heparinic Acids: Determination of Equivalent Weights and Sulfate to Carboxyl Ratios  

Microsoft Academic Search

By means of an automatic titration apparatus, a polyelectrolyte of biological origin, heparin, from two animal sources, was found to have an average equivalent weight of 170.0, a sulfate content of 34.44 percent, and a sulfate to carboxyl ratio of 2.59.

Klaus E. Kuettner; Arthur Lindenbaum

1964-01-01

316

Coumarin-3-carboxylic acid derivatives as potentiators and inhibitors of recombinant and native N-Methyl-D-Aspartate receptors  

PubMed Central

N-Methyl-D-aspartate receptors (NMDARs) are known to be involved in a range of neurological and neurodegenerative disorders and consequently the development of compounds that modulate the function of these receptors has been the subject of intense interest. We have recently reported that 6-bromocoumarin-3-carboxylic acid (UBP608) is a negative allosteric modulator with weak selectivity for GluN2A-containing NMDARs. In the present study, a series of commercially available and newly synthesized coumarin derivatives have been evaluated in a structure-activity relationship (SAR) study as modulators of recombinant NMDAR activity. The main conclusions from this SAR study were that substituents as large as iodo were accommodated at the 6-position and that 6,8-dibromo or 6,8-diiodo substitution of the coumarin ring enhanced the inhibitory activity at NMDARs. These coumarin derivatives are therefore excellent starting points for the development of more potent and GluN2 subunit selective inhibitors, which may have application in the treatment of a range of neurological disorders such as neuropathic pain, epilepsy and depression. Surprisingly, 4-methyl substitution of UBP608 to give UBP714, led to conversion of the inhibitory activity of UBP608 into potentiating activity at recombinant GluN1/GluN2 receptors. UBP714 also enhanced NMDAR mediated field EPSPs in the CA1 region of the hippocampus. UBP714 is therefore a novel template for the development of potent and subunit selective NMDAR potentiators that may have therapeutic applicability in the treatment of patients with cognitive deficits or schizophrenia. PMID:22265875

Irvine, Mark W.; Costa, Blaise M.; Volianskis, Arturas; Fang, Guangyu; Ceolin, Laura; Collingridge, Graham L.; Monaghan, Daniel T.; Jane, David E.

2012-01-01

317

Multiple effects of anthracene-9-carboxylic acid on the TMEM16B/anoctamin2 calcium-activated chloride channel.  

PubMed

Ca(2+)-activated Cl(-) currents (CaCCs) play important roles in many physiological processes. Recent studies have shown that TMEM16A/anoctamin1 and TMEM16B/anoctamin2 constitute CaCCs in several cell types. Here we have investigated for the first time the extracellular effects of the Cl(-) channel blocker anthracene-9-carboxylic acid (A9C) and of its non-charged analogue anthracene-9-methanol (A9M) on TMEM16B expressed in HEK 293T cells, using the whole-cell patch-clamp technique. A9C caused a voltage-dependent block of outward currents and inhibited a larger fraction of the current as depolarization increased, whereas the non-charged A9M produced a small, not voltage dependent block of outward currents. A similar voltage-dependent block by A9C was measured both when TMEM16B was activated by 1.5 and 13?M Ca(2+). However, in the presence of 1.5?M Ca(2+) (but not in 13?M Ca(2+)), A9C also induced a strong potentiation of tail currents measured at -100mV after depolarizing voltages, as well as a prolongation of the deactivation kinetics. On the contrary, A9M did not produce potentiation of tail currents, showing that the negative charge is required for potentiation. Our results provide the first evidence that A9C has multiple effects on TMEM16B and that the negative charge of A9C is necessary both for voltage-dependent block and for potentiation. Future studies are required to identify the molecular mechanisms underlying these complex effects of A9C on TMEM16B. Understanding these mechanisms will contribute to the elucidation of the structure and functional properties of TMEM16B channels. PMID:25620774

Cherian, O Lijo; Menini, Anna; Boccaccio, Anna

2015-04-01

318

Estimation of carboxylic acid metabolite of clopidogrel in Wistar rat plasma by HPLC and its application to a pharmacokinetic study.  

PubMed

A new HPLC method was developed for the estimation of carboxylic acid metabolite of clopidogrel bisulfate in rat plasma using atorvastatin as internal standard. Plasma samples were extracted with a mixture of ethyl acetate and di-chloro methane (80:20, v/v) followed by subsequent reconstitution in a mixture of water:methanol:acetonitrile (40:40:20, v/v). The chromatographic separation was achieved with gradient elution on Kromasil ODS, 250 mm x 4.6 mm i.d., 5 microm analytical column maintained at 30 degrees C. Carboxylic acid metabolite of clopidogrel as well as the internal standard were detected at a wavelength of 220 nm. The method was validated as per USFDA guidelines. Calibration curves were linear in the concentration range of 125.0-32,000 ng/ml and the correlation coefficient was better than 0.999. The extraction efficiency for the carboxylic acid metabolite of clopidogrel was more than 85.76%. The intra-day accuracy ranged from 98.9% to 101.5% with a precision of 1.30% to 6.06%. Similarly, the inter-day accuracy was between 96.2% and 101.1% with a precision of 3.47% to 4.30%. The drug containing plasma samples were stable at -70 degrees C for 48 days and at ambient temperature for 24h. In the auto-sampler maintained at 15 degrees C, the processed and reconstituted samples were stable for 35 h. The drug containing frozen plasma samples were stable enough to with stand three freeze thaw cycles. The method was successfully applied to the pharmacokinetic study of the two different polymorphs of clopidogrel bisulfate in Wistar rat. PMID:15935741

Singh, Sonu S; Sharma, Kuldeep; Barot, Deepak; Mohan, P Ram; Lohray, Vidya B

2005-07-25

319

Metabolic degradation of phenazine-1-carboxylic acid by the strain Sphingomonas sp. DP58: the identification of two metabolites.  

PubMed

The biotransformation of phenazine-1-carboxylic acid (PCA) by PCA-degrading strain Sphingomonas sp. DP58 yielded small quantities of metabolites and was demonstrated for the first time. The metabolites were isolated by using preparative high-performance liquid chromatography (HPLC). In addition, these were subsequently characterized by gas chromatography (GC)-mass spectrum (MS) after N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) derivatization and (1)H-nuclear magnetic resonance (NMR). They were identified as 4-hydroxy-1-(2-carboxyphenyl) azacyclobut-2-ene-2-carbonitrile (HPAEC) and 4-hydroxy-1-(2-carboxyphenyl)-2-azetidinecarbonitrile (HPAC). The two metabolites had transformational relationship between each other. PMID:18097645

Chen, Kuaikuai; Hu, Hongbo; Wang, Wei; Zhang, Xuehong; Xu, Yuquan

2008-09-01

320

Selective conversion of alcohols in water to carboxylic acids by in situ generated ruthenium trans dihydrido carbonyl PNP complexes.  

PubMed

In this work, we present a mild method for direct conversion of primary alcohols into carboxylic acids with the use of water as an oxygen source. Applying a ruthenium dihydrogen based dehydrogenation catalyst for this cause, we investigated the effect of water on the catalytic dehydrogenation process of alcohols. Using 1 mol% of the catalyst we report up to high yields. Moreover, we isolated key intermediates which most likely play a role in the catalytic cycle. One of the intermediates was identified as a trans dihydrido carbonyl complex which is generated in situ in the catalytic process. PMID:25019331

Choi, Jong-Hoo; Heim, Leo E; Ahrens, Mike; Prechtl, Martin H G

2014-12-14

321

Synthesis of 3-(4-heteroaryl-phenyl)-8-oxabicyclo[3.2.1]octane-2-carboxylic acid methyl esters  

Microsoft Academic Search

Cross coupling protocols were applied for the synthesis of 3-(4-heteroaryl-phenyl)-8-oxabicyclo[3.2.1]oct-2-ene-2-carboxylic acid methyl esters. Stille conditions produced the corresponding products in reasonable yields. Samarium iodide reduction of the resulting coupling products produced the 2?-carbomethoxy-3?-aryl-8-oxabicyclo[3.2.1]octane diastereoisomers as the major, and the 2?-carbomethoxy-3?-aryl-8-oxabicyclo[3.2.1]octane diastereoisomer as the minor products. Both diastereomers manifested inhibition of the dopamine (DAT) and serotonin (SERT) transporters, with some selectivity

Lokman Torun; Shanghao Liu; Bertha K. Madras; Peter C. Meltzer

2006-01-01

322

The direct electrocatalysis of phenazine-1-carboxylic acid excreted by Pseudomonas alcaliphila under alkaline condition in microbial fuel cells.  

PubMed

In this paper, we reported a kind of exoelectrogens, Pseudomonas alcaliphila (P. alcaliphila) strain MBR, which could excrete phenazine-1-carboxylic acid (PCA) to transfer electron under alkaline condition in microbial fuel cells (MFCs). The electrochemical activity of strain MBR and the extracellular electron transfer mechanism in MFCs were evaluated by cyclic voltammetry (CV) and electricity generation curve measurement. The results indicated a soluble mediator was the key factor for extracellular electron transfer of strain MBR under alkaline condition. The soluble mediator was PCA detected by gas chromatography-mass (GC-MS) analyses. PMID:21596560

Zhang, Tingtao; Zhang, Lixia; Su, Wentao; Gao, Ping; Li, Daping; He, Xiaohong; Zhang, Yashu

2011-07-01

323

Development of carboxylic acid replacements in indole-N-acetamide inhibitors of hepatitis C virus NS5B polymerase.  

PubMed

Allosteric inhibition of the hepatitis C virus (HCV) NS5B RNA-dependent RNA polymerase enzyme has recently emerged as a viable strategy toward blocking replication of viral RNA in cell-based systems. We report here 2 series of indole-N-acetamides, bearing physicochemically diverse carboxylic acid replacements, which show potent affinity for the NS5B enzyme with reduced potential for formation of glucuronide conjugates. Preliminary optimization of these series furnished compounds that are potent in the blockade of subgenomic HCV RNA replication in HUH-7 cells. PMID:17681757

Stansfield, Ian; Pompei, Marco; Conte, Immacolata; Ercolani, Caterina; Migliaccio, Giovanni; Jairaj, Mark; Giuliano, Claudio; Rowley, Michael; Narjes, Frank

2007-09-15

324

Absolute stereochemistry of guaianolides, of matricin and its epimers, of yarrow proazulenes, and of chamazulene carboxylic acid.  

PubMed

Known determinations of the absolute configuration of guaianolides were collected and found to be few. The absolute configurations of guaianolides rest on the assumption that 7-H always has alpha-orientation. For matricin, only the relative configuration was determined. On the basis of a detailed study of the NMR spectra of matricin and its epimers, and of synthetic, NMR, and CD studies with its decomposition product, chamazulene carboxylic acid, we were able to reconfirm the accepted 3S,3aR,4S,9R,9aS,9bS configuration of matricin. PMID:11400185

Imming, P; Goeters, S; Pawlitzki, G; Hempel, B

2001-07-01

325

Surface properties of calcium and magnesium oxide nanopowders grafted with unsaturated carboxylic acids studied with inverse gas chromatography.  

PubMed

Inverse gas chromatography (IGC) was applied at infinite dilution to evaluate the surface properties of calcium and magnesium oxide nanoparticles and the effect of surface grafted unsaturated carboxylic acid on the nanopowder donor-acceptor characteristics. The dispersive components (?(s)(D)) of the free energy of the nanopowders were determined by Gray's method, whereas their tendency to undergo specific interactions was estimated based on the electron donor-acceptor approach presented by Papirer. The calcium and magnesium oxide nanoparticles exhibited high surface energies (79 mJ/m² and 74 mJ/m², respectively). Modification of nanopowders with unsaturated carboxylic acids decreased their specific adsorption energy. The lowest value of ?(s)(D) was determined for nanopowders grafted with undecylenic acid, approximately 55 mJ/m². The specific interactions were characterised by the molar free energy (?G(A)(SP)) and molar enthalpy (?H(A)(SP)) of adsorption as well as the donor and acceptor interaction parameters (K(A), K(D)). PMID:22907042

Maciejewska, Magdalena; Krzywania-Kaliszewska, Alicja; Zaborski, Marian

2012-09-28

326

Novel inhibitors of the MDM2-p53 interaction featuring hydrogen bond acceptors as carboxylic acid isosteres.  

PubMed

We previously reported the discovery of potent and selective morpholinone and piperidinone inhibitors of the MDM2-p53 interaction. These inhibitors have in common a carboxylic acid moiety that engages in an electrostatic interaction with MDM2-His96. Our continued search for potent and diverse inhibitors led to the discovery of novel replacements for these acids uncovering new interactions with the MDM2 protein. In particular, using pyridine or thiazole as isosteres of the carboxylic acid moiety resulted in very potent analogues. From these, AM-6761 (4) emerged as a potent inhibitor with remarkable biochemical (HTRF IC50 = 0.1 nM) and cellular potency (SJSA-1 EdU IC50 = 16 nM), as well as favorable pharmacokinetic properties. Compound 4 also shows excellent antitumor activity in the SJSA-1 osteosarcoma xenograft model with an ED50 of 11 mg/kg. Optimization efforts toward the discovery of these inhibitors as well as the new interactions observed with the MDM2 protein are described herein. PMID:24601644

Gonzalez, Ana Z; Li, Zhihong; Beck, Hilary P; Canon, Jude; Chen, Ada; Chow, David; Duquette, Jason; Eksterowicz, John; Fox, Brian M; Fu, Jiasheng; Huang, Xin; Houze, Jonathan; Jin, Lixia; Li, Yihong; Ling, Yun; Lo, Mei-Chu; Long, Alexander M; McGee, Lawrence R; McIntosh, Joel; Oliner, Jonathan D; Osgood, Tao; Rew, Yosup; Saiki, Anne Y; Shaffer, Paul; Wortman, Sarah; Yakowec, Peter; Yan, Xuelei; Ye, Qiuping; Yu, Dongyin; Zhao, Xiaoning; Zhou, Jing; Olson, Steven H; Sun, Daqing; Medina, Julio C

2014-04-10

327

4Hydroxy2-quinolones. 177*. Study of a structure-diuretic activity relationship in a series of 4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid N-R-amides  

Microsoft Academic Search

With the aim of deducing a structure-biological dependence we have carried out the synthesis of quinoline-3-carboxylic acid\\u000a N-R-amides with a p-methoxyphenyl substituent in the amide part of the molecule. The effects of the compounds prepared on the excretory function\\u000a of the kidney are discussed. Using a system of simplex descriptors and the method of tree type classification a QSAR model

I. V. Ukrainets; N. L. Bereznyakova; L. A. Grinevich; V. E. Kuz’min; A. G. Artemenko

2010-01-01

328

Silylesterification of oxidized multi-wall carbon nanotubes by catalyzed dehydrogenative cross-coupling between carboxylic and hydrosilane functions  

NASA Astrophysics Data System (ADS)

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.

Seffer, J.-F.; Detriche, S.; Nagy, J. B.; Delhalle, J.; Mekhalif, Z.

2014-06-01

329

Theoretical modeling of the OH stretch infrared spectrum of carboxylic acid dimers based on first-principles anharmonic couplings  

NASA Astrophysics Data System (ADS)

Carboxylic acid dimers serve as prototypical systems for modeling the unusual spectral behavior of the hydride stretch fundamental. Large anharmonic effects associated with the pair of cooperatively strengthened OH⋯O=C hydrogen bonds produces complicated infrared spectra in which the OH stretch oscillator strength is spread over hundreds of wave numbers, resulting in a complicated band sub-structure. In this work cubic anharmonic constants are computed along internal coordinates associated with the intramolecular OH stretch, intermolecular stretch, and OH bend internal coordinates for the formic acid and benzoic acid dimers. These are then projected onto the normal coordinates to produce mixed states that are used in computing the OH stretch infrared spectrum. For the benzoic acid dimer the calculations accurately reproduce for three deuterated isotopomers the overall breadth and much of the vibrational sub-structure in the observed spectra. For the formic acid dimer, the spectrum is calculated using a model employing a subset of the cubic force constants as well as using the full cubic force field. The spectra calculated for the formic acid dimer are sparser and somewhat more sensitive to the exact positions of the anharmonically coupled states than that of the benzoic acid dimer. Again semiquantitative agreement with experiment is obtained.

Florio, Gina M.; Zwier, Timothy S.; Myshakin, Evgeniy M.; Jordan, Kenneth D.; Sibert, Edwin L.

2003-01-01

330

[Determination of the residues of 3-methyl-quinoxaline-2-carboxylic acid and quinoxaline-2-carboxylic acid in animal origin foods by high performance liquid chromatography-tandem mass spectrometry].  

PubMed

A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/ MS) method was developed for the simultaneous quantitative determination of 3-methyl-quinoxaline-2-carboxylic acid (MQCA) and quinoxaline-2-carboxylic acid (QCA) as the marker residues for carbadox (CBX) and olaquindox (OLA), respectively, in the muscles and livers of porcine and chicken and in the muscles of fish and shrimp. The MQCA and QCA were deproteinated with 5% metaphosphoric acid in 10% methanol followed by liquid-liquid extraction. Further clean-up was performed by solid phase extraction (SPE) through mixed mode anion-exchange columns (Oasis MAX SPE). The separation of the compounds was carried on a Waters Xterra MS C18 column (150 mm x 2.1 mm, 5 microm) by a gradient elution using methanol and 0.2% formic acid as mobile phases. The analytes were detected by tandem mass spectrometry in multiple reaction monitoring (MRM) mode with positive electrospray ionization. The MQCA and QCA were quantified by internal standard method. The linear ranges were 1.0-20.0 microg/L and the correlation coefficients were not less than 0.9996. The average recoveries and relative standard deviations ranged from 62.4%-118% and 1.48%-28.1% respectively at the spiked levels of 0.1, 0.2 and 1.0 microg/kg for the both markers. The limit of quantitation (LOQ) was 0.1 microg/kg. The method is sensitive, accurate and suitable for the determination and confirmation of MQCA and QCA in animal origin foods. PMID:23189659

Zheng, Ling; Wu, Yujie; Li, Yong; Li, Lihua

2012-07-01

331

Photometric determination of carboxylic acid impurities in polymers and organic liquids with the use of the ion pair of trinonyloctadecylammonium and Bromothymol Blue as the colored reagent  

Microsoft Academic Search

A method was proposed for the photometric determination of carboxylic acid impurities in polyvinylchloride, food and machine oils, and other samples. The method is based on the interaction of the acid groups of the sample with the ion pair of Bromothymol Blue and the trinonyloctadecylammonium cation in the binary solvent toluene-tetrahydrofuran. The method is highly sensitive and reproducible and was

E. M. Rakhman’ko; V. V. Zhilko; V. V. Egorov

2005-01-01

332

Speciation of aqueous Ni(II)-carboxylate and Ni(II)-fulvic acid solutions: Combined ATR-FTIR and XAFS analysis  

NASA Astrophysics Data System (ADS)

Aqueous solutions containing Ni(II) and a series of structurally related carboxylic acids were analyzed using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Ni K-edge X-ray absorption fine structure spectroscopy (XAFS). XAFS spectra were also collected for solutions containing Ni 2+ and chelating ligands (ethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA)) as well as soil fulvic acid. Limited spectral changes are observed for aqueous Ni(II) complexes with monocarboxylates (formate, acetate) and long-chain polycarboxylates (succinate, tricarballylate), where individual donor groups are separated by multiple bridging methylene groups. These spectral changes indicate weak interactions between Ni(II) and carboxylates, and the trends are similar to some earlier reports for crystalline Ni(II)-acetate solids, for which X-ray crystallography studies have indicated monodentate Ni(II)-carboxylate coordination. Nonetheless, electrostatic or outer-sphere coordination cannot be ruled out for these complexes. However, spectral changes observed for short-chain dicarboxylates (oxalate, malonate) and carboxylates that contain an alcohol donor group adjacent to one of the carboxylate groups (lactate, malate, citrate) demonstrate inner-sphere metal coordination by multiple donor groups. XAFS spectral fits of Ni(II) solutions containing soil fulvic acid are consistent with inner-sphere Ni(II) coordination by one or more carboxylate groups, but spectra are noisy and outer-sphere modes of coordination cannot be ruled out. These molecular studies refine our understanding of the interactions between carboxylates and weakly complexing divalent transition metals, such as Ni(II).

Strathmann, Timothy J.; Myneni, Satish C. B.

2004-09-01

333

Solubility of selected dibasic carboxylic acids in water, in ionic liquid of [Bmim][BF 4], and in aqueous [Bmim][BF 4] solutions  

Microsoft Academic Search

The solubilities of three dibasic carboxylic acids (adipic acid, glutaric acid, and succinic acid) in water, in the ionic liquid of 1-butyl-3-methyl-imidazolim tetrafluoroborate ([Bmim][BF4]), and in the aqueous [Bmim][BF4] solutions have been measured by a solid-disapperance method. The binodal curve of water+[Bmim][BF4] was also determined experimentally from solid–liquid–liquid coexistence temperature up to near the upper critical solution temperature. Experimental results

Ho-Mu Lin; Hsin-Yi Tien; Ying-Tzu Hone; Ming-Jer Lee

2007-01-01

334

Benzene-Poly-Carboxylic Acid Complex, a Novel Anti-Cancer Agent Induces Apoptosis in Human Breast Cancer Cells  

PubMed Central

Some cases of breast cancer are composed of clones of hormonal-independent growing cells, which do not respond to therapy. In the present study, the effect of Benzene-Poly-Carboxylic Acid Complex (BP-C1) on growth of human breast-cancer cells was tested. BP-C1 is a novel anti-cancer complex of benzene-poly-carboxylic acids with a very low concentration of cis-diammineplatinum (II) dichloride. Human breast cancer cells, MCF-7 and T47D, were used. Cell viability was detected by XTT assay and apoptosis was detected by Flow Cytometry and by annexin V/FITC/PI assay. Caspases were detected by western blot analysis and gene expression was measured by using the Applied Biosystems® TaqMan® Array Plates. The results showed that exposure of the cells to BP-C1 for 48 h, significantly (P<0.001) reduced cell viability, induced apoptosis and activated caspase 8 and caspace 9. Moreover, gene expression experiments indicated that BP-C1 increased the expression of pro-apoptotic genes (CASP8AP1, TNFRSF21, NFkB2, FADD, BCL10 and CASP8) and lowered the level of mRNA transcripts of inhibitory apoptotic genes (BCL2L11, BCL2L2 and XIAP. These findings may lead to the development of new therapeutic strategies for treatment of human cancer using BP-C1 analog. PMID:24523856

Fares, Fuad; Azzam, Naiel; Fares, Basem; Larsen, Stig; Lindkaer-Jensen, Steen

2014-01-01

335

Synthesis of 6-fluoro-1,4-dihydro-4-oxo-quinoline-3-carboxylic acid derivatives as potential antimicrobial agents.  

PubMed

In the present study, a series of 1-ethyl/benzyl-6-fluoro-7-(substituted piperazin-1-yl)1,4-dihydro-4-oxo-quinoline-3-carboxylic acid were synthesized and characterized by IR, 1H-NMR, mass spectral and elemental analysis. The in vitro antibacterial and antifungal activities of the compounds were evaluated by paper disc diffusion method. The minimum inhibitory concentrations (MIC) of the compounds were also determined by agar streak dilution method. The in vivo antibacterial activity of the compounds against Escherichia coli was also evaluated by mouse protection test. All the compounds exhibited significant antibacterial and weak antifungal activities. The in vivo antibacterial activity (ED50) against E. coli was 50-160 mg kg(-1) in the order of 7<9<8<10. 1-ethyl-6-fluoro-7-(2,5-dioxo-piperazin-1-yl)1,4-dihydro-4-oxo-quinoline-3-carboxylic acid (7) was found to exhibit the most potent in vitro antimicrobial activity with MIC of 4.1, 3.1, 3.1, 2.4, 1, 1, 25 and >100 microg mL(-1) against Staphylococcus aureus, Staphylococcus epidermidis, Micrococcus luteus, Bacillus cereus, E. coli, Klebsiella pneumoniae, Candida albicans and Aspergillus niger. PMID:14642332

Rameshkumar, Natesh; Ashokkumar, Mohan; Subramanian, Ekambaram Harihara; Ilavarasan, Raju; Sridhar, Seshaiah Krishnan

2003-01-01

336

Intracellular Sites of Synthesis and Storage of 1-(Malonylamino)cyclopropane-1-Carboxylic Acid in Acer pseudoplatanus Cells 1  

PubMed Central

Vacuoles were isolated from Acer pseudoplatanus cells that were incubated with [14C]1-aminocyclopropane-1-carboxylic acid (ACC). The kinetics of [14C]1-(malonylamino)cyclopropane-1-carboxylic acid (MACC) formation are consistent with the interpretation that MACC is synthesized in the cytosol, transported through the tonoplast, and accumulated in the vacuole. Twenty hours after chasing the labeled ACC with unlabeled ACC and adding 1 millimolar unlabeled MACC, all the [14C]MACC synthesized is located in the vacuole. Whole cells preloaded with [14C]MACC and then submitted to a continuous washing out, readily release their cytosolic MACC until complete exhaustion. The half-time of MACC efflux from the cytosol, calculated by the technique of compartmental analysis, is about 22 minutes. In contrast, vacuolar MACC remains sequestered within the vacuole. The transport of labeled MACC into the vacuole is stimulated by the presence of unlabeled MACC in the suspension medium, probably as a result of a reduced efflux of the labeled MACC from the cytosol into the suspending medium. PMID:16666357

Bouzayen, Mondher; Latché, Alain; Alibert, Gilbert; Pech, Jean-Claude

1988-01-01

337

DNA damage in human skin keratinocytes caused by multiwalled carbon nanotubes with carboxylate functionalization.  

PubMed

Water-soluble carbon nanotubes have been found to be one of the most promising nanomaterials in biological- and biomedical-based applications. However, there have been major concerns on their ability to cause cellular and DNA damages upon exposure. In this work, we explore the toxic effects of three multiwalled carbon nanotubes (MWCNTs: nonpurified, purified and carboxylate-functionalized) on human skin keratinocytes (HaCaT). Cytotoxicity tests using the conventional thiazolyl blue tetrazolium bromide (MTT) and the water-soluble tetrazolium (WST-1) assays for 0.5 or 24 h exposure to 20 ?g/mL of MWCNTs show that all three caused minimum cytotoxicity that is generally not statistically significant. Assessment of direct and oxidative DNA damages using both alkaline Comet assay and formamidopyrimidine DNA glycosylase-modified Comet assay reveals that the treatment with 20 ?g/mL of MWCNTs does not cause significant direct DNA damages, but causes great amount of oxidative DNA damages in HaCaT cells. The oxidative DNA damage reaches the maximum amount at 4 h of incubation in Dulbecco's minimum essential medium, but decreases to the minimum at 8 and 24 h of incubation, indicating repair of the oxidative damages by the intrinsic DNA repair mechanism of the cells. PMID:23012341

McShan, Danielle; Yu, Hongtao

2014-07-01

338

Comparative Metabolite Profiling of Carboxylic Acids in Rat Urine by CE-ESI MS/MS through Positively Pre-charged and 2H-coded Derivatization  

PubMed Central

A new approach for the selective comparative metabolite profiling of carboxylic acids in rat urine was established using capillary electrophoresis-mass spectrometry (CE-MS) and a method for positively pre-charged and 2H-coded derivatization. Novel derivatizing reagents, N-alkyl-4-aminomethylpyridinum iodide (alkyl=butyl, butyl-d9 or hexyl), containing quaternary amine and stable isotope atoms (deuterium), were introduced for the derivatization of carboxylic acids. CE separation in positive polarity showed high reproducibility (0.99 –1.32% RSD of migration time) and eliminated problems with capillary coating known in CE-MS anion analyses. Essentially complete ionization and increased hydrophobicity after the derivatization also enhanced MS detection sensitivity (e.g. formic acid was detected at 0.5 pg). Simultaneous derivatization of one sample using two structurally similar reagents, N-butyl-4-aminomethylpyridinum iodide (BAMP) and N-hexyl-4-aminomethylpyridinum iodide (HAMP), provided additional information for recognizing a carboxylic acid in an unknown sample. Moreover, characteristic fragmentation acquired by online CE-MS/MS allowed for identification and categorization of carboxylic acids. Applying this method on rat urine, we found 59 ions matching the characteristic patterns of carboxylic acids. From these 59, 32 ions were positively identified and confirmed with standards. For comparative analysis, 24 standard carboxylic acids were derivatized by chemically identical but isotopically distinct BAMP and BAMP-d9, and their derivatization limits and linearity ranges were determined. Comparative analysis was also performed on two individual urine samples derivatized with BAMP and BAMP-d9. The metabolite profiling variation between these two samples was clearly visualized. PMID:19035407

Yang, Wen-Chu; Regnier, Fred E.; Adamec, Jiri

2012-01-01

339

Direct Synthesis of Amides from Carboxylic Acids and Amines Using B(OCH2CF3)3  

PubMed Central

B(OCH2CF3)3, prepared from readily available B2O3 and 2,2,2-trifluoroethanol, is as an effective reagent for the direct amidation of a variety of carboxylic acids with a broad range of amines. In most cases, the amide products can be purified by a simple filtration procedure using commercially available resins, with no need for aqueous workup or chromatography. The amidation of N-protected amino acids with both primary and secondary amines proceeds effectively, with very low levels of racemization. B(OCH2CF3)3 can also be used for the formylation of a range of amines in good to excellent yield, via transamidation of dimethylformamide. PMID:23586467

2013-01-01

340

Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part II. Recovery of Ammonia from Sour Waters  

SciTech Connect

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, SUCCiOlC 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-based distribution ratios increase from 0.11 to 0.46 as the aqueous phase pH increases from 7.18 to 8.15. Regeneration of the organic extractant solution was carried out by stripping at elevated temperatures to remove the ammonia, with 99% recovery of the ammonia being obtained at 125 C.

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

1990-03-01

341

Carrier-Mediated Uptake of 1-(Malonylamino)cyclopropane-1-Carboxylic Acid in Vacuoles Isolated from Catharanthus roseus Cells 1  

PubMed Central

The uptake of 1-(malonylamino)cyclopropane-1-carboxylic acid (MACC), the conjugated form of the ethylene precursor, into vacuoles isolated from Catharanthus roseus cells has been studied by silicone layer floatation filtering. The transport across the tonoplast of MACC is stimulated fourfold by 5 millimolar MgATP, has a Km of about 2 millimolar, an optimum pH around 7, and an optimum temperature at 30°C. Several effectors known to inhibit ATPase (N,N?-dicyclohexylcarbodiimide) and to collapse the transtonoplastic H+ electrochemical gradient (carbonylcyanide m-chlorophenylhydrazone, gramicidin, and benzylamine) all reduced MACC uptake. Abolishing the membrane potential with SCN? and valinomycin also greatly inhibited MACC transport. Our data demonstrate that MACC accumulates in the vacuole against a concentration gradient by means of a proton motive force generated by a tonoplastic ATPase. The involvement of a protein carrier is suggested by the strong inhibition of uptake by compounds known to block SH—, OH—, and NH2— groups. MACC uptake is antagonized competitively by malonyl-d-tryptophan, indicating that the carrier also accepts malonyl-d-amino acids. Neither the moities of these compounds taken separately [1-aminocyclopropane-1-carboxylic acid, malonate, d-tryptophan or d-phenylalanine] nor malate act as inhibitors of MACC transport. The absence of inhibition of malate uptake by MACC suggests that MACC and malate are taken up by two different carriers. We propose that the carrier identified here plays an important physiological role in withdrawing from the cytosol MACC and malonyl-d-amino acids generated under stress conditions. PMID:16667182

Bouzayen, Mondher; Latché, Alain; Pech, Jean-Claude; Marigo, Gérard

1989-01-01

342

THz and mid-IR spectroscopy of interstellar ice analogs: methyl and carboxylic acid groups.  

PubMed

A fundamental problem in astrochemistry concerns the synthesis and survival of complex organic molecules (COMs) throughout the process of star and planet formation. While it is generally accepted that most complex molecules and prebiotic species form in the solid phase on icy grain particles, a complete understanding of the formation pathways is still largely lacking. To take full advantage of the enormous number of available THz observations (e.g., Herschel Space Observatory, SOFIA, and ALMA), laboratory analogs must be studied systematically. Here, we present the THz (0.3-7.5 THz; 10-250 cm(-1)) and mid-IR (400-4000 cm(-1)) spectra of astrophysically-relevant species that share the same functional groups, including formic acid (HCOOH) and acetic acid (CH3COOH), and acetaldehyde (CH3CHO) and acetone ((CH3)2CO), compared to more abundant interstellar molecules such as water (H2O), methanol (CH3OH), and carbon monoxide (CO). A suite of pure and mixed binary ices are discussed. The effects on the spectra due to the composition and the structure of the ice at different temperatures are shown. Our results demonstrate that THz spectra are sensitive to reversible and irreversible transformations within the ice caused by thermal processing, suggesting that THz spectra can be used to study the composition, structure, and thermal history of interstellar ices. Moreover, the THz spectrum of an individual species depends on the functional group(s) within that molecule. Thus, future THz studies of different functional groups will help in characterizing the chemistry and physics of the interstellar medium (ISM). PMID:25302394

Ioppolo, S; McGuire, B A; Allodi, M A; Blake, G A

2014-01-01

343

Comparison of CO2 and oxygen DC submerged thermal plasmas for decomposition of carboxylic acid in aqueous solution  

NASA Astrophysics Data System (ADS)

The feasibility of the carboxylic acid decomposition with two different direct current (DC) thermal plasma torches was investigated. An oxygen DC submerged thermal plasma torch and a newly designed submerged DC plasma torch operating with a mixture of carbon dioxide and methane (CO2/CH4) were used. Sebacic acid was selected as a representative of pollutants in the most wastewater produced by chemical process industries. The effect of different operational conditions including treatment time, the reactor pressure as well as the role of oxidizing agents such as (H2O2) were investigated on the decomposition rate of sebacic acid. Concentration of sebacic acid was quantified by Ion Chromatography/Mass Spectrometry (IC/MS). The oxygen plasma showed higher decomposition rate in basic medium. Adding H2O2 into aqueous solution enhanced the sebacic acid decomposition rate with the CO2/CH4 plasma up to the same decomposition rate of the oxygen plasma. Increasing the pressure also increased the decomposition rate for both plasmas with an increase twice higher for the CO2/CH4 plasma than that of the oxygen plasma. This work therefore presents the conditions in which these plasmas can provide the same decomposition rate for contaminants in aqueous solution.

Safa, S.; Hekmat-Ardakan, A.; Soucy, G.

2014-11-01

344

Polystyrene-bound Mn(T4PyP): a highly efficient and reusable catalyst for biomimetic oxidative decarboxylation of carboxylic acids with sodium periodate.  

PubMed

In this report, highly efficient oxidative decarboxylation of carboxylic acids with sodium periodate catalyzed by a supported manganese(III) porphyrin is described. In the presence of manganese(III) tetra(4-pyridyl)porphyrin supported on cross-linked chloromethylated polystyrene, [Mn(T4PyP)-CMP], as catalyst, carboxylic acids were converted to their corresponding carbonyl compounds via oxidative decarboxylation with sodium periodate using imidazole as axial ligand. The oxidation of anti-inflammatory drugs such Indomethacin and Ibuprofen was carried out successfully and the decarboxylated products were obtained. This catalyst can be reused several times without loss of its catalytic activity in the oxidation reactions. PMID:19359183

Moghadam, Majid; Tangestaninejad, Shahram; Mirkhani, Valiollah; Mohammadpoor-Baltork, Iraj; Sirjanian, Narges; Parand, Somayeh

2009-05-01

345

Crystal structure of (2S,4S)-5,5-dimethyl-2-(pyridin-2-yl)-1,3-thia­zolidine-4-carb­oxy­lic acid  

PubMed Central

In the title compound, C11H14N2O2S, the thia­zolidine ring has an envelope conformation with the C atom bonded to the carb­oxy­lic acid group at the flap. Two C atoms of the thia­zolidine ring adopt S conformations. In the crystal, O—H?N hydrogen bonds between the amine and carb­oxy­lic acid groups construct a helical chain structure along the a-axis direction. The chains are further connected via weak C—H?? contacts, forming a layer parallel to the ac plane. PMID:25553035

Laskar, Payel; Kuwamura, Naoto; Yoshinari, Nobuto; Konno, Takumi

2014-01-01

346

Sugar fragmentation in the maillard reaction cascade: formation of short-chain carboxylic acids by a new oxidative alpha-dicarbonyl cleavage pathway.  

PubMed

The formation of short-chain carboxylic acids was studied in Maillard model systems (90 degrees C, pH 6-10) with emphasis on the role of oxygen and water. The total amount of acetic acid formed did not depend on the reaction atmosphere. In the presence of labeled dioxygen or water (18O2, H2 17O), labeled oxygen was partially incorporated into acetic acid. Thermal treatment of 1-deoxy-d-erythro-2,3-hexodiulose (1) and 3-deoxy-d-erythro-hexos-2-ulose in the presence of 17O-enriched water under alkaline conditions led to acetic and formic acid, respectively, as indicated by 17O NMR spectroscopy. The suggested mechanism involves an oxidative alpha-dicarbonyl cleavage leading to an intermediary mixed acid anhydride that releases the acids, e.g., acetic and erythronic acid, from 1. Similarly, glyceric and lactic acids were formed from 1-deoxy-3,4-hexodiuloses, corroborated by complementary analytical techniques. This paper provides for the first time evidence for the direct formation of acids from C6-alpha-dicarbonyls by an oxidative mechanism and incorporation of a 17OH group into the carboxylic moiety. The experimental data obtained support the coexistence of at least two newly described reaction mechanisms leading to carboxylic acids, i.e., (i) a hydrolytic beta-dicarbonyl cleavage as a major pathway and (ii) an alternative minor pathway via oxidative alpha-dicarbonyl cleavage induced by oxidizing species. PMID:16939326

Davídek, Tomas; Robert, Fabien; Devaud, Stéphanie; Vera, Francia Arce; Blank, Imre

2006-09-01

347

Five binary supramolecular organic salts constructed from 2-aminoheterocyclic compounds and carboxylic acid derivatives through strong and weak non-covalent interactions  

NASA Astrophysics Data System (ADS)

Studies concentrating on hydrogen bonding between the base of 2-aminoheterocyclic compounds 5,7-dimethyl-1,8-naphthyridine-2-amine, 4-phenylthiazol-2-amine, and carboxylic acid derivatives have led to an increased understanding of the role 2-aminoheterocyclic compounds have in binding with carboxylic acid derivatives. Here anhydrous and hydrous multicomponent adducts of 2-aminoheterocyclic compounds such as 5,7-dimethyl-1,8-naphthyridine-2-amine, and 4-phenylthiazol-2-amine have been prepared with 2-chloronicotinic acid, p-hydroxy benzoic acid, maleic acid, and phthalic acid. The five crystalline forms reported are organic salts of which the crystals and complexes were characterized by X-ray diffraction analysis, IR, mp, and elemental analysis. All supramolecular architectures of salts 1- 5 are stabilized by N sbnd H···O hydrogen bonds as well as other non-covalent interactions. These weak interactions combined, all the complexes displayed 3D structure.

Jin, Shouwen; Zhang, Wenbiao; Liu, Li; Wang, Daqi; He, Haidong; Shi, Tao; Lin, Feng

2011-04-01

348

Hydrophilic carboxylic acids and iridoid glycosides in the juice of American and European cranberries (Vaccinium macrocarpon and V. oxycoccos), lingonberries (V. vitis-idaea), and blueberries (V. myrtillus).  

PubMed

Analysis of the hydrophilic fraction of cranberry juice by reversed-phase HPLC using an Aqua LUNA column with diode array or MS detection revealed the presence of quinic acid, malic acid, shikimic acid, and citric acid. For the first time, two iridoid glucosides were found in the juice. The two iridoid glucosides were shown to be monotropein and 6,7-dihydromonotropein by MS and NMR spectroscopy. A fast reversed-phase HPLC method for quantification of the hydrophilic carboxylic acids was developed and used for analyses of cranberry, lingonberry, and blueberry juices. The level of hydrophilic carboxylic acids in cranberries was 2.67-3.57% (w/v), in lingonberries 2.27-3.05%, and in blueberries 0.35-0.75%. In lingonberries both iridoid glucosides were present, whereas only monotropein was present in blueberries. PMID:12405790

Jensen, Heidi D; Krogfelt, Karen A; Cornett, Claus; Hansen, S Honoré; Christensen, S Brøgger

2002-11-01

349

Dioxouranium(VI)--carboxylate complexes. Interaction with dicarboxylic acids in aqueous solution: speciation and structure.  

PubMed

In this paper we report the results of an investigation performed by potentiometric (H+-glass electrode) and visible spectrophotometric measurements on the interaction of UO2(2+) ion towards some carboxylic ligands (acetate, malonate, succinate, azelate). The measurements were carried out at T= 25 degrees C in different ionic media (KNO3 and NaCl) at different ionic strengths (0.1 < or = I/mol L(-1) < or = 1.0, NaCl; I/mol L(-1) = 0.1, KNO3). The dependence on ionic strength of formation constants was taken into account by using both a simple Debye-Hückel type equation and the SIT (Specific ion Interaction Theory) approach. Different speciation models (depending on concentration of reagents, ionic strength, pH-range) both for different carboxylates and different ionic media have been obtained. Linear combinations between formation constants, stoichiometric coefficients and length of alkyl chain of dicarboxylates have been observed and predicted formation constants at I= 0 mol L(-1) are reported for the interaction of UO2(2+) with HOOC-(CH2)n-COOH with 1 < or = n < or = 7. Finally, a visible absorption spectrum for each complex reaching a significant percentage of formation in solution (KNO3 medium) has been calculated to characterise the compounds found by pH-metric refinement. PMID:16948430

Berto, Silvia; Crea, Francesco; Daniele, Pier G; De Stefano, Concetta; Prenesti, Enrico; Sammartano, Silvio

2006-01-01

350

Predictions of the Fluorine NMR Chemical Shifts of Perfluorinated Carboxylic Acids, CnF2n+1COOH (n = 6-8)  

NASA Astrophysics Data System (ADS)

Perfluorinated carboxylic acids (PFCAs) are a class of persistent environmental pollutants. Commercially available PFCAs are mixtures of linear and branched isomers, possibly with impurities. Different isomers have different physical and chemical properties and toxicities. However, little is known about the properties and the finer details of the structures of the individual branched isomers. Full geometry optimizations for the linear n-alkane (C6-C27) PFCAs indicated that all have helical structures. The helical angle increases slightly with increasing chain length, from 16.3° in C6F13COOH to 17.0° in C27F55COOH. This study predicts 19F NMR parameters for 69 linear and branched isomers of the perfluoro carboxylic acids C6F13COOH, C7F15COOH, and C8F17COOH. B3LYP-GIAO/6-31++G(d,p)//B3LYP/6-31G(d,p) was used for the NMR calculations with analysis of the chemical shifts by the natural bond orbital method. The predictions of the 19F chemical shifts revealed the differences among the CF3, CF2, and CF groups. In general, the absolute values for the chemical shifts for the CF3 group are smaller than 90 ppm, for the CF larger than 160 ppm, and for the CF2 between 110 and 130 ppm. The chemical shifts of the branched isomers are smaller in magnitude than the linear ones. The decrease is correlated with the steric hindrance of the CF3 groups, the more hindered the CF3, the greater the decrease in the 19F chemical shifts. The predicted 19F chemical shifts are similar to those for analogous perfluoro compounds with other terminal functional groups such as -SO3H or -SO3NH2CH2CH3.

Liu, Zizhong; Goddard, John D.

2009-10-01

351

Simple and practical derivatization procedure for enhanced detection of carboxylic acids in liquid chromatography-electrospray ionization-tandem mass spectrometry.  

PubMed

A simple and practical derivatization procedure for increasing the detection responses of carboxylic acids in liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) has been developed. 2-Hydrazinopyridine (HP) and 2-picolylamine (PA) rapidly reacted with biologically and clinically important carboxylic acids [chenodeoxycholic acid, glycochenodeoxycholic acid, prostaglandin E2, 2-(-carboxyethyl)-6-hydroxy-2,7,8-trimethylchroman (gamma-CEHC),alpha-lipoic acid, homovanillic acid (HVA) and 5-hydroxyindole-3-acetic acid] in the presence of 2,2'-dipyridyl disulfide and triphenylphosphine. The resulting HP- and PA-derivatives were highly responsive in ESI-MS operating in the positive-ion mode and gave characteristic product ions during MS/MS, which enabled the sensitive detection using selected reaction monitoring. Among the two reagents, PA was of more practical use; the detection responses of the PA-derivatives were increased by 9-158-fold over the intact carboxylic acids and the limits of detection were in the low femtomole range (1.5-5.6 fmol on column). The PA-derivatization was successfully applied to a biological sample analysis; the derivatization followed by LC-ESI-MS/MS enabled the detection of trace amounts of bile acids, gamma-CEHC and HVA in human saliva with a simple pretreatment, small sample volume and short analysis time. PMID:20376914

Higashi, Tatsuya; Ichikawa, Takuya; Inagaki, Shinsuke; Min, Jun Zhe; Fukushima, Takeshi; Toyo'oka, Toshimasa

2010-09-01

352

Extraction of benzene and naphthalene carboxylic acids using quaternary ammonium salts as a model study for the separation of coal oxidation products  

SciTech Connect

The ion-pair solvent extraction of benzene- and naphthalene-carboxylic acids has been investigated as a model study for the separation of coal oxidation products, which are formed by treatment with alkaline solutions at high temperatures. It was possible that benzene- and naphthalene-dicarboxylic acids are extracted into several types of organic solvents with quaternary ammonium ions. The extraction equilibrium constants (K{sub ex}) for benzoic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 1-naphthoic acid, 2-naphthoic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid into chloroform were determined at 20{sup o}C. The difference of K{sub ex} among the aromatic acids was sufficiently large for designing a separation method for these aromatic acids. It was unexpected that the extraction of dicarboxylic acids was slower than that of monocarboxylic acids, although the ion-pair formation of aromatic carboxylate ion with quaternary ammonium ion is normally considered as a diffusion control reaction in aqueous phase. Thus, this fact suggests that the phase transfer of the ion-pair from aqueous to organic phase is the rate-determining step. Liner-free-energy relationship was observed for the monocarboxylic acids using different quaternary ammonium salts while that was ambiguous for the dicarboxylic acids. This is due to the steric influence of the counter ions for the magnitude of K{sub ex}.

Kawamura, K.; Nagano, H.; Okuwaki, A. [Tohoku University, Miyagi (Japan). Graduate School of Environmental Studies

2005-07-01

353

Separation and characterization of carboxyl-linked glucuronides of bile acids in incubation mixture of rat liver microsomes.  

PubMed

The carboxyl-linked 24-glucuronides of common bile acids have been identified by means of liquid chromatography (LC)/atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) in an incubation mixture with a male Wistar rat liver microsomal fraction. The authentic specimens of bile acid 24-glucuronide acetate-methyl esters were synthesized unequivocally using the Mitsunobu reaction, and the APCI-mass spectrometric properties of these glucuronide derivatives were also characterized. After incubation of common unconjugated bile acids with hepatic microsomes, glucuronides were extracted and purified with a Sep-Pak C18 cartridge and lipophilic ion exchange gel, piperidino-hydroxypropyl Sephadex LH-20, and then derivatized into the acetate-methyl esters. Subsequent resolution into alpha- and beta-isomers at the glucuronosyl linkage was attained by LC on Cosmosil 5C8 and Sumichiral OA-2500 columns using 200 mM ammonium acetate (pH 7.0)-methanol (1:4, v/v), where 24-glucuronides were monitored with characteristic positive ions [M + NH4]+. The 24-glucuronides of lithocholic, chenodeoxycholic, deoxycholic, ursodeoxycholic and cholic acid were definitely characterized, in contrast to no formation of corresponding 3-glucuronides. PMID:9589552

Goto, J; Murao, N; Nakada, C; Motoyama, T; Oohashi, J; Yanagihara, T; Niwa, T; Ikegawa, S

1998-04-01

354

Anaerobic fermentation of rice straw and chicken manure to carboxylic acids  

E-print Network

). The highest acid productivity of 1.69 g/(L�·d) was at a total acid concentration of 32.4 g/L. The highest conversion and yield were 0.692 g VS digested/g VS fed and 0.29 g total acids/g VS fed, respectively. The continuum particle distribution model (CPDM...

Agbogbo, Frank Kwesi

2007-04-25

355

ANALYSIS OF PERFLUORINATED CARBOXYLIC ACIDS IN SOILS: DETECTION AND QUANTITATION ISSUES AT LOW CONCENTRATIONS  

EPA Science Inventory

Methods were developed for the extraction from soil, identification, confirmation and quantitation by LC/MS/MS of trace levels of perfluorinated octanoic acid (PFOA), perfluorinated nonanoic acid (PFNA) and perfluorinated decanoic acid (PFDA). Whereas PFOA, PFNA and PFDA all can...

356

Experimental and calculated 1H, 13C and 31P NMR spectra of pyridine-2-phosphono-4-carboxylic acid  

NASA Astrophysics Data System (ADS)

Pyridine-2-phosphono-4-carboxylic acid (MC1) is a compound that possesses potential neuroactivity. In this work the 1H, 13C and 31P NMR spectra of MC1 dissolved in D 2O in solution, in the 1.5-9.0 pD range, are presented. Theoretical calculations of the NMR spectra, as well as structural parameters of expected compounds, were performed at the B3PW91/6-311G** and B3PW91/6-31G** level, respectively, for all five possible forms of MC1 (cation, zwitteranion and three anions). Consecutive deprotonation of MC1 and its influence on the structure of the ligand are discussed in detail.

Chruszcz, Katarzyna; Bara?ska, Ma?gorzata; Czarniecki, Krzysztof; Boduszek, Bogdan; Proniewicz, Leonard M.

2003-03-01

357

Biosynthesis of 8-hydroxyquinoline-2-carboxylic acid, an iron chelator from the gut of the lepidopteran Spodoptera littoralis.  

PubMed

In the regurgitate (foregut content) of Spodoptera larvae we found high concentrations (0.5-5 mM) of 8-hydroxyquinoline-2-carboxylic acid (8-HQA). In a survey of different lepidopteran species, this compound was only detected in species belonging to the family of Noctuidae. 8-HQA was shown to derive from tryptophan metabolism. The amount of 8-HQA in the regurgitate was strongly dependent on the tryptophan content of the diet. In the insect 8-HQA is generated from tryptophan via kynurenine and 3-hydroxykynurenine. 8-HQA is produced by the larvae and not by their commensal gut bacteria. Analysis of different life stages of Spodoptera larvae revealed that 8-HQA is formed during the larval stage, probably acting as an iron chelator to control the gut microbiome. PMID:25356857

Pesek, Jelena; Svoboda, Ji?í; Sattler, Martina; Bartram, Stefan; Boland, Wilhelm

2015-01-01

358

A pH-dependent SERS study of thiophene-2-carboxylic acid adsorbed on Ag-sols  

NASA Astrophysics Data System (ADS)

SERS is observed for thiophene-2-carboxylic acid (TCA) adsorbed on Ag-sols. The enhancement is maximum when TCA concentration, in Ag-sol, is 5 × 10 -3 M. The SER spectra of TCA are different at different pH values, which suggest that the adsorption geometry is pH dependent. This is further supported by the absorption spectra at different pH values. It is inferred that the chemisorption takes place through both the S-atom and COOH group for pH ? 7 and through the ?-electronic system for pH=10.5. Quick desulphurization at pH=2 and stable perpendicular and parallel surface bonding for pH=7 and 10.5, respectively, is revealed.

Sarkar, Uttam K.

2003-06-01

359

Design, synthesis, and fungicidal activity of novel carboxylic acid amides represented by N-benzhydryl valinamode carbamates.  

PubMed

Carboxylic acid amide (CAA) fungicides are an important class of agricultural fungicide with oomycete activity and low toxicity toward mammalian cells. To find CAA analogues with high activity against resistant pathogens, a series of substituted N-benzhydryl valinamide carbamate derivatives were designed and synthesized by introducing substituted aromatic rings into valinamide carbamate leads. Bioassays showed that some title compounds exhibited very good in vitro fungicidal activity against Phytophthora capsici and in vivo fungicidal activities against Pseudoperonospora cubensis. Topomer CoMFA was performed to explore the structure-activity relationship on the basis of the in vitro data. The dimethoxy substituted aromatic analogue 9e was found to display higher in vitro fungicidal activity against Phytophthora capsici than iprovalicarb but lower activity than mandipropamid, and higher in vivo fungicidal activity against Pseudoperonospora cubensis than dimethomorph at a dosage of 6.25 ?g mL(-1). PMID:24935054

Du, Xiu-Jiang; Bian, Qiang; Wang, Hong-Xue; Yu, Shu-Jing; Kou, Jun-Jie; Wang, Zhi-Peng; Li, Zheng-Ming; Zhao, Wei-Guang

2014-08-01

360

Carboxylate-assisted formation of alkylcarbonate species from CO(2) and tetramethylammonium salts with a ?-amino acid anion.  

PubMed

Tetramethylammonium-based molten salts bearing a ?-amino acid anion (TMAAs) are synthesized through Michael addition reactions of amines with methyl acrylate followed by hydrolysis and subsequent neutralization by using aqueous tetramethylammonium hydroxide. The CO(2) capture performances of the TMAAs are evaluated and are shown to interact with CO(2) in a 1:1 mode in both water and alcohol. FTIR and (13)C NMR spectroscopic studies on the interactions of TMAAs with CO(2) indicate that the type of CO(2) adduct varies with the solvent used. When water is used as the solvent, a bicarbonate species is produced, whereas hydroxyethylcarbonate and methylcarbonate species are generated in ethylene glycol and methanol, respectively. Computational calculations show that the carboxylate groups of TMAAs contribute towards the formation and stabilization of 1:1 CO(2) adducts through hydrogen bonding interactions with the hydrogen atoms of the amino groups. PMID:23576306

Hong, Sung Yun; Cheon, Youngeun; Shin, Seung Hoon; Lee, Hyunjoo; Cheong, Minserk; Kim, Hoon Sik

2013-05-01

361

A new extraction technique for in situ analyses of amino and carboxylic acids on Mars by gas chromatography mass spectrometry  

NASA Astrophysics Data System (ADS)

In order to target key organic compounds in the Martian regolith using gas chromatography mass spectrometry (GC-MS), we have developed a new extraction procedure coupled with chemical derivatization. This new technique was tested on a Mars analog soil sample collected from the Atacama Desert in Chile. We found that amino and carboxylic acids can be extracted from the Atacama soil in a 1:1 mixture of isopropanol and water after ultrasonic treatment for 30 min. The extracted organic compounds were then derivatized in a single-step reaction using N-methyl- N-( tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) as the silylating agent in order to transform these compounds into volatile species that can then be detected by GC-MS. We are currently developing a miniaturized reaction cell suited for spaceflight, where both organic extraction and chemical derivatization processes can take place in a single step.

Buch, A.; Glavin, D. P.; Sternberg, R.; Szopa, C.; Rodier, C.; Navarro-González, R.; Raulin, F.; Cabane, M.; Mahaffy, P. R.

2006-12-01

362

Preparation and characterization of carboxyl functionalization of chitosan derivative magnetic nanoparticles  

Microsoft Academic Search

The functionalized magnetic Fe3O4-chitosan derivative nanoparticles have been prepared by the covalent binding of alpha-ketoglutaric acid chitosan (KCTS) onto the surface of Fe3O4 magnetic nanoparticles via carbodiimide activation. Transmission electron microscopy (TEM) showed that the KCTS-bound Fe3O4 nanoparticles were regular spheres with a mean diameter of 26nm. X-ray diffraction (XRD) patterns indicated that the Fe3O4 nanoparticles were pure Fe3O4 with

Gui-yin Li; Ke-long Huang; Yu-ren Jiang; Ping Ding; Dong-liang Yang

2008-01-01

363

Synthesis of 1-(Substituted Phenylcarbonyl/sulfonylamino)-1,2,3,6-tetrahydropyridine-5-carboxylic acid diethylamides as Potential Anti-inflammatory Agents  

PubMed Central

Fifteen novel 1-(substituted phenylcarbonyl/sulfonylamino)-1,2,3,6-tetrahydro- pyridine-5-carboxylic acid diethylamide (7, 15) were synthesized in fair to good yields via sodium borohydride reduction of the corresponding 1-(substituted phenylcarbonyl/ sulfonylimino)-3-diethylcarbamoyl pyridinium ylides (6, 14) in absolute ethanol. PMID:20721309

Gangapuram, Madhavi

2010-01-01

364

Discovery of thiophene-2-carboxylic acids as potent inhibitors of HCV NS5B polymerase and HCV subgenomic RNA replication. Part 1: Sulfonamides.  

PubMed

The discovery of a novel class of HCV NS5B polymerase inhibitors, 3-arylsulfonylamino-5-phenyl-thiophene-2-carboxylic acids is described. SAR studies have yielded several potent inhibitors of HCV polymerase as well as of HCV subgenomic RNA replication in Huh-7 cells. PMID:14741291

Chan, Laval; Das, Sanjoy K; Reddy, T Jagadeeswar; Poisson, Carl; Proulx, Mélanie; Pereira, Oswy; Courchesne, Marc; Roy, Caroline; Wang, Wuyi; Siddiqui, Arshad; Yannopoulos, Constantin G; Nguyen-Ba, Nghe; Labrecque, Denis; Bethell, Richard; Hamel, Martine; Courtemanche-Asselin, Philippe; L'Heureux, Lucille; David, Maud; Nicolas, Olivier; Brunette, Stéphanie; Bilimoria, Darius; Bédard, Jean

2004-02-01

365

Immunopurification and characterization of a 40-kD 1-aminocyclopropane- 1-carboxylic acid N-malonyltransferase from mung bean seedling hypocotyls  

Microsoft Academic Search

1 -Aminocyclopropane-1 -carboxylic acid (ACC) Kmalonyltrans- ferase catalyzes the transfer of the malonyl group from malonyl coenzyme A to ACC to form malonyl ACC. Using partially purified ACC Kmalonyltransferase from the hypocotyls of mung bean (Vigna radiafa) seedlings, we produced two mouse monoclonal antibodies (1 H5 and 2C3) to this enzyme. These antibodies bind to sites other than the active

Wallace S. H. Chick; Chow Leung

1997-01-01

366

THERMAL DESORPTION MASS SPECTROMETRIC ANALYSIS OF ORGANIC AEROSOL FORMED FROM REACTIONS OF 1-TETRADECENE AND O3 IN THE PRESENCE OF ALCOHOLS AND CARBOXYLIC ACIDS. (R826235)  

EPA Science Inventory

The chemistry of secondary organic aerosol formation from reactions of 1-tetradecene and O3 in dry air in the presence of excess alcohols and carboxylic acids was investigated in an environmental chamber using a thermal desorption particle beam mass spec...

367

HIGH-PERFORMANCE LIQUID CHROMATOGRAPHIC/MASS SPECTROMETRIC DETERMINATION OF VOLATILE CARBOXYLIC ACIDS USING ION-PAIR EXTRACTION AND THERMALLY INDUCED ALKYLATION  

EPA Science Inventory

Low molecular weight volatile carboxylic acids have been analyzed by high-performance liquid chromatography/mass spectrometry (HPLC/MS) using post-column derivatization and a moving belt interface. In order to prevent loss of the volatile solutes during transport to the mass spec...

368

Delignification of wheat straw using a mixture of carboxylic acids and peroxoacids  

Microsoft Academic Search

Wheat straw was pulping by an Organosolv process using a mixture of acetic acid\\/formic acid\\/water (AA\\/FA\\/water). In order to make easier the bleaching step, it was possible to improve the delignification in an efficient and selective manner by using peroxoacids in acidic organic medium. First a solution of peroxoacids was synthesized by adding hydrogen peroxide in a mixture of acetic

Long Kham; Yves Le Bigot; Michel Delmas; Gérard Avignon

2005-01-01

369

Amperometric uric acid biosensor based on poly(vinylferrocene)-gelatin-carboxylated multiwalled carbon nanotube modified glassy carbon electrode.  

PubMed

In this study, a new uric acid biosensor was constructed based on ferrocene containing polymer poly(vinylferrocene) (PVF), carboxylated multiwalled carbon nanotubes (c-MWCNT) and gelatin (GEL) modified glassy carbon electrode (GCE). Uricase enzyme (UOx) was immobilized covalently through N-ethyl-N'-(3-dimethyaminopropyl) carbodiimide (EDC) and N-hydroxyl succinimide (NHS) chemistry onto c-MWCNT/GEL/PVF/GCE. The c-MWCNT/GEL/PVF composite was characterized by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Various experimental parameters such as pH, applied potential, enzyme loading, PVF and c-MWCNT concentration were investigated in detail. Under the optimal conditions the dynamic linear range of uric acid was 2.0×10(-7)M-7.1×10(-4)M (R=0.9993) with the detection limit low to 2.3×10(-8)M. With good selectivity and sensitivity, the biosensor was successfully applied to determine the uric acid in human serum. The results of the biosensor were in good agreement with those obtained from standard method. Therefore, the presented biosensor could be a good promise for practical applications in real samples. PMID:25618698

Erden, P?nar Esra; Kaçar, Ceren; Öztürk, Funda; K?l?ç, Esma

2015-03-01

370

Determination of short chain carboxylic acids in vegetable oils and fats using ion exclusion chromatography electrospray ionization mass spectrometry.  

PubMed

A new method for quantification of short chain C1-C6 carboxylic acids in vegetable oils and fats by employing Liquid Chromatography Mass Spectrometry (LC-MS) has been developed. The method requires minor sample preparation and applies non-conventional Electrospray Ionization (ESI) liquid phase chemistry. Samples are first dissolved in chloroform and then extracted using water that has been spiked with stable isotope labeled internal standards that are used for signal normalization and absolute quantification of selected acids. The analytes are separated using Ion Exclusion Chromatography (IEC) and detected with Electrospray Ionization Mass Spectrometry (ESI-MS) as deprotonated molecules. Prior to ionization the eluent that contains hydrochloric acid is modified post-column to ensure good ionization efficiency of the analytes. The averaged within run precision and between run precision were generally lower than 8%. The accuracy was between 85 and 115% for most of the analytes. The Lower Limit of Quantification (LLOQ) ranged from 0.006 to 7mg/kg. It is shown that this method offers good selectivity in cases where UV detection fails to produce reliable results. PMID:25627971

Viidanoja, Jyrki

2015-02-27

371

Degradation of 1-deoxy-D-erythro-hexo-2,3-diulose in the presence of lysine leads to formation of carboxylic acid amides.  

PubMed

A novel species of amides formed from degradation of one of the most important key intermediates in Maillard hexose chemistry-1-deoxyhexo-2,3-diulose-was investigated. In 1-deoxyhexo-2,3-diulose/N(alpha)-t-BOC-lysine reaction mixtures four amides, N(epsilon)-acetyl lysine, N(epsilon)-formyl lysine, N(epsilon)-lactoyl lysine and N(epsilon)-glycerinyl lysine, were identified and their structures verified by authentic reference standards. Amides and corresponding carboxylic acids (acetic acid, formic acid, lactic acid and glyceric acid) accumulated over time. Both N(epsilon)-lysine amides and carboxylic acids were thus determined as stable Maillard end products. Results of model incubations suggested the synthesis of amides to be mechanistically closely related to the formation of their corresponding carboxylic acids by beta-dicarbonyl cleavage. Due to the different chemical properties of all the compounds monitored, various analytical strategies had to be carried out (LC-MS(2), GC-MS, GC-FID, enzymatic determination). PMID:20429584

Smuda, Mareen; Voigt, Michael; Glomb, Marcus A

2010-05-26

372

Long-chain carboxylic acids in pyrolysates of Green River kerogen  

NASA Technical Reports Server (NTRS)

Long-chain fatty acids (C10-C32), as well as C14-C21 isoprenoid acids (except for C18), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200-400 degrees C, 2-1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C16 followed by lesser amounts of C18 and C22 acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C14, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C18 and C30. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300 degrees C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.

Kawamura, K.; Tannenbaum, E.; Huizinga, B. J.; Kaplan, I. R.

1986-01-01

373

Approaches to ?-amino acids via rearrangement to electron-deficient nitrogen: Beckmann and Hofmann rearrangements of appropriate carboxyl-protected substrates  

PubMed Central

Summary The titled approaches were effected with various 2-substituted benzoylacetic acid oximes 3 (Beckmann) and 2-substituted malonamic acids 9 (Hofmann), their carboxyl groups being masked as a 2,4,10-trioxaadamantane unit (an orthoacetate). The oxime mesylates have been rearranged with basic Al2O3 in refluxing CHCl3, and the malonamic acids with phenyliodoso acetate and KOH/MeOH. Both routes are characterized by excellent overall yields. Structure confirmation of final products was conducted with X-ray diffraction in selected cases. The final N-benzoyl and N-(methoxycarbonyl) products are ?-amino acids with both carboxyl and amino protection; hence, they are of great interest in peptide synthesis. PMID:23019476

Rao, V Mohana

2012-01-01

374

Linear and cyclic aliphatic carboxamides of the Murchison meteorite: Hydrolyzable derivatives of amino acids and other carboxylic acids  

NASA Astrophysics Data System (ADS)

Analyses of fractionated aqueous extracts of the Murchison meteorite by gas chromatographymass spectrometry after silylation with N-methyl-N ( tert-butyldimethylsilyl) trifluoroacetamide have revealed an extensive series of linear and cyclic aliphatic amides. These include monocarboxylic acid amides, dicarboxylic acid monoamides, hydroxy acid amides, lactams, carboxy lactams, lactims, N-acetyl amino acids, and substituted hydantoins. Numerous isomers and homologues through at least C 8 were observed in all cases, except for the N-acetyl amino acids and hydantoins. Carboxy lactams, lactams, hydantoins, and N-acetyl amino acids are converted to amino acids by acid hydrolysis, thus, these compounds qualitatively account for the earlier observation of acid-labile amino acid precursors in meteoritic extracts. Laboratory studies of the spontaneous decomposition of N-carbamyl-?-amino acids and their dehydration products, the 5-substituted hydantoins, have led to the recognition of a series of aqueous phase reactions by which amino acids and cyanic acid/cyanate ion in the primitive parent body might have given rise to several of the observed classes of amides, as well as to monocarboxylic acids, dicarboxylic acids, and hydroxy acids. A previously undescribed reaction of 5-substituted hydantoins with cyanic acid/cyanate ion to give carboxamides of the 5-substituent groups was observed in the course of these studies. The presence of an extensive suite of amides in a CM chondrite appears to be consistent with the interstellar-parent body formation hypothesis for the organic compounds of these meteorites. The presence of carboxy lactams and lactams along with free amino acids suggests the possibility of further chemical evolution of meteorite amino acids by thermal polymerization. The cyclic amides, given their potential for hydrogen-bonded pair formation, might be considered candidate bases for a primitive sequence coding system.

Cooper, G. W.; Cronin, J. R.

1995-03-01

375

Rapid degradation of Pseudomonas fluorescens 1-aminocyclopropane-1-carboxylic acid deaminase proteins expressed in transgenic Arabidopsis.  

PubMed

1-Aminocyclopropane-1-carboxylate (ACC) deaminase is commonly produced by plant growth-promoting rhizobacteria (PGPR) and has been suggested to facilitate the growth and stress tolerance of hosts via a reduction in levels of ethylene. However, the regulatory mechanism of ACC deaminase (AcdS) protein within host plant cells is largely unknown. Here, we demonstrated beneficial effects and post-translational modification of PGPR-originated AcdS proteins in plants. Compared with the wild-type, transgenic Arabidopsis expressing the Pseudomonas fluorescens acdS (PfacdS) gene displayed increased root elongation and reduced sensitivity to 10 ?M exogenous ACC, an ethylene precursor. Arabidopsis expressing PfacdS also showed increased tolerance to high salinity (150 mM NaCl). PfAcdS proteins accumulated in transgenic Arabidopsis were rapidly degraded, which was potentially mediated by the 26S proteasome pathway. The degradation of PfAcdS was alleviated in the presence of exogenous ACC. In conclusion, our data suggest that the plant growth-promoting effects of bacterial AcdS proteins are potentially modulated via protein turnover inside the host plant cells. Such post-translational modification plays a physiological role in the mutualistic interactions between microorganisms and plants in the rhizospheric and/or endospheric niche. PMID:24801274

Kim, Kangmin; Park, Sung-Hee; Chae, Jong-Chan; Soh, Byoung Yul; Lee, Kui-Jae

2014-06-01

376

Synthesis and fluorescence properties of Eu-anthracene-9-carboxylic acid towards N-acetyl amino acids and nucleotides in different solvents.  

PubMed

Europium (III) complex with anthracene-9-carboxylic acid (9-AA) has been synthesized and characterized by elemental analysis, FT-IR, and TG-DTG techniques. The results indicated that the composition of this complex is Eu (9-AA)(3). The luminescence properties of the complex in different solvents and at different pH values have been investigated. The results show that the complex exhibits more efficient luminescence in THF and ethyl acetate. The interactions of Eu-complex with different N-acetyl amino acids and nucleotides in different solvents have been investigated by fluorescence measurements. Enhancement of the fluorescence intensities has been observed in cyclohexane, acetone, acetonitrile, and tetrahydrofuran whereas the fluorescence intensities of the investigated complex in ethanol, water, and ethyl acetate exhibit relatively low intensity. PMID:19926521

Azab, H A; El-Korashy, S A; Anwar, Z M; Hussein, B H M; Khairy, G M

2010-01-01

377

Synthesis and fluorescence properties of Eu-anthracene-9-carboxylic acid towards N-acetyl amino acids and nucleotides in different solvents  

NASA Astrophysics Data System (ADS)

Europium (III) complex with anthracene-9-carboxylic acid (9-AA) has been synthesized and characterized by elemental analysis, FT-IR, and TG-DTG techniques. The results indicated that the composition of this complex is Eu (9-AA) 3. The luminescence properties of the complex in different solvents and at different pH values have been investigated. The results show that the complex exhibits more efficient luminescence in THF and ethyl acetate. The interactions of Eu-complex with different N-acetyl amino acids and nucleotides in different solvents have been investigated by fluorescence measurements. Enhancement of the fluorescence intensities has been observed in cyclohexane, acetone, acetonitrile, and tetrahydrofuran whereas the fluorescence intensities of the investigated complex in ethanol, water, and ethyl acetate exhibit relatively low intensity.

Azab, H. A.; El-Korashy, S. A.; Anwar, Z. M.; Hussein, B. H. M.; Khairy, G. M.

2010-01-01

378

Oxidation of alpha-ketoglutarate is required for reductive carboxylation in cancer cells with mitochondrial defects  

PubMed Central

Summary 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 ?-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. PMID:24857658

Mullen, Andrew R.; Hu, Zeping; Shi, Xiaolei; Jiang, Lei; Boroughs, Lindsey K.; Kovacs, Zoltan; Boriack, Richard; Rakheja, Dinesh; Sullivan, Lucas B.; Linehan, W. Marston; Chandel, Navdeep S.; DeBerardinis, Ralph J.

2014-01-01

379

Promotion of tomato ( Lycopersicon esculentum Mill.) plant growth by rhizosphere competent 1-aminocyclopropane-1-carboxylic acid deaminase-producing streptomycete actinomycetes  

Microsoft Academic Search

The ability of streptomycete actinomycetes to promote growth of tomato through the production of 1-aminocyclopropane-1-carboxylic\\u000a acid (ACC) deaminase was evaluated under gnotobiotic and greenhouse conditions. To achieve this, 64 isolates of Streptomyces spp. obtained from a tomato rhizosphere in the United Arab Emirates were initially selected for their ability to produce\\u000a ACC deaminase as well as indole-3-acetic acid (IAA) and

Khaled A. El-Tarabily

2008-01-01

380

Hydrogel with chains functionalized with carboxyl groups as universal 3D platform in DNA biosensors.  

PubMed

Application of hydrogel based on N-isopropylacrylamide with carboxyl groups grafted to the chains enabled the immobilization of DNA at an extent exceeding that for flat surfaces by at least one order of magnitude. The probe DNA strands in the 3D platform were fully available for the hybridization process. The examination of the gels containing different amounts of grafted carboxyl groups (1-10%) was done using quartz crystal microbalance, electrochemical impedance spectroscopy, chronoamperometry and ionic coupled plasma with laser ablation. The optimal carboxyl group content was determined to be 5%. A very good agreement of the data obtained with independent techniques on content of DNA in the gel was obtained. In comparison to the other methods of immobilization of DNA the new platform enabled complete removal of DNA after the measurements and analysis and, therefore, could be used many times. After a 10-fold exchange of the DNA-sensing layer the efficiency of hybridization and analytical signal did not change by more than 5%. The sensor response increased linearly with logarithm of concentration of target DNA in the range 1×10(-13)-1×10(-6) M. The obtained detection limit was circa 8×10(-13) M of target DNA in the sample which is a substantial improvement over the planar sensing layers. PMID:24287408

Kowalczyk, Agata; Fau, Michal; Karbarz, Marcin; Donten, Mikolaj; Stojek, Zbigniew; Nowicka, Anna M

2014-04-15

381

Preparation and Properties of Enterosorbents Based on Carboxylated Microcrystalline Cellulose  

Microsoft Academic Search

Features of a non-traditional method of preparation of cellulose-based cation-exchange enterosorbents using nitrogen (IV) oxide are discussed. The proposed approach involves sequential use of oxidative and acid-hydrolyzing functions of nitrogen (IV) oxide to convert ordinary cellulose into carboxylated microcrystalline cellulose. X-ray phase analysis and transmission electron microscopy data show evidence of a topochemical character of cellulose microcrystal modification with carboxyl

E. V. Gert; V. I. Torgashov; O. V. Zubets; F. N. Kaputskii

2005-01-01

382

Permeability and toxicity characteristics of L-cysteine and 2-methyl-thiazolidine-4-carboxylic acid in Caco-2 cells.  

PubMed

Acetaldehyde is a known mutagenic substance and has been classified as a group-one carcinogen by the WHO. It is possible to bind acetaldehyde locally in the gastrointestinal (GI) tract with the semi-essential amino acid l-cysteine, which reacts covalently with acetaldehyde and forms compound 2-methyl-thiozolidine-4-carboxylic acid (MTCA). The Caco-2 cell line was used to determine the permeation of l-cysteine and MTCA, as well as the possible cell toxicity of both substances. Neither of the substances permeated through the Caco-2 cells at the concentrations used in this study, and only the highest concentration of MTCA affected the viability of the cells in the MTT (3-[4,5-dimethylthiazol-2yl]-2,5-diphenyltetrazolium bromide) test. These results showed that when l-cysteine is administered in formulations releasing it locally in the lower parts of GI tract, it is not absorbed but can react with acetaldehyde, and that neither l-cysteine nor MTCA is harmful to the cells when present locally in the upper parts of GI tract. This study also shows that MTCA is sensitive at a lower pH of 5.5. Since stable MTCA is desired in different parts of the GI tract, this observation raises concern over the influence of lower pH on l-cysteine-containing product ability to bind and eliminate carcinogenic acetaldehyde. PMID:22356486

Kartal-Hodzic, Alma; Marvola, Tuuli; Schmitt, Mechthild; Harju, Kirsi; Peltoniemi, Marikki; Sivén, Mia

2013-01-01

383

Estimation of the acid dissociation constant of perfluoroalkyl carboxylic acids through an experimental investigation of their water-to-air transport.  

PubMed

The acid dissociation constants (pKas) of perfluoroalkyl carboxylic acids (PFCAs) have been the subject of discussion in the literature; for example, values from -0.2 to 3.8 have been suggested for perfluorooctanoic acid (PFOA). The dissociated anionic conjugate bases of PFCAs have negligible air-water partition coefficients (KAWs) and do not volatilize from water. The neutral acids, however, have relatively high KAWs and volatilization from water has been demonstrated. The extent of volatilization of PFCAs in the environment will depend on the water pH and their pKa. Knowledge of the pKas of PFCAs is therefore vital for understanding their environmental transport and fate. We investigated the water-to-air transfer of PFCAs in a novel experimental setup. We used ?1 ?g L(-1) of PFCAs in water (above environmental background concentrations but below the concentration at which self-association occurs) at different water pH (pH 0.3 to pH 6.9) and sampled the PFCAs volatilized from water during a 2-day experiment. Our results suggest that the pKas of C4-11 PFCAs are <1.6. For PFOA, we derived a pKa of 0.5 from fitting the experimental measurements with a volatilization model. Perfluoroalkane sulfonic acids were not volatilized, suggesting that their pKas are below the investigated pH range (pKa <0.3). PMID:23952814

Vierke, Lena; Berger, Urs; Cousins, Ian T

2013-10-01

384

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS  

NASA Astrophysics Data System (ADS)

The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, "dead-end" U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).

Boyanov, Maxim I.; O'Loughlin, Edward J.; Roden, Eric E.; Fein, Jeremy B.; Kemner, Kenneth M.

2007-04-01

385

Pilot-scale fermentation of office paper and chicken manure to carboxylic acids  

E-print Network

paper and 20 wt% chicken manure. Calcium carbonate was used as a neutralizing agent and iodoform served as a methane inhibitor. The fermentor temperature was 40 oC and the pH was 6.0. The highest total acid concentration obtained was 32.4 g/L, operating...

Moody, Andrew Garret

2006-08-16

386

5-Benzoylamino-3-bromo-4-(4-methoxyphenyl)-4,5-dihydroisoxazole-5-carboxylic acid.  

PubMed

The title compound, C18H15BrN2O5, a promising N-protected alpha-amino acid, was synthesized directly from an unusual bromo dipole and a 4-(arylmethylene)oxazolone. The crystal packing of the title compound is a racemic mixture. Peculiar graph-set motifs driven by the most important hydrogen bonds are described. PMID:15237175

Bruno, Giuseppe; Rotondo, Archimede; Grassi, Giovanni; Foti, Francesco; Risitano, Francesco; Nicoló, Francesco

2004-07-01

387

Molecular structure, vibrational spectra, natural bond orbital and thermodynamic analysis of 3,6-dichloro-4-methylpyridazine and 3,6-dichloropyridazine-4-carboxylic acid by dft approach  

NASA Astrophysics Data System (ADS)

Vibrational spectral analysis of the molecules 3,6-dichloro-4-methylpyridazine (DMP) and 3,6-dichloropyridazine-4-carboxylic acid (DPC) was carried out using FT-IR and FT-Raman spectroscopic techniques. The molecular structure and vibrational spectra of DMP and DPC were obtained by the density functional theory (DFT) method, using B3LYP functional, with 6-311++G(d,p) basis set. A detailed interpretation of the Infrared and Raman spectra of the two molecules were reported based on potential energy distribution (PED). The theoretically predicted FTIR and FT-Raman spectra of the titled molecules have been simulated and were compared with the experimental spectra. Determination of electric dipole moment (?) and hyperpolarizability ?0 helps to study the non-linear optical (NLO) behavior of DMP and DPC. Stability of the molecules arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. 13C and 1H NMR spectra were recorded and 13C and 1H NMR chemical shifts of the molecules were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compounds was also recorded in the region 200-1100 nm and electronic properties, HOMO (Highest Occupied Molecular Orbitals) and LUMO (Lowest Unoccupied Molecular Orbitals) energies were measured by time-dependent TD-DFT approach. Charge density distribution and site of chemical reactivity of the molecule have been studied by mapping electron density isosurface with molecular electrostatic potential (MESP).

Prabavathi, N.; Senthil Nayaki, N.; Venkatram Reddy, B.

2015-02-01

388

Molecular structure, vibrational spectra, natural bond orbital and thermodynamic analysis of 3,6-dichloro-4-methylpyridazine and 3,6-dichloropyridazine-4-carboxylic acid by dft approach.  

PubMed

Vibrational spectral analysis of the molecules 3,6-dichloro-4-methylpyridazine (DMP) and 3,6-dichloropyridazine-4-carboxylic acid (DPC) was carried out using FT-IR and FT-Raman spectroscopic techniques. The molecular structure and vibrational spectra of DMP and DPC were obtained by the density functional theory (DFT) method, using B3LYP functional, with 6-311++G(d,p) basis set. A detailed interpretation of the Infrared and Raman spectra of the two molecules were reported based on potential energy distribution (PED). The theoretically predicted FTIR and FT-Raman spectra of the titled molecules have been simulated and were compared with the experimental spectra. Determination of electric dipole moment (?) and hyperpolarizability ?0 helps to study the non-linear optical (NLO) behavior of DMP and DPC. Stability of the molecules arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. (13)C and (1)H NMR spectra were recorded and (13)C and (1)H NMR chemical shifts of the molecules were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compounds was also recorded in the region 200-1100nm and electronic properties, HOMO (Highest Occupied Molecular Orbitals) and LUMO (Lowest Unoccupied Molecular Orbitals) energies were measured by time-dependent TD-DFT approach. Charge density distribution and site of chemical reactivity of the molecule have been studied by mapping electron density isosurface with molecular electrostatic potential (MESP). PMID:25459510

Prabavathi, N; Senthil Nayaki, N; Venkatram Reddy, B

2015-02-01

389

Cell Wall Integrity Controls Root Elongation via a General 1-Aminocyclopropane-1-Carboxylic Acid-Dependent, Ethylene-Independent Pathway1[W  

PubMed Central

Cell expansion in plants requires cell wall biosynthesis and rearrangement. During periods of rapid elongation, such as during the growth of etiolated hypocotyls and primary root tips, cells respond dramatically to perturbation of either of these processes. There is growing evidence that this response is initiated by a cell wall integrity-sensing mechanism and dedicated signaling pathway rather than being an inevitable consequence of lost structural integrity. However, the existence of such a pathway in root tissue and its function in a broader developmental context have remained largely unknown. Here, we show that various types of cell wall stress rapidly reduce primary root elongation in Arabidopsis (Arabidopsis thaliana). This response depended on the biosynthesis of 1-aminocyclopropane-1-carboxylic acid (ACC). In agreement with the established ethylene signaling pathway in roots, auxin signaling and superoxide production are required downstream of ACC to reduce elongation. However, this cell wall stress response unexpectedly does not depend on the perception of ethylene. We show that the short-term effect of ACC on roots is partially independent of its conversion to ethylene or ethylene signaling and that this ACC-dependent pathway is also responsible for the rapid reduction of root elongation in response to pathogen-associated molecular patterns. This acute response to internal and external stress thus represents a novel, noncanonical signaling function of ACC. PMID:21508182

Tsang, Dat L.; Edmond, Clare; Harrington, Jennifer L.; Nühse, Thomas S.

2011-01-01

390

Streptomyces kebangsaanensis sp. nov., an endophytic actinomycete isolated from an ethnomedicinal plant, which produces phenazine-1-carboxylic acid.  

PubMed

A spore-forming streptomycete designated strain SUK12(T) was isolated from a Malaysian ethnomedicinal plant. Its taxonomic position, established using a polyphasic approach, indicates that it is a novel species of the genus Streptomyces. Morphological and chemical characteristics of the strain were consistent with those of members of the genus Streptomyces. Analysis of the almost complete 16S rRNA gene sequence placed strain SUK12(T) in the genus Streptomyces where it formed a distinct phyletic line with recognized species of this genus. The strain exhibited highest sequence similarity to Streptomyces corchorusii DSM 40340(T) (98.2?%) followed by Streptomyces chrestomyceticus NRRL B-3310(T) (98.1?%). The G+C content of the genomic DNA was 74 mol%. Chemotaxonomic data [MK-9(H8) as the major menaquinone; LL-diaminopimelic acid as a component of cell-wall peptidoglycan; C12?:?0, C14?:?0, C15?:?0 and C17?:?1 as the major fatty acids; phospholipid type II] supported the affiliation of strain SUK12(T) to the genus Streptomyces. The results of the phylogenetic analysis and phenotypic data derived from this and previous studies allowed the genotypic and phenotypic differentiation of strain SUK12(T) from the related species of the genus Streptomyces. The DNA-DNA relatedness value between strain SUK12(T) and S. corchorusii DSM 40340(T) is 18.85±4.55?%. Strain SUK12(T) produces phenazine-1-carboxylic acid, known as tubermycin B, an antibacterial agent. It is proposed, therefore, that strain SUK12(T) (?=?DSM 42048(T)?=?NRRL B-24860(T)) be classified in the genus Streptomyces as the type strain of Streptomyces kebangsaanensis sp. nov. PMID:23645019

Sarmin, Nurul' Izzah Mohd; Tan, Geok Yuan Annie; Franco, Christopher M M; Edrada-Ebel, RuAngelie; Latip, Jalifah; Zin, Noraziah Mohamad

2013-10-01

391

Evaluation of modeled cloud chemistry mechanism against laboratory irradiation experiments: The HxOy/iron/carboxylic acid chemical system  

NASA Astrophysics Data System (ADS)

Currently, cloud chemistry models are including more detailed and explicit multiphase mechanisms based on laboratory experiments that determine such values as kinetic constants, stability constants of complexes and hydration constants. However, these models are still subject to many uncertainties related to the aqueous chemical mechanism they used. Particularly, the role of oxidants such as iron and hydrogen peroxide in the oxidative capacity of the cloud aqueous phase has typically never been validated against laboratory experimental data. To fill this gap, we adapted the M2C2 model (Model of Multiphase Cloud Chemistry) to simulate irradiation experiments on synthetic aqueous solutions under controlled conditions (e.g., pH, temperature, light intensity) and for actual cloud water samples. Various chemical compounds that purportedly contribute to the oxidative budget in cloud water (i.e., iron, oxidants, such as hydrogen peroxide: H2O2) were considered. Organic compounds (oxalic, formic and acetic acids) were taken into account as target species because they have the potential to form iron complexes and are good indicators of the oxidative capacity of the cloud aqueous phase via their oxidation in this medium. The range of concentrations for all of the chemical compounds evaluated was representative of in situ measurements. Numerical outputs were compared with experimental data that consisted of a time evolution of the concentrations of the target species. The chemical mechanism in the model describing the “oxidative engine” of the HxOy/iron (HxOy = H2O2, HO2rad /O2rad - and HOrad ) chemical system was consistent with laboratory measurements. Thus, the degradation of the carboxylic acids evaluated was closely reproduced by the model. However, photolysis of the Fe(C2O4)+ complex needs to be considered in cloud chemistry models for polluted conditions (i.e., acidic pH) to correctly reproduce oxalic acid degradation. We also show that iron and formic acid lead to a stable complex whose photoreactivity has currently not been investigated. The updated aqueous chemical mechanism was compared with data from irradiation experiments using natural cloud water. The new reactions considered in the model (i.e., iron complex formation with oxalic and formic acids) correctly reproduced the experimental observations.

Long, Yoann; Charbouillot, Tiffany; Brigante, Marcello; Mailhot, Gilles; Delort, Anne-Marie; Chaumerliac, Nadine; Deguillaume, Laurent

2013-10-01

392

Synthesis and characterization of tri( o-fluorobenzyl)tin esters of heteroaromatic carboxylic acid and crystal structures of tri( o-fluorobenzyl)tin esters of 4-pyridinecarboxylic acid and 3-pyridinecarboxylic acid  

Microsoft Academic Search

Reaction of tri(o-fluorobenzyl)tin chloride with sodium of heteroaromatic carboxylic acid in 1:1 stoichiometry yielded complexes of the type (2-F-Bz)3SnOOCR (R=2-furanyl, 2-furanvingl, 2-thiophenyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-indolyl, 3-indolmethyl and 3-indolpropyl), respectively. These complexes have been characterized by elemental analyses, IR and 1H NMR spectroscopy. The crystal structures of tri(o-fluorobenzyl)tin esters of 4-pyridinecarboxylic acid (5) and 3-pyridinecarboxylic acid (6) were determined by

Handong D. Yin; Chuanhua Wang; Chunlin Ma; Daqi Wang

2004-01-01

393

Photovoltaic enhancement of dye-sensitized solar cell prepared from [TiO 2\\/ethyl cellulose\\/terpineol] paste employing TRITON™ X-based surfactant with carboxylic acid group in the oxyethylene chain end  

Microsoft Academic Search

This paper describes the formulation of nanocrystalline TiO2 paste for dye-sensitized solar cell (DSSC) applications employing a series of TRITON™ X-based surfactants with an octyl phenol ethoxylate (OPE) backbone and various chain ends. Five different functional group-terminated TRITON™ X (or OPE) derivatives, [OPE5-OH], [OPE5-COOH], [OPE5-NH2], [OPE5-Imidazole], and [OPE5-OPO(OH)2], were prepared from OPE of 5 oxyethylene units (n=5). The carboxylic acid-terminated

Jung-Gyu Nam; Eun-Sung Lee; Won-Cheol Jung; Young-Jun Park; Byung-Hee Sohn; Sang-Cheol Park; Joo Sung Kim; Jin-Young Bae

2009-01-01

394

An unexplored O2-involved pathway for the decarboxylation of saturated carboxylic acids by TiO2 photocatalysis: an isotopic probe study.  

PubMed

The aerobic decarboxylation of saturated carboxylic acids (from C(2) to C(5)) in water by TiO(2) photocatalysis was systematically investigated in this work. It was found that the split of C(1)-C(2) bond of the acids to release CO(2) proceeds sequentially (that is, a C(5) acid sequentially forms C(4) products, then C(3) and so forth). As a model reaction, the decarboxylation of propionic acid to produce acetic acid was tracked by using isotopic-labeled H(2)(18)O. As much as ?42% of oxygen atoms of the produced acetic acids were from dioxygen ((16)O(2)). Through diffuse reflectance FTIR measurements (DRIFTS), we confirmed that an intermediate pyruvic acid was generated prior to the cut-off of the initial carboxyl group; this intermediate was evidenced by the appearance of an absorption peak at 1772 cm(-1) (attributed to C=O stretch of ?-keto group of pyruvic acid) and the shift of this peak to 1726 cm(-1) when H(2)(16)O was replaced by H(2)(18)O. Consequently, pyruvic acid was chosen as another model molecule to observe how its decarboxylation occurs in H(2)(16)O under an atmosphere of (18)O(2). With the ?-keto oxygen of pyruvic acid preserved in the carboxyl group of acetic acid, ?24% new oxygen atoms of the produced acetic acid were from molecular oxygen at near 100% conversion of pyruvic acid. The other ?76% oxygen atoms were provided by H(2)O through hole/OH radical oxidation. In the presence of conduction band electrons, O(2) can independently accomplish such C(1)-C(2) bond cleavage of pyruvic acid to generate acetic acid with ?100% selectivity, as confirmed by an electrochemical experiment carried out in the dark. More importantly, the ratio of O(2) participation in decarboxylation increased along with the increase of pyruvic acid conversion, indicating the differences between non-substituted acids and ?-keto acids. This also suggests that the O(2)-dependent decarboxylation competes with hole/OH-radical-promoted decarboxylation and depends on TiO(2) surface defects at which Ti(4c) sites are available for the simultaneous coordination of substrates and O(2). PMID:20857460

Wen, Bo; Li, Yue; Chen, Chuncheng; Ma, Wanhong; Zhao, Jincai

2010-10-18

395

Polar organic marker compounds in atmospheric aerosol in the Po Valley during the Supersito campaigns - Part 1: Low molecular weight carboxylic acids in cold seasons  

NASA Astrophysics Data System (ADS)

In the framework of the “Supersito” project, three intensive experimental campaigns were conducted in the Po Valley (Northern Italy) in cold seasons, such as late autumn, pre-winter and deep-winter, over three years from 2011 to 2013. As a part of a study on polar marker compounds, including carboxylic acids, sugar derivatives and lignin phenols, the present study reports a detailed discussion on the atmospheric concentrations of 14 low molecular weight carboxylic acids, mainly dicarboxylic and oxo-hydroxy carboxylic acids, as relevant markers of primary and secondary organic aerosols. PM2.5 samples were collected in two monitoring sites, representing urban and rural background stations. The total quantities of carboxylic acids were 262, 167 and 249 ng m-3 at the urban site and 308, 115, 248 ng m-3 at the rural site in pre-winter, fall and deep-winter, respectively. These high concentrations can be explained by the large human emission sources in the urbanized region, combined with the stagnant atmospheric conditions during the cold seasons that accumulate the organic precursors and accelerate the secondary atmospheric reactions. The distribution profiles of the investigated markers suggest the dominant contributions of primary anthropogenic sources, such as traffic, domestic heating and biomass burning. These results are confirmed by comparison with additional emission tracers, such as anhydro-saccharides for biomass burning and fatty acids originated from different anthropogenic sources. In addition, some secondary constituents were detected in both sites, as produced by in situ photo-chemical reactions from both biogenic (e.g. pinonic acid) and anthropogenic precursors (e.g. phthalic and adipic acids). The impact of different sources from human activities was elucidated by investigating the week pattern of carboxylic and fatty acid concentrations. The weekly trends of analytes during the warmer campaign (fall 2012; mean temperature: 12 °C) may be related to emissions from motor vehicle traffic and industrial activities. Otherwise, the random pattern of the markers suggests the prevalent contribution of primary emissions from residential heating in the colder deep-winter (mean temperature: 5 °C).

Pietrogrande, Maria Chiara; Bacco, Dimitri; Visentin, Marco; Ferrari, Silvia; Poluzzi, Vanes

2014-04-01

396

Saponin Biosynthesis in Saponaria vaccaria. cDNAs Encoding ?-Amyrin Synthase and a Triterpene Carboxylic Acid Glucosyltransferase1[OA  

PubMed Central

Saponaria vaccaria (Caryophyllaceae), a soapwort, known in western Canada as cowcockle, contains bioactive oleanane-type saponins similar to those found in soapbark tree (Quillaja saponaria; Rosaceae). To improve our understanding of the biosynthesis of these saponins, a combined polymerase chain reaction and expressed sequence tag approach was taken to identify the genes involved. A cDNA encoding a ?-amyrin synthase (SvBS) was isolated by reverse transcription-polymerase chain reaction and characterized by expression in yeast (Saccharomyces cerevisiae). The SvBS gene is predominantly expressed in leaves. A S. vaccaria developing seed expressed sequence tag collection was developed and used for the isolation of a full-length cDNA bearing sequence similarity to ester-forming glycosyltransferases. The gene product of the cDNA, classified as UGT74M1, was expressed in Escherichia coli, purified, and identified as a triterpene carboxylic acid glucosyltransferase. UGT74M1 is expressed in roots and leaves and appears to be involved in monodesmoside biosynthesis in S. vaccaria. PMID:17172290

Meesapyodsuk, Dauenpen; Balsevich, John; Reed, Darwin W.; Covello, Patrick S.

2007-01-01

397

The cytotoxicity of benzaldehyde nitrogen mustard-2-pyridine carboxylic acid hydrazone being involved in topoisomerase II? inhibition.  

PubMed

The antitumor property of iron chelators and aromatic nitrogen mustard derivatives has been well documented. Combination of the two pharmacophores in one molecule in drug designation is worth to be explored. We reported previously the syntheses and preliminary cytotoxicity evaluation of benzaldehyde nitrogen mustard pyridine carboxyl acid hydrazones (BNMPH) as extended study, more tumor cell lines (IC50 for HepG2: 26.1 ± 3.5 ?M, HCT-116: 57.5 ± 5.3 ?M, K562: 48.2 ± 4.0 ?M, and PC-12: 19.4 ± 2.2 ?M) were used to investigate its cytotoxicity and potential mechanism. In vitro experimental data showed that the BNMPH chelating Fe(2+) caused a large number of ROS formations which led to DNA cleavage, and this was further supported by comet assay, implying that ROS might be involved in the cytotoxicity of BNMPH. The ROS induced changes of apoptosis related genes, but the TFR1 and NDRG1 metastatic genes were not obviously regulated, prompting that BNMPH might not be able to deprive Fe(2+) of ribonucleotide reductase. The BNMPH induced S phase arrest was different from that of iron chelators (G1) and alkylating agents (G2). BNMPH also exhibited its inhibition of human topoisomerase II?. Those revealed that the cytotoxic mechanism of the BNMPH could stem from both the topoisomerase II inhibition, ROS generation and DNA alkylation. PMID:24995306

Fu, Yun; Zhou, Sufeng; Liu, Youxun; Yang, Yingli; Sun, Xingzhi; Li, Changzheng

2014-01-01

398

Identification of indole-3-carboxylic acids as non-ATP-competitive Polo-like kinase 1 (Plk1) inhibitors.  

PubMed

A series of indole-3-carboxylic acids were designed as novel small molecular non-ATP-competitive Plk1 inhibitors. The designed compounds were synthesized and evaluated. Most of the targeted compounds showed potent Plk1 inhibitory activities and anti-proliferative characters. Particularly, 4f and 4g showed Plk1 inhibitory activity with IC50 values of 0.41 and 0.13?M, which were about 5 and 17 times more potent compared to thymoquinone, respectively. Compound 4g also showed inhibitory activity to HeLa and MCF-7 cell lines with IC50 values of 0.72 and 1.15?M, which was almost 3 and 4 times more potent than thymoquinone. Study of mechanism of action suggested that 4g was an ATP-independent and substrate-dependent Plk1 inhibitor. Moreover, 4g showed excellent Plk1 inhibitory selectivity against Plk2 and Plk3. Fluorescein isothiocyanate Annexin V/propidium iodide (PI) double-staining assay and western-blot results indicate that induction of apoptosis by 4g is involved in its anti-tumor activity. This study may provide a support for further optimization of non-ATP-competitive Plk1 inhibitors. PMID:25556101

Liu, Meng; Huang, Jie; Chen, Dong-Xing; Jiang, Cheng

2015-02-01

399

Molecular structures and ab initio molecular orbital calculations of the optically active derivatives of 1-aminocyclopropane-1-carboxylic acid  

NASA Astrophysics Data System (ADS)

The novel optically active derivatives of 2,2'-disubstituted-1-aminocyclopropane-1-carboxylic acid (-)- 2 and (+)- 3 were synthesised from the spiro-azlactone (+)- 1. Oxidation of the diol moiety of (+)- 3 gave by ring enlargement the racemic mixture of 2,3-dihydrofuran derivative (±)- 6. This conversion is explained by stepwise rearrangement of the initially formed tetrasubstituted cyclopropanecarbaldehyde 4 through zwitterionic's reactive intermediate 5. The formation of (±)- 6 is preferred energetically as established by ab initio calculations of the ground states and possible intermediates for that rearrangement. The crystal structure and absolute configuration of the compounds (+)- 1, (-)- 2, (+)- 3 and (-)- 7 were determined by single-crystal X-ray diffraction method. All four compounds possess Z-configuration of the cyclopropane ring. The dioxolane ring in the structures (+)- 1 and (-)- 2 adopts half-chair conformation, while the cyclopropane ring and geminally substituted groups in the structures (-)- 2, (+)- 3 and (-)- 7 possess the anticlinal conformation. The molecules of the compound (+)- 1 are connected by very weak intermolecular hydrogen bond of C-H⋯O type. In the compounds (-)- 2, (+)- 3 and (-)- 7inter- and intramolecular hydrogen bonds of N-H⋯O type were observed. The spiro-compound (+)- 1 exhibited a more pronounced inhibitory activity against the proliferation of murine leukemia and human T-lymphocytes cells than other type of tumor cell lines and normal human fibroblast cells.

Džoli?, Zoran; Cetina, Mario; Kova?ek, Damir; Hergold-Brundi?, Antonija; Mrvoš-Sermek, Draginja; Nagl, Ante; Slade, Neda; Paveli?, Krešimir; Balzarini, Jan; De Clercq, Erik; Zerbe, Oliver; Folkers, Gerd; Scapozza, Leonardo; Mintas, Mladen

2003-07-01

400

(CF3CO)2O/CF3SO3H-mediated synthesis of 1,3-diketones from carboxylic acids and aromatic ketones.  

PubMed

A very simple and convenient reaction for 1,3-diketone preparation from carboxylic acids and aromatic ketones in TFAA/TfOH system is described. When the ?-phenylpropionic acids were used as starting materials, they initially gave 1-indanones and then underwent further acylation with the formation of 2-(?-phenylpropionyl)-1-indanones as the main reaction products. In addition, the application of the proposed protocol allowed for the synthesis of selected polysubstituted pyrazoles in a one-pot procedure directly from acids and ketones. PMID:25298794

Kim, JungKeun; Shokova, Elvira; Tafeenko, Victor; Kovalev, Vladimir

2014-01-01

401

(CF3CO)2O/CF3SO3H-mediated synthesis of 1,3-diketones from carboxylic acids and aromatic ketones  

PubMed Central

Summary A very simple and convenient reaction for 1,3-diketone preparation from carboxylic acids and aromatic ketones in TFAA/TfOH system is described. When the ?-phenylpropionic acids were used as starting materials, they initially gave 1-indanones and then underwent further acylation with the formation of 2-(?-phenylpropionyl)-1-indanones as the main reaction products. In addition, the application of the proposed protocol allowed for the synthesis of selected polysubstituted pyrazoles in a one-pot procedure directly from acids and ketones. PMID:25298794

Kim, JungKeun; Shokova, Elvira; Tafeenko, Victor

2014-01-01

402

Lysine Carboxylation in Proteins: OXA-10 -Lactamase Jason B. Cross,1  

E-print Network

for the functions of these proteins. These examples demonstrate the utility of this un- usual amino acid in acid-base chemistry, in expan- sion of function beyond those of the 20 standard amino acids. In this study, the ONIOM field. The barriers for unas- sisted carboxylation of neutral lysine by carbon dioxide or bicarbonate

Schlegel, H. Bernhard

403

Structure of the PLP Degradative Enzyme 2-Methyl-3-hydroxypyridine-5-carboxylic Acid Oxygenase from Mesorhizobium loti MAFF303099 and Its Mechanistic Implications  

SciTech Connect

A vitamin B{sub 6} degradative pathway has recently been identified and characterized in Mesorhizobium loti MAFF303099. One of the enzymes on this pathway, 2-methyl-3-hydroxypyridine-5-carboxylic acid oxygenase (MHPCO), is a flavin-dependent enzyme and catalyzes the oxidative ring-opening of 2-methyl-3-hydroxypyridine-5-carboxylic acid to form E-2-(acetamino-methylene)succinate. The gene for this enzyme has been cloned, and the corresponding protein has been overexpressed in Escherichia coli and purified. The crystal structure of MHPCO has been solved to 2.1 {angstrom} using SAD phasing with and without the substrate MHPC bound. These crystal structures provide insight into the reaction mechanism and suggest roles for active site residues in the catalysis of a novel oxidative ring-opening reaction.

McCulloch, Kathryn M.; Mukherjee, Tathagata; Begley, Tadhg P.; Ealick, Steven E.; Cornell

2009-06-12

404

Calix[n]arene carboxylic acid derivatives as regulators of enzymatic reactions: enhanced enantioselectivity in lipase-catalyzed hydrolysis of (R/S)-naproxen methyl ester.  

PubMed

Candida rugosa lipase was immobilized with a sol-gel encapsulation procedure in the presence and absence of a calix[n]arene carboxylic acid derivative grafted onto magnetic nanoparticles or in the presence of the calix[n]arene carboxylic acid derivative with Fe3O4 magnetic nanoparticles as an additive. Through the enantioselective hydrolysis of racemic naproxen methyl ester and the hydrolysis of p-nitrophenylpalmitate, the relative enzyme activity was evaluated and tested. These results show that the encapsulated lipase without supports has lower conversion and enantioselectivity compared to the Calix[n]COOH-based encapsulated lipase. It has also been observed that the Calix[4]COOH-based encapsulated lipase has excellent enantioselectivity (enantiomeric ratio (E)?> 400) as compared to encapsulated-free lipase enantioselectivity (E = 137), and it also has an enantiomeric excess value of ~98 % for S-naproxen. PMID:24092454

Akoz, Enise; Akbulut, Osman Y; Yilmaz, Mustafa

2014-01-01

405

Light- and temperature-entrained circadian regulation of activity and mRNA accumulation of 1-aminocyclopropane-1-carboxylic acid oxidase in Stellaria longipes.  

PubMed

Stem and leaf tissues of Stellaria longipes Goldie (prairie ecotype) exhibit circadian rhythmicity in the activity and mRNA abundance for 1-aminocyclopropane-1-carboxylic acid oxidase (EC 1.4.3). The steady-state mRNA levels and enzymatic activity levels fluctuated with a period of approximately 24 h and reached their maxima by the middle of the light phase and minima by the middle of the dark phase. The oscillations showed damping under constant light, constant dark and constant temperature conditions, indicating that the rhythm is entrained by an external signal. The results indicate that light/dark cycles have greater entraining effects than temperature cycles. A 15-min red light pulse, but not a blue light pulse, could reset rhythm in continuous darkness, suggesting the possible role of a red-light signal transduction pathway in the circadian regulation of 1-aminocyclopropane-1-carboxylic acid oxidase. PMID:8771799

Kathiresan, A; Reid, D M; Chinnappa, C C

1996-01-01

406

Structure of the PLP Degradative Enzyme 2-Methyl-3-hydroxypyridine-5-carboxylic acid Oxygenase from Mesorhizobium loti MAFF303099 and its Mechanistic Implications†‡  

PubMed Central

A vitamin B6 degradative pathway has recently been identified and characterized in Mesorhizobium loti MAFF303099. One of the enzymes on this pathway, 2-methyl-3-hydroxypyridine-5-carboxylic acid oxygenase (MHPCO), is a flavin-dependent enzyme and catalyzes the oxidative ring opening of 2-methyl-3-hydroxypyridine-5-carboxylic acid to form E-2-acetaminomethylene succinate. The gene for this enzyme has been cloned and the corresponding protein has been overexpressed in Escherichia coli and purified. The crystal structure of MHPCO has been solved to 2.1 Å using SAD phasing with and without the substrate MHPC bound. These crystal structures provide insight into the reaction mechanism and suggest roles for active site residues in the catalysis of a novel oxidative ring-opening reaction. PMID:19317437

McCulloch, Kathryn M.; Mukherjee, Tathagata; Begley, Tadhg P.; Ealick, Steven E.

2009-01-01

407

A comparative study on the concentrations of 11-nor-?9-tetrahydrocannabinol-9-carboxylic acid (THCCOOH) in head and pubic hair.  

PubMed

In this study, the concentrations of 11-nor-?(9)-tetrahydrocannabinol-9-carboxylic acid (THCCOOH) in pubic, axillary and beard hair were measured and the correlation between the concentrations of THCCOOH in head and pubic hair from same cannabis users were evaluated. The papers on body hair analysis for THCCOOH were rarely found although police officers submit body hair as a complimentary specimen to forensic laboratories in case cannabis users had no hair. Head, pubic, axillary, and beard hair were collected. All hair samples were cut into 0.5mm segments and decontaminated with methanol, digested with 1 mL of 1M NaOH at 85 °C for 30 min and extracted in 2 mL of n-hexane:ethyl acetate (9:1) two times after adding 1 mL of 0.1N sodium acetate buffer (pH = 4.5) and 200 ?L of acetic acid followed by derivatization with 50 ?L of PFPA and 25 ?L of PFPOH for 30 min at 70 °C. The extracts were analyzed using gas chromatography tandem mass spectrometry operating in negative chemical ionization mode (GC/MS/MS-NCI). We determined the concentrations of THCCOOH in both pubic and head hair. The concentrations of THCCOOH in pubic hair were higher than those in head hair. We also evaluated the concentrations of THCCOOH in body hair (pubic, axillary and beard hair) and head hair according to the positive/negative urine test results. There was no statistically significant difference in the concentrations of THCCOOH in head and body hair according to urine results. PMID:21802874

Han, Eunyoung; Choi, Hwakyung; Lee, Sangki; Chung, Heesun; Song, Joon Myong

2011-10-10

408

Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics.  

PubMed

This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity. PMID:18222595

Anirudhan, T S; Divya, L; Suchithra, P S

2009-01-01

409

Binding of cyclic carboxylates to octa-acid deep-cavity cavitand.  

PubMed

As part of the fourth statistical assessment of modeling of proteins and ligands (sampl.eyesopen.com) prediction challenge, the strength of association of nine guests (1-9) binding to octa-acid host was determined by a combination of (1)H NMR and isothermal titration calorimetry. Association constants in sodium tetraborate buffered (pH 9.2) aqueous solution ranged from 5.39 × 10(2) M(-1) in the case of benzoate 1, up to 3.82 × 10(5) M(-1) for trans-4-methylcyclohexanoate 7. Overall, the free energy difference between the free energies of complexation of these weakest and strongest binding guests was ??G° = 3.88 kcal mol(-1). Based on a multitude of previous studies, the anticipated order of strength of binding was close to that which was actually obtained. However, the binding of guest 3 (4-ethylbenzoate) was considerably stronger than initially estimated. PMID:24218290

Gibb, Corinne L D; Gibb, Bruce C

2014-04-01

410

Atmospheric oxidation of polyfluorinated amides: historical source of perfluorinated carboxylic acids to the environment.  

PubMed

Polyfluorinated amides (PFAMs) are a class of fluorinated compounds which were produced as unintentional byproducts in the electrochemical fluorination process used for polyfluorinated sulfonamide synthesis in 1947-2002. To investigate the historical potential of PFAMs as an atmospheric perfluorinated acid (PFCA) source we studied N-ethylperfluorobutyramide (EtFBA) as a surrogate for longer chained PFAMs. Smog chamber relative rate techniques were used to measure bimolecular rate coefficients for reactions of EtFBA with chlorine atoms and hydroxyl radicals. It was found kCl = (2.08 ± 0.15) × 10(-11) cm(3) molecule(-1) s(-1) and kOH = (2.65 ± 0.50) × 10(-12) cm(3) molecule(-1) s(-1) and the atmospheric lifetime of EtFBA with respect to reaction with OH was estimated to be approximately 4.4 days. Offline sampling with both GC-MS and LC-MS/MS techniques was used to determine the products and hence a plausible pathway of atmospheric oxidation of EtFBA. Three primary oxidation products were observed by GC-MS, the N-dealkylation product C3F7C(O)NH2 and two carbonyl products, probably C3F7C(O)N(H)C(O)CH3 and C3F7C(O)N(H)CH2CHO. These primary products react further to give perfluorocarboxylic acids (PFCAs) as detected by LC-MS/MS, suggesting that eight carbon PFAMs were a historical source of PFCAs to remote regions, including the Canadian Arctic. PMID:23586598

Jackson, Derek A; Wallington, Timothy J; Mabury, Scott A

2013-05-01

411

Selective synthesis of ?,?-dideuterio alcohols by the reduction of carboxylic acids using SmI2 and D2O as deuterium source under SET conditions.  

PubMed

The first general method for the chemoselective synthesis of ?,?-dideuterio alcohols directly from feedstock carboxylic acids under single electron transfer conditions using SmI2 is reported. This reaction proceeds after the activation of Sm(II) with a Lewis base, results in excellent levels of deuterium incorporation across a wide range of substrates, and represents an attractive alternative to processes mediated by pyrophoric alkali metal deuterides. PMID:25247236

Szostak, Michal; Spain, Malcolm; Procter, David J

2014-10-01

412

Discovery of thiophene-2-carboxylic acids as potent inhibitors of HCV NS5B polymerase and HCV subgenomic RNA replication. Part 2: tertiary amides.  

PubMed

Further SAR studies on the thiophene-2-carboxylic acids are reported. These studies led to the identification of a series of tertiary amides that show inhibition of both HCV NS5B polymerase in vitro and HCV subgenomic RNA replication in Huh-7 cells. Structural insights about the bioactive conformation of this class of molecules were deduced from a combination of modeling and transferred NOE (trNOE) studies. PMID:14741292

Chan, Laval; Pereira, Oswy; Reddy, T Jagadeeswar; Das, Sanjoy K; Poisson, Carl; Courchesne, Marc; Proulx, Mélanie; Siddiqui, Arshad; Yannopoulos, Constantin G; Nguyen-Ba, Nghe; Roy, Caroline; Nasturica, Daniel; Moinet, Christophe; Bethell, Richard; Hamel, Martine; L'Heureux, Lucille; David, Maud; Nicolas, Olivier; Courtemanche-Asselin, Philippe; Brunette, Stéphanie; Bilimoria, Darius; Bédard, Jean

2004-02-01

413

Electrocatalytic carboxylation of 2-amino-5-bromopyridine with CO 2 in ionic liquid 1-butyl-3-methyllimidazoliumtetrafluoborate to 6-aminonicotinic acid  

Microsoft Academic Search

A new electrochemical procedure for the electrocatalytic carboxylation of 2-amino-5-bromopyridine with CO2 in ionic liquid, 1-butyl-3-methyllimidazolium tetrafluoborate (BMIMBF4), to 6-aminonicotinic acid was investigated for the first time. The experiments were carried out in three electrodes undivided cell under mild conditions, and the use of volatile and toxic solvents and catalysts, as well as any other additional supporting electrolytes, was avoided.

Qiuju Feng; Kelong Huang; Suqin Liu; Xuanyun Wang

2010-01-01

414

Light and temperature-entrained circadian regulation of activity and mRNA accumulation of 1-aminocyclopropane-1-carboxylic acid oxidase in Stellaria longipes  

Microsoft Academic Search

Stem and leaf tissues of Stellaria longipes Goldie (prairie ecotype) exhibit circadian rhythmicity in the activity and mRNA abundance for 1-aminocyclopropane-1-carboxylic acid oxidase (EC 1.4.3). The steady-state mRNA levels and enzymatic activity levels fluctuated with a period of approximately 24 h and reached their maxima by the middle of the light phase and minima by the middle of the dark

Arumugam Kathiresan; D. M. Reid; C. C. Chinnappa

1996-01-01

415

Improved growth performance of the mangrove Avicennia marina seedlings using a 1-aminocyclopropane-1-carboxylic acid deaminase-producing isolate of Pseudoalteromonas maricaloris  

Microsoft Academic Search

Out of 62 bacterial isolates obtained from the mangrove Avicennia\\u000a marina rhizosphere that grows along the Abu Dhabi coast, United Arab Emirates (UAE), an isolate of Pseudoalteromonas maricaloris (Wild type strain) (WT) produced relatively high levels of 1-aminocyclopropane-1-carboxylic acid (ACC) deaminase in vitro.\\u000a Application of this WT strain under greenhouse conditions to A. marina seedlings significantly (P P in planta endogenous plant

Khaled A. El-Tarabily; Tarek Youssef

416

Optimization of nutrient components for enhanced phenazine-1-carboxylic acid production by gacA -inactivated Pseudomonas sp. M18G using response surface method  

Microsoft Academic Search

The nutritional requirements for phenazine-1-carboxylic acid (PCA) production using Pseudomonas sp. M18G, a gacA chromosomal-inactivated mutant of the strain M18, with a high PCA yield, were optimized statistically in shake flask experiments.\\u000a Based on a single-factor experiment design, we implemented the two-level Plackett–Burman (PB) design with 11 variables to\\u000a screen medium components that significantly influence PCA production. Soybean meal, glucose,

Yaqian Li; Haixia Jiang; Yuquan Xu; Xuehong Zhang

2008-01-01

417

Single wall carbon nanotube/bis carboxylic acid-ICG as a sensitive contrast agent for in vivo tumor imaging in photoacoustic tomography  

NASA Astrophysics Data System (ADS)

In this study, we present a novel photoacoustic contrast agent which is based on bis-carboxylic acid derivative of Indocyanine green (ICG) covalently conjugated to single-wall carbon nanotubes (ICG/SWCNT). Covalently attaching ICG to the functionalized SWCNT provides a more robust system that delivers much more ICG to the tumor site. The detection sensitivity of the new contrast agent in mouse tumor model is demonstrated in vivo by our custom built photoacoustic imaging system. PAT summation signal is defined to show the long-term light absorption of tumor areas in ICG injected mice and ICG/SWCNT injected mice. It is shown that ICG is able to provide 33% enhancement at approximately 20 minutes peak response time referred to pre-injection PAT summation level, while ICG/SWCNT provides 128% enhancement at 80 minutes and even higher enhancement of 196% at the end point of experiments (120 minutes on average). Additionally, the ICG/SWCNT enhancement was mainly observed at the tumor periphery as confirmed by fluorescence images of the tumor samples. This feature is highly valuable in guiding surgeons to assess tumor boundaries and dimensions in vivo and improve surgical resection of tumors for achieving clean tumor margins.

Zanganeh, Saeid; Li, Hai; Kumavor, Patrick; Alqasemi, Umar; Aguirre, Andres; Mohammad, Innus; Stanford, Courtney; Smith, Michael B.; Zhu, Quing

2013-03-01

418

Fluorescence quantum efficiency of CdSe/CdS magic-sized quantum dots functionalized with carboxyl or hydroxyl groups  

NASA Astrophysics Data System (ADS)

The present letter reports the thermo-optical properties of functionalized CdSe/CdS magic-sized quantum dots (MSQDs) (sizes 1.9-2.3 nm) with carboxyl (R-COOH) or hydroxyl (R-OH) groups in aqueous solutions. Atomic force microscopy and infrared transmittance measurements were used to determine the size of the QDs and to highlight the functionalized groups. Absolute nonradiative quantum efficiency (?) and radiative quantum efficiency (?) values were determined by applying two techniques: thermal lens (TL) and an alternative method that analyzes the ring patterns generated in a laser beam due to thermally induced self-phase-modulation effects known as the conical diffraction. Fluorescence measurements corroborate the TL results.

Pilla, Viviane; de Lima, Sthanley R.;