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1

Green process for chemical functionalization of nanocellulose with carboxylic acids.  

PubMed

An environmentally friendly and simple method, named SolReact, has been developed for a solvent-free esterification of cellulose nanocrystals (CNC) surface by using two nontoxic carboxylic acids (CA), phenylacetic acid and hydrocinnamic acid. In this process, the carboxylic acids do not only act as grafting agent, but also as solvent media above their melting point. Key is the in situ solvent exchange by water evaporation driving the esterification reaction without drying the CNC. Atomic force microscopy and X-ray diffraction analyses showed no significant change in the CNC dimensions and crystallinity index after this green process. The presence of the grafted carboxylic was characterized by analysis of the "bulk" CNC with elemental analysis, infrared spectroscopy, and (13)C NMR. The ability to tune the surface properties of grafted nanocrystals (CNC-g-CA) was evaluated by X-ray photoelectron spectroscopy analysis. The hydrophobicity behavior of the functionalized CNC was studied through the water contact-angle measurements and vapor adsorption. The functionalization of these bionanoparticles may offer applications in composite manufacturing, where these nanoparticles have limited dispersibility in hydrophobic polymer matrices and as nanoadsorbers due to the presence of phenolic groups attached on the surface. PMID:25353612

Espino-Pérez, Etzael; Domenek, Sandra; Belgacem, Naceur; Sillard, Cécile; Bras, Julien

2014-12-01

2

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

PubMed

Degradable aliphatic polyesters such as poly(lactic acid) are widely used in biomedical applications, however, they lack functional moieties along the polymer backbone that are amenable for functionalization reactions or could be the basis for interactions with biological systems. Here we present a straightforward route for the synthesis of functional ?-? epoxyesters as comonomers for lactide polymerization. Salient features of these highly functionalized epoxides are versatility in functionality and a short synthetic route of less than four steps. The ?-? epoxyesters presented serve as a means to introduce carboxylic acid and amine functional groups into poly(lactic acid) polymers via ring-opening copolymerization. PMID:25786163

Heiny, Markus; Shastri, V Prasad

2015-01-01

3

Preparation and self-assembly of carboxylic acid-functionalized silica  

Microsoft Academic Search

A simple method for the fabrication of silica nanoparticle film based on the covalent-bonding interaction between carboxylic acid-functionalized silica nanoparticles (SiO2–COOH) and amino-terminated silicon wafer was developed. Prior to assembly, silica nanoparticles with an average diameter 80 nm were prepared using the Stöber method, amino-functionalized silica nanoparticles (SiO2–NH2) were prepared by a silanization with 3-aminopropyltriethoxysilane (APTES), while carboxylic acid-functionalized silica

Yanqing An; Miao Chen; Qunji Xue; Weimin Liu

2007-01-01

4

Gas-Phase Reactivity of Carboxylic Acid Functional Groups with Carbodiimides  

PubMed Central

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. PMID:23208744

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

2012-01-01

5

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

6

Synthesis and Functionalization of Cyclic Sulfonimidamides: A Novel Chiral Heterocyclic Carboxylic Acid Bioisostere  

PubMed Central

An efficient synthesis of aryl substituted cyclic sulfonimidamides designed as chiral nonplanar heterocyclic carboxylic acid bioisosteres is described. The cyclic sulfonimidamide ring system could be prepared in two steps from a trifluoroacetyl protected sulfinamide and methyl ester protected amino acids. By varying the amino acid, a range of different C-3 substituted sulfonimidamides could be prepared. The compounds could be further derivatized in the aryl ring using standard cross-coupling reactions to yield highly substituted cyclic sulfonimidamides in excellent yields. The physicochemical properties of the final compounds were examined and compared to those of the corresponding carboxylic acid and tetrazole derivatives. The unique nonplanar shape in combination with the relatively strong acidity (pKa 5–6) and the ease of modifying the chemical structure to fine-tune the physicochemical properties suggest that this heterocycle can be a valuable addition to the range of available carboxylic acid isosteres. PMID:24900513

2012-01-01

7

Expression of a functional jasmonic acid carboxyl methyltransferase is negatively correlated with strawberry fruit development.  

PubMed

The volatile metabolite methyl jasmonate (MeJA) plays an important role in intra- and interplant communication and is involved in diverse biological processes. In this study, we report the cloning and functional characterization of a S-adenosyl-l-methionine:jasmonic acid carboxyl methyltransferase (JMT) from Fragaria vesca and Fragaria×ananassa. Biochemical assays and comprehensive transcript analyses showed that JMT has been erroneously annotated as gene fusion with a carboxyl methyltransferase (CMT) (gene15184) in the first published genome sequence of F. vesca. Recombinant FvJMT catalyzed the formation of MeJA with KM value of 22.3?M while FvCMT and the fusion protein were almost inactive. Activity of JMT with benzoic acid and salicylic acid as substrates was less than 1.5% of that with JA. Leucine at position 245, an amino acid missing in other JMT sequences is essential for activity of FvJMT. In accordance with MeJA levels, JMT transcript levels decreased steadily during strawberry fruit ripening, as did the expression levels of JA biosynthesis and regulatory genes. It appears that CMT has originated by a recent duplication of JMT and lost its enzymatic activity toward JA. In the newest version of the strawberry genome sequence (June 2014) CMT and JMT are annotated as separate genes in accordance with differential temporal and spatial expression patterns of both genes in Fragaria sp. In conclusion, MeJA, the inactive derivative of JA, is probably involved in early steps of fruit development by modulating the levels of the active plant hormone JA. PMID:25046752

Preuß, Anja; Augustin, Christiane; Figueroa, Carlos R; Hoffmann, Thomas; Valpuesta, Victoriano; Sevilla, José F; Schwab, Wilfried

2014-09-15

8

Solid phase extraction of petroleum carboxylic acids using a functionalized alumina as stationary phase.  

PubMed

Petroleum essentially consists of a mixture of organic compounds, mainly containing carbon and hydrogen, and, in minor quantities, compounds with nitrogen, sulphur, and oxygen. Some of these compounds, such as naphthenic acids, can cause corrosion in pipes and equipment used in processing plants. Considering that the methods of separation or clean up the target compounds in low concentrations and in complex matrix use large amounts of solvents or stationary phases, is necessary to study new methodologies that consume smaller amounts of solvent and stationary phases to identify the acid components present in complex matrix, such as crude oil samples. The proposed study aimed to recover acid compounds using the solid phase extraction method, employing different types of commercial stationary ion exchange phases (SAX and NH(2)) and new phase alumina functionalized with 1,4-bis(n-propyl)diazoniabicyclo[2.2.2]octane chloride silsesquioxane (Dab-Al(2)O(3)), synthesized in this work. Carboxylic acids were used as standard mixture in the solid phase extraction for further calculation of recovery yield. Then, the real sample (petroleum) was fractionated into saturates, aromatics, resins, and asphaltenes, and the resin fraction of petroleum (B1) was eluted through stationary ion exchange phases. The stationary phase synthesized in this work showed an efficiency of ion exchange comparable to that of the commercial stationary phases. PMID:22589166

de Conto, Juliana Faccin; Nascimento, Juciara dos Santos; de Souza, Driele Maiara Borges; da Costa, Luiz Pereira; Egues, Silvia Maria da Silva; Freitas, Lisiane Dos Santos; Benvenutti, Edilson Valmir

2012-04-01

9

Understanding biocatalyst inhibition by carboxylic acids.  

PubMed

Carboxylic acids are an attractive biorenewable chemical in terms of their flexibility and usage as precursors for a variety of industrial chemicals. It has been demonstrated that such carboxylic acids can be fermentatively produced using engineered microbes, such as Escherichia coli and Saccharomyces cerevisiae. However, like many other attractive biorenewable fuels and chemicals, carboxylic acids become inhibitory to these microbes at concentrations below the desired yield and titer. In fact, their potency as microbial inhibitors is highlighted by the fact that many of these carboxylic acids are routinely used as food preservatives. This review highlights the current knowledge regarding the impact that saturated, straight-chain carboxylic acids, such as hexanoic, octanoic, decanoic, and lauric acids can have on E. coli and S. cerevisiae, with the goal of identifying metabolic engineering strategies to increase robustness. Key effects of these carboxylic acids include damage to the cell membrane and a decrease of the microbial internal pH. Certain changes in cell membrane properties, such as composition, fluidity, integrity, and hydrophobicity, and intracellular pH are often associated with increased tolerance. The availability of appropriate exporters, such as Pdr12, can also increase tolerance. The effect on metabolic processes, such as maintaining appropriate respiratory function, regulation of Lrp activity and inhibition of production of key metabolites such as methionine, are also considered. Understanding the mechanisms of biocatalyst inhibition by these desirable products can aid in the engineering of robust strains with improved industrial performance. PMID:24027566

Jarboe, Laura R; Royce, Liam A; Liu, Ping

2013-01-01

10

Biocatalytic reduction of carboxylic acids.  

PubMed

An increasing demand for non-petroleum-based products is envisaged in the near future. Carboxylic acids such as citric acid, succinic acid, fatty acids, and many others are available in abundance from renewable resources and they could serve as economic precursors for bio-based products such as polymers, aldehyde building blocks, and alcohols. However, we are confronted with the problem that carboxylic acid reduction requires a high level of energy for activation due to the carboxylate's thermodynamic stability. Catalytic processes are scarce and often their chemoselectivity is insufficient. This review points at bio-alternatives: currently known enzyme classes and organisms that catalyze the reduction of carboxylic acids are summarized. Two totally distinct biocatalyst lines have evolved to catalyze the same reaction: aldehyde oxidoreductases from anaerobic bacteria and archea, and carboxylate reductases from aerobic sources such as bacteria, fungi, and plants. The majority of these enzymes remain to be identified and isolated from their natural background in order to evaluate their potential as industrial biocatalysts. PMID:24737783

Napora-Wijata, Kamila; Strohmeier, Gernot A; Winkler, Margit

2014-06-01

11

Detection of a CO and NH3 gas mixture using carboxylic acid-functionalized single-walled carbon nanotubes  

PubMed Central

Carbon nanotubes (CNT) are extremely sensitive to environmental gases. However, detection of mixture gas is still a challenge. Here, we report that 10 ppm of carbon monoxide (CO) and ammonia (NH3) can be electrically detected using a carboxylic acid-functionalized single-walled carbon nanotubes (C-SWCNT). CO and NH3 gases were mixed carefully with the same concentrations of 10 ppm. Our sensor showed faster response to the CO gas than the NH3 gas. The sensing properties and effect of carboxylic acid group were demonstrated, and C-SWCNT sensors with good repeatability and fast responses over a range of concentrations may be used as a simple and effective detection method of CO and NH3 mixture gas. PMID:23286690

2013-01-01

12

An NHC-Catalyzed In Situ Activation Strategy to ?-Functionalize Saturated Carboxylic Acid: An Enantioselective Formal [3+2] Annulation for Spirocyclic Oxindolo-?-butyrolactones.  

PubMed

An in situ NHC-catalyzed activation strategy to ?-functionalize saturated carboxylic acid was developed. This asymmetric formal [3+2] annulation could deliver spirocyclic oxindolo-?-butyrolactones from saturated carboxylic acid and isatin in good yields with high to excellent enantioselectivities. The easy availability of the starting materials, direct installation of functional units at unreactive carbon atom and the convergent assembly make this protocol attractive in the field of organic synthesis. PMID:25689040

Xie, Yuanwei; Yu, Chenxia; Li, Tuanjie; Tu, Shujiang; Yao, Changsheng

2015-03-27

13

Integrated engineering of ?-oxidation reversal and ?-oxidation pathways for the synthesis of medium chain ?-functionalized carboxylic acids.  

PubMed

An engineered reversal of the ?-oxidation cycle was exploited to demonstrate its utility for the synthesis of medium chain (6-10-carbons) ?-hydroxyacids and dicarboxylic acids from glycerol as the only carbon source. A redesigned ?-oxidation reversal facilitated the production of medium chain carboxylic acids, which were converted to ?-hydroxyacids and dicarboxylic acids by the action of an engineered ?-oxidation pathway. The selection of a key thiolase (bktB) and thioesterase (ydiI) in combination with previously established core ?-oxidation reversal enzymes, as well as the development of chromosomal expression systems for the independent control of pathway enzymes, enabled the generation of C6-C10 carboxylic acids and provided a platform for vector based independent expression of ?-functionalization enzymes. Using this approach, the expression of the Pseudomonas putida alkane monooxygenase system, encoded by alkBGT, in combination with all ?-oxidation reversal enzymes resulted in the production of 6-hydroxyhexanoic acid, 8-hydroxyoctanoic acid, and 10-hydroxydecanoic acid. Following identification and characterization of potential alcohol and aldehyde dehydrogenases, chnD and chnE from Acinetobacter sp. strain SE19 were expressed in conjunction with alkBGT to demonstrate the synthesis of the C6-C10 dicarboxylic acids, adipic acid, suberic acid, and sebacic acid. The potential of a ?-oxidation cycle with ?-oxidation termination pathways was further demonstrated through the production of greater than 0.8g/L C6-C10 ?-hydroxyacids or about 0.5g/L dicarboxylic acids of the same chain lengths from glycerol (an unrelated carbon source) using minimal media. PMID:25638687

Clomburg, James M; Blankschien, Matthew D; Vick, Jacob E; Chou, Alexander; Kim, Seohyoung; Gonzalez, Ramon

2015-03-01

14

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

15

Conversion of carboxylate salts to carboxylic acids via reactive distillation  

E-print Network

on the conversion of the carboxylate salts produced via fermentation into their corresponding acids via reactive distillation. The primary objective is to determine the optimal operating conditions of the distillation. A secondary objective is to optimize...

Williamson, Shelly Ann

2000-01-01

16

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

17

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

18

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

19

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

20

An efficient general method for esterification of aromatic carboxylic acids  

Microsoft Academic Search

Treatment of variety of aromatic carboxylic acids with alcohols in the presence of thionyl chloride results in excellent yields of corresponding esters. This esterification system is compatible with a wide assortment of functional groups.

Bhaskar D. Hosangadi; Rajesh H. Dave

1996-01-01

21

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

22

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

23

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.degree. and 80.degree. C. in the substantial absence of a hydrogenation or carbonylation catalyst.

Tustin, Gerald Charles (Kingsport, TN); Dickson, Todd Jay (Kingsport, TN)

1998-01-01

24

Scanning thermal lithography of tailored tert-butyl ester protected carboxylic acid functionalized (meth)acrylate polymer platforms.  

PubMed

In this paper, we report on the development of tailored polymer films for high-resolution atomic force microscopy based scanning thermal lithography (SThL). In particular, full control of surface chemical and topographical structuring was sought. Thin cross-linked films comprising poly(tert-butyl methacrylate) (MA(20)) or poly(tert-butyl acrylate) (A(20)) were prepared via UV initiated free radical polymerization. Thermogravimetric analysis (TGA) and FTIR spectroscopy showed that the heat-induced thermal decomposition of MA(20) by oxidative depolymerization is initially the primary reaction followed by tert-butyl ester thermolysis. By contrast, no significant depolymerization was observed for A(20). For A(20) and MA(20) (at higher temperatures and/or longer reaction times) the thermolysis of the tert-butyl ester liberates isobutylene and yields carboxylic acid groups, which react further intramolecularly to cyclic anhydrides. The values of the apparent activation energies (E(a)) for the thermolysis were calculated to be 125 ± 13 kJ mol(-1) and 116 ± 7 kJ mol(-1) for MA(20) and A(20), respectively. Both MA(20) and A(20) films showed improved thermomechanical stability during SThL compared to non cross-linked films. Carboxylic acid functionalized lines written by SThL in A(20) films had a typically ~10 times smaller width compared to those written in MA(20) films regardless of the tip radius of the heated probe and did not show any evidence for thermochemically or thermomechanically induced modification of film topography. These observations and the E(a) of 45 ± 3 kJ mol(-1) for groove formation in MA(20) estimated from the observed volume loss are attributed to oxidative thermal depolymerization during SThL of MA(20) films, which is considered to be the dominant reaction mechanism for MA(20). The smallest line width values obtained for MA(20) and A(20) films with SThL were 83 ± 7 nm and 21 ± 2 nm, whereas the depth of the lines was below 1 nm, respectively. PMID:21919505

Duvigneau, Joost; Schönherr, Holger; Vancso, G Julius

2011-10-01

25

Kinetics of the esterification of active pharmaceutical ingredients containing carboxylic acid functionality in polyethylene glycol: formulation implications.  

PubMed

Polyethylene glycols (PEGs) are attractive as excipients in the manufacture of drug products because they are water soluble and poorly immunogenic. They are used in various pharmaceutical preparations. However, because of their terminal hydroxyl groups, PEGs can participate in esterification reactions. In this study, kinetics of two active pharmaceutical ingredients, cetirizine and indomethacin possessing carboxylic acid functionality, has been studied in PEG 400 and PEG 1000 at 50 °C, 60 °C, 70 °C, and 80 °C. HPLC-UV was applied for the determination of concentrations in the kinetic studies, whereas HPLC-MS was used to identify reaction products. The esterification reactions were observed to be reversible. A second-order reversible kinetic model was applied and rate constants were determined. The rate constants demonstrated that cetirizine was esterified about 240 times faster than indomethacin at 80 °C. The shelf-life for cetirizine in a PEG 400 formulation at 25 °C expressed as t(95%) was predicted to be only 30 h. Further, rate constants for esterification of cetirizine in PEG 1000 in relation to PEG 400 decreased by a factor of 10, probably related to increased viscosity. However, it is important to be aware of this drug-excipient interaction, as it can reduce the shelf-life of a low-average molecular weight PEG formulation considerably. PMID:24961667

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

2014-08-01

26

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

27

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

28

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

29

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

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

30

Sonochemical Esterification of Carboxylic Acids in Presence of Sulphuric Acid  

Microsoft Academic Search

A mild and convenient method for the sonochemical esterif ication of aliphatic, aroma tic, ?,?-unsaturated, mono-and di-carboxylic acids in presence of catalytic amounts of sulphuric acid has been reported.

Jitender M. Khurana; Prabhat K. Sahoo; Golak C. Maikap

1990-01-01

31

Recovery of Carboxylic Acids from Fermentation Broth via Acid Springing  

E-print Network

RECOVERY OF CARBOXYLIC ACIDS FROM FERMENTATION BROTH VIA ACID SPRINGING A Thesis by JIPENG DONG Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree... of MASTER OF SCIENCE December 2008 Major Subject: Chemical Engineering RECOVERY OF CARBOXYLIC ACIDS FROM FERMENTATION BROTH VIA ACID SPRINGING A Thesis by JIPENG DONG Submitted to the Office of Graduate Studies of Texas A...

Dong, Jipeng

2010-01-14

32

Carboxylic Acid Unknowns and Titration 90 CARBOXYLIC ACID UNKNOWN  

E-print Network

, and the hydroxide runs out, you won't get full dissolving. · NaHCO3/H2O: An acid-base reaction should lead to solution, but the other unique thing is that acid-base protonation of bicarbonate leads to CO2 bubbles the # of moles of base used. Since the mole/mole stoichiometry is 1 mole of base per 1 mole of acid

Jasperse, Craig P.

33

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

34

Communication: The ionization spectroscopy of mixed carboxylic acid dimers.  

PubMed

We report mass analyzed threshold ionization spectroscopy of supersonically cooled gas phase carboxylic complexes with 9-hydroxy-9-fluorenecarboxylic acid (9HFCA), an analog of glycolic acid. The vibrationally resolved cation spectrum for the 9HFCA complex with formic acid allows accurate determination of its ionization potential (IP), 64,374 ± 8 cm(-1). This is 545 cm(-1) smaller than the IP of 9HFCA monomer. The IPs of 9HFCA complexes with acetic acid and benzoic acid shift by -1133 cm(-1) and -1438 cm(-1), respectively. Density functional calculations confirm that Cs symmetry is maintained upon ionization of the 9HFCA monomer and its acid complexes, in contrast to the drastic geometric rearrangement attending ionization in complexes of 9-fluorene carboxylic acid. We suggest that the marginal geometry changes and small IP shifts are primarily due to the collective interactions among one intramolecular and two intermolecular hydrogen bonds in the dimer. PMID:24160490

Yang, Zhijun; Gu, Quanli; Trindle, Carl O; Knee, J L

2013-10-21

35

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

36

Pyrolysis Mechanisms of Aromatic Carboxylic Acids  

SciTech Connect

Although decarboxylation of carboxylic acids is widely used in organic synthesis, there is limited mechanistic information on the uncatalyzed reaction pathways of aromatic carboxylic acids at 300-400 {degrees} C. The pyrolysis mechanisms of 1,2-(3,3-dicarboxyphenyl)ethane, 1,2-(4,4-dicarboxylphenyl)ethane, 1-(3-carboxyphenyl)-2-(4- biphenyl)ethane, and substituted benzoic acids have been investigated at 325-425 {degrees} C neat and diluted in an inert solvent. Decarboxylation is the dominant pyrolysis path. Arrhenius parameters, substituent effects, and deuterium isotope effects are consistent with decarboxylation by an electrophilic aromatic substitution reaction. Pyrolysis of benzoic acid in naphthalene, as a solvent, produces significant amounts of 1- and 2-phenylnaphthalenes. The mechanistic pathways for decarboxylation and arylation with be presented.

Britt, P.F.; Eskay, T.P.; Buchanan, A.C. III

1997-12-31

37

Cu(I)-catalyzed (11)C carboxylation of boronic acid esters: a rapid and convenient entry to (11)C-labeled carboxylic acids, esters, and amides.  

PubMed

Rapid and direct: the carboxylation of boronic acid esters with (11)CO(2) provides [(11)C]carboxylic acids as a convenient entry into [(11)C]esters and [(11)C]amides. This conversion of boronates is tolerant to diverse functional groups (e.g., halo, nitro, or carbonyl). PMID:22308017

Riss, Patrick J; Lu, Shuiyu; Telu, Sanjay; Aigbirhio, Franklin I; Pike, Victor W

2012-03-12

38

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

39

40 CFR 721.2950 - Carboxylic acid glycidyl esters.  

Code of Federal Regulations, 2010 CFR

40 Protection of Environment 30 2010-07-01 2010-07-01 false Carboxylic acid glycidyl esters. 721.2950...721.2950 Protection of Environment ENVIRONMENTAL PROTECTION... § 721.2950 Carboxylic acid glycidyl esters....

2010-07-01

40

40 CFR 721.2950 - Carboxylic acid glycidyl esters.  

Code of Federal Regulations, 2011 CFR

40 Protection of Environment 31 2011-07-01 2011-07-01 false Carboxylic acid glycidyl esters. 721.2950...721.2950 Protection of Environment ENVIRONMENTAL PROTECTION... § 721.2950 Carboxylic acid glycidyl esters....

2011-07-01

41

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

42

Omega-3-carboxylic Acid (epanova) for hypertriglyceridemia.  

PubMed

Hypertriglyceridemia is a prevalent yet under-addressed condition, often seen in association with uncontrolled diabetes mellitus, obesity, and physical inactivity. The control of triglyceride (TG) levels is essential to prevent the development of coronary artery disease and pancreatitis associated with hypertriglyceridemia. Omega-3-carboxylic acid (Epanova) is the third prescription omega-3 fatty acid product approved in the United States as an adjunct to diet for treating severe hypertriglyceridemia (?500?mg/dL). At the approved dosage, it reduced baseline serum TG levels by 25-30% in a placebo-controlled study. It reduced serum TG levels by an additional 8-15% in patients who were already taking statin therapy. It appeared to have a better bioavailability profile compared with an equivalent dose of omega-3-acid ethyl ester (Lovaza) in both low-fat and high-fat diets. However, evidence behind the effects of omega-3-carboxylic acid on cardiovascular morbidity and mortality, and pancreatitis risk, is lacking. Overall, it is well tolerated, but may induce common gastrointestinal side effects, such as abdominal pain, nausea, and diarrhea. At this time, omega-3-carboxylic acid is an alternative adjunct therapy (in addition to diet) for hypertriglyceridemia. Its potential clinical benefits over other omega-3 formulations have yet to be evaluated. PMID:25580706

Zhao, Alan; Lam, Sum

2015-01-01

43

Comparison of silatrane, phosphonic acid, and carboxylic acid functional groups for attachment of porphyrin sensitizers to TiO2 in photoelectrochemical cells.  

PubMed

A tetra-arylporphyrin dye was functionalized with three different anchoring groups used to attach molecules to metal oxide surfaces. The physical, photophysical and electrochemical properties of the derivatized porphyrins were studied, and the dyes were then linked to mesoporous TiO2. The anchoring groups were ?-vinyl groups bearing either a carboxylate, a phosphonate or a siloxy moiety. The siloxy linkages were made by treatment of the metal oxide with a silatrane derivative of the porphyrin. The surface binding and lability of the anchored molecules were studied, and dye performance was compared in a dye-sensitized solar cell (DSSC). Transient absorption spectroscopy was used to study charge recombination processes. At comparable surface concentration, the porphyrin showed comparable performance in the DSSC, regardless of the linker. However, the total surface coverage achievable with the carboxylate was about twice that obtainable with the other two linkers, and this led to higher current densities for the carboxylate DSSC. On the other hand, the carboxylate-linked dyes were readily leached from the metal oxide surface under alkaline conditions. The phosphonates were considerably less labile, and the siloxy-linked porphyrins were most resistant to leaching from the surface. The use of silatrane proved to be a practical and convenient way to introduce the siloxy linkages, which can confer greatly increased stability on dye-sensitized electrodes with photoelectrochemical performance comparable to that of the other linkers. PMID:23959453

Brennan, Bradley J; Llansola Portolés, Manuel J; Liddell, Paul A; Moore, Thomas A; Moore, Ana L; Gust, Devens

2013-10-21

44

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

NASA Astrophysics Data System (ADS)

Molecular dynamics and molecular mechanics methods have been used to investigate additive-polymer interfacial properties in single walled carbon nanotube – polyethylene and single walled carbon nanotube – polyacrylonitrile composites. Properties such as the interfacial shear stress and bonding energy are similar for the two composites. In contrast, functionalizing the single walled carbon nanotubes 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 single walled carbon nanotube wall.

Haghighatpanah, Shayesteh; Bohlén, Martin; Bolton, Kim

2014-09-01

45

A simple and efficient method of preparing ?-bromo carboxylic acids  

Microsoft Academic Search

A new and convenient method for ?-bromination of aliphatic carboxylic acids is reported. Heating carboxylic acids for 16 hours at 85 °C in trifluoroacetic acid with 1.5 equivalents of N-bromosuccinimide and a catalytic amount of concentrated H2SO4 leads to good yields of the respective ?-bromocarboxylic acids.

Lian Hao Zhang; Jianxin Duan; Yuelian Xu; William R. Dolbier

1998-01-01

46

Palladium-catalyzed decarboxylative trifluoroethylation of aryl alkynyl carboxylic acids.  

PubMed

A trifluoroethylation of alkynes through a palladium-catalyzed decarboxylative coupling reaction was developed. When alkynyl carboxylic acids and ICH2CF3 were allowed to react with [Pd(?(3)-allyl)Cl]2/XantPhos and Cs2CO3 in N,N-dimethylformamide (DMF) at 80 °C for 1 h, the desired products were formed in good yields. This catalytic system showed high functional group tolerance. PMID:24628537

Hwang, Jinil; Park, Kyungho; Choe, Juseok; Min, Hongkeun; Song, Kwang Ho; Lee, Sunwoo

2014-04-01

47

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

48

Characterization and diagenesis of strong-acid carboxyl groups in humic substances  

USGS Publications Warehouse

A small fraction of carboxylic acid functional groups in humic substances are exceptionally acidic with pKa values as low as 0.5. A review of acid-group theory eliminated most models and explanations for these exceptionally acidic carboxyl groups. These acidic carboxyl groups in Suwannee River fulvic acid were enriched by a 2-stage fractionation process and the fractions were characterized by elemental, molecular-weight, and titrimetric analyses, and by infrared and 13C- and 1H-nuclear magnetic resonance spectrometry. An average structural model of the most acidic fraction derived from the characterization data indicated a high density of carboxyl groups clustered on oxygen-heterocycle alicyclic rings. Intramolecular H-bonding between adjacent carboxyl groups in these ring structures enhanced stabilization of the carboxylate anion which results in low pKa1 values. The standard, tetrahydrofuran tetracarboxylic acid, was shown to have similar acidity characteristics to the highly acidic fulvic acid fraction. The end products of 3 known diagenetic pathways for the formation of humic substances were shown to result in carboxyl groups clustered on oxygen-heterocycle alicyclic rings.

Leenheer, J.A.; Wershaw, R.L.; Brown, G.K.; Reddy, M.M.

2003-01-01

49

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

50

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

51

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

52

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

Code of Federal Regulations, 2010 CFR

...Oxabicycloalkane carboxylic acid alkanediyl ester (generic). 721.10142 Section 721...Oxabicycloalkane carboxylic acid alkanediyl ester (generic). (a) Chemical substance...oxabicycloalkane carboxylic acid alkanediyl ester (PMN P-06-199) is subject to...

2010-07-01

53

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

54

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

55

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

56

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

57

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

58

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

59

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

60

Microwave-Assisted Esterification of Diverse Carboxylic Acids and Chiral Amino Acids  

Microsoft Academic Search

A facile and efficient synthetic method of esters from their corresponding carboxylic acids and amino acids is described. The esterification reaction of carboxylic acids and amino acids could be greatly accelerated under microwave irradiation because the reactions described in this article took place in only 5 min with almost quantitative yields, and distinct acidity of catalytic acids was well tolerated. Unlike

Qian Yang; Xiao-jian Wang; Zhi-yu Li; Li Sun; Qi-dong You

2008-01-01

61

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

Code of Federal Regulations, 2014 CFR

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

2014-07-01

62

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

Code of Federal Regulations, 2013 CFR

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

2013-07-01

63

Amine-based systems for carboxylic acid recovery  

SciTech Connect

Several carboxylic acids are prominent commercial products, and their number and importance will probably grow. Getting these acids out of aqueous solution is necessary in petrochemical manufacture, fermentation, and the environmentally and economically important recovery from waste streams. In this paper, the authors discuss the methods possible to extract acids such as citric, lactic, and succinic from complex mixtures. Carboxylic acids are also readily made by fermentation and are among the most attractive substances that could be manufactured from biomass. Branches of this cycle lead to acetic, lactic, propionic, and formic acids, among others. Carboxylic acids are promising intermediates in a bioprocessing complex, because the oxygen of the biomass is placed in a form that is useful for further reaction with many other products. Citric acid is manufactured on a large scale by fermentation, and lactic and fumaric acids, among others, were manufactured that way in the past.

King, C.J.

1992-05-01

64

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...

65

Durable press finishing of cotton fabrics with polyamino carboxylic acids.  

PubMed

In this study, a polyamino carboxylic acid was synthesized by reaction of a commercial polyvinylamine and bromoacetic acid. The reaction product was used for crosslinking of cotton fabric by a pad-dry-cure process. Crosslinking of the finished cotton occurred via the formation of ester bonds between the carboxylic groups of the polyamino carboxylic acid and the hydroxyl groups of cellulose. Ester bonds were confirmed by appearance of the corresponding absorbance at 1730 cm(-1) in the FTIR spectrum of the finished cotton. The created durable press effect on the finished cotton with polyamino carboxylic acid was evaluated by measuring the wrinkle recovery angle (WRA). Impact of this finishing agent on the physical properties of the cotton was studied by evaluating the tensile strength and whiteness index, and softness of the finished cotton. The easy care effect was durable against laundering. Softness, whiteness, and tensile strength of the finished cotton have not changed significantly. PMID:24750758

Dehabadi, Vahid Ameri; Buschmann, Hans-Jürgen; Gutmann, Jochen Stefan

2012-06-20

66

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

67

Conversion of sugarcane bagasse to carboxylic acids under thermophilic conditions  

E-print Network

CONVERSION OF SUGARCANE BAGASSE TO CARBOXYLIC ACIDS UNDER THERMOPHILIC CONDITIONS A Dissertation by ZHIHONG FU Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements... for the degree of DOCTOR OF PHILOSOPHY May 2007 Major Subject: Chemical Engineering CONVERSION OF SUGARCANE BAGASSE TO CARBOXYLIC ACIDS UNDER THERMOPHILIC CONDITIONS A Dissertation by ZHIHONG FU Submitted to the Office...

Fu, Zhihong

2009-05-15

68

Palladium-catalyzed asymmetric hydrogenation of furan carboxylic acids  

Microsoft Academic Search

Enantioselective hydrogenation of aromatic and heteroaromatic compounds is the field where chirally modified metal hydrogenation catalysts have the biggest potential compared to homogeneous chiral transition metal complexes. Here we report the hydrogenation of furan and benzofuran carboxylic acids over a cinchonidine-modified 5 wt% Pd\\/Al2O3 catalyst. (S)-Tetrahydrofuran-2-carboxylic acid was synthesized in 4 h at rt and 30 bar with 95% yield and

Mihaela Maris; Wolf-Rüdiger Huck; Tamas Mallat; Alfons Baiker

2003-01-01

69

An efficient and general method for resolving cyclopropene carboxylic acids  

Microsoft Academic Search

A general method is described for the resolution of cycloprop-2-ene carboxylic acids via diastereomeric N-acyloxazolidines prepared from enantiomerically pure oxazolidinones. Although a number of oxazolidinones were shown to resolve cyclopropene carboxylic acids, the oxazolidinones of S-phenylalaninol, S-phenylglycine and (1S,2R)-cis-1-amino-2-indanol are optimal in terms of resolving power and cost effectiveness. Separations were performed using simple flash chromatography, and because there is

Lian-an Liao; Fan Zhang; Ni Yan; James A. Golen; Joseph M. Fox

2004-01-01

70

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

71

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

72

A Convenient Procedure for Esterification of Thermally Unstable Carboxylic Acids  

Microsoft Academic Search

There are many new methods for esterifying carboxylic acids but some have specific limitations such as harsh conditions, inconvenience of procedure, expense and inaccessibility of reagents we have prepared several novel bicyclic ?–keto acids as intermediates for the synthesis of heterocyclic systems. Since these ?–keto acids readily decarboxylate on heating, esterification by a simple low temperature procedure was necessary.

J. Fairhurst; D. C. Horwell

1976-01-01

73

62 Langmuir 1987,3, 62-76 Reactivity of Carboxylic Acid and Ester Groups in the  

E-print Network

on structure in ways having no analogy in reactions in solution. For example, the rate of base62 Langmuir 1987,3, 62-76 Reactivity of Carboxylic Acid and Ester Groups in the Functionalized Interfacial Region of "Polyethylene Carboxylic Acid" (PE-C02H) and Its Derivatives: Differentiation

Prentiss, Mara

74

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

75

IV. -Amino Acids: carboxyl and amino groups bonded to -Carbo n A. Acid/Base properties  

E-print Network

IV. -Amino Acids: carboxyl and amino groups bonded to -Carbo n A. Acid/Base properties 1. carboxyl group is proton donor ! weak acid 2. amino group is proton acceptor ! weak base 3. At physiological p natural amino acids (few exceptions) 2. 20 different R groups C. Classification based on R-group - know

Frey, Terry

76

Solvent extraction of rare-earth metals by carboxylic acids  

SciTech Connect

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 chloride solutions was also investigated. The dependence of the extraction properties of the carboxylic acids on the atomic number of the lanthanide shows a definite relationship to the steric bulk of the carboxylic acid molecule quantified by means of the steric parameter, E{sub s}{prime} of the substituent alkyl group. The stoichiometries of the extracted complexes for representative light (La), middle (Gd) and heavy (Lu) rare-earth metals were investigated by the slope-analysis technique for a sterically hindered acid (Versatic 10 acid; -E{prime}{sub s} = 3.83) and an acid with low steric hindrance (3-cyclohexylpropanoic acid; -E{prime}{sub s} = 0.28). 14 refs., 13 figs., 3 tabs.

Preez, A.C. du; Preston, J.S. [Mintek, Randburg (South Africa)

1992-04-01

77

Separation of aromatic carboxylic acids using quaternary ammonium salts on reversed-phase HPLC. 1. Separation behavior of aromatic carboxylic acids  

SciTech Connect

In order to develop separation processes and analytical methods for aromatic carboxylic acids for the coal oxidation products, the separation behavior of aromatic carboxylic acids on a reversed-phase HPLC using eluent containing quaternary ammonium salt has been investigated. The retention mechanism of aromatic carboxylic acids was discussed on the basis of both ion-pair partition model and ion-exchange model. The retention behavior of aromatic carboxylic acids possessing one (or two) carboxylic acid group(s) followed the ion-pair partition model, where linear free energy relationship was observed between the capacity factor and the extraction equilibrium constants of benzoic acid and naphthalene carboxylic acid. Besides, the retention behavior followed ion-exchange model with increasing the number of carboxylic acids, where the capacity factor of benzene polycarboxylic acids is proportional to the association constants between aromatic acids and quaternary ammonium ions calculated on the basis of an electrostatic interaction model.

Kawamura, K.; Okuwaki, A.; Verheyen, T.; Perry, G.J. [Tohoku University, Miyagi (Japan). Graduate School of Environmental Studies

2006-02-15

78

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

79

Silver-catalyzed protodecarboxylation of heteroaromatic carboxylic acids.  

PubMed

A simple and highly efficient protodecarboxylation procedure for a variety of heteroaromatic carboxylic acids catalyzed by Ag(2)CO(3) and AcOH in DMSO is described. This methodology can also perform the selective monoprotodecarboxylation of several aromatic dicarboxylic acids. PMID:19924891

Lu, Pengfei; Sanchez, Carolina; Cornella, Josep; Larrosa, Igor

2009-12-17

80

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...

81

The role of carboxylic acids in TALSQueak separations  

SciTech Connect

Recent reports have indicated TALSPEAK-type separations chemistry can be improved through the replacement of bis-2-ethyl(hexyl) phosphoric acid (HDEHP) and diethylenetriamine-N,N,N,N,N-pentaacetic acid (DTPA) with the weaker reagents 2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA), respectively. This modified TALSPEAK has been provided with an adjusted acronym of TALSQueak (Trivalent Actinide Lanthanide Separation using Quicker Extractants and Aqueous Komplexes). Among several benefits, TALSQueak chemistry provides more rapid phase transfer kinetics, is less reliant on carboxylic acids to mediate lanthanide extraction and allows a simplified thermodynamic description of the separations process that generally requires only parameters available in the literature to describe metal transfer. This manuscript focuses on the role of carboxylic acids in aqueous ternary (M-HEDTA-carboxylate) complexes, americium/lanthanide separations, and extraction kinetics. Spectrophotometry (UV-vis) of the Nd hypersensitive band indicates the presence of aqueous ternary species (K111 = 1.83 {+-} 0.01 at 1.0 M ionic strength, Nd(HEDTA) + Lac <-> Nd(HEDTA)Lac). Varying the carboxylic acid does not have a significant impact on Ln/Am separations or extraction kinetics. TALSqueak separations come to equilibrium in five minutes at the conventional operational pH of 3.6 using only 0.1 M total lactate or citrate.

Braley, Jenifer C.; Carter, Jennifer C.; Sinkov, Sergey I.; Nash, Ken L.; Lumetta, Gregg J.

2012-04-13

82

Synthesis and HPLC evaluation of carboxylic acid phases on a hydride surface.  

PubMed

Three organic moieties containing carboxylic acid functional groups are attached to a particulate silica surface through silanization/hydrosilation. Two compounds (undecylenic acid and 10-undecynoic acid) have 11 carbon chains and the other is a five-carbon acid (pentenoic acid). Bonding is confirmed through carbon elemental analysis, diffuse reflectance infrared fourier transform spectroscopy, and carbon-13 and silicon-29 CP-MAS NMR spectroscopy. The bonded phases are tested by HPLC using PTH amino acids, nucleic acids, theophylline-related compounds, anilines, benzoic acid compounds, choline, and tobramycin. The latter two compounds are used to investigate the aqueous normal phase properties of the three bonded materials. PMID:16830499

Pesek, Joseph J; Matyska, Maria T; Gangakhedkar, Surekha; Siddiq, Rukhsana

2006-04-01

83

(2S)-1-Carbamoylpyrrolidine-2-carboxylic acid.  

PubMed

In the title compound, also known as N-carbamoyl-L-proline, C(6)H(10)N(2)O(3), the pyrrolidine ring adopts a half-chair conformation, whereas the carboxyl group and the mean plane of the ureide group form an angle of 80.1 (2) degrees. Molecules are joined by N-H...O and O-H...O hydrogen bonds into cyclic structures with graph-set R(2)(2)(8), forming chains in the b-axis direction that are further connected via N-H...O hydrogen bonds into a three-dimensional network. PMID:17478918

Seijas, Luis E; Delgado, Gerzon E; Mora, Asiloé J; Bahsas, Ali; Briceño, Alexander

2007-05-01

84

Porosity, crystal phase, and morphology of nanoparticle derived alumina as a function of the nanoparticle's carboxylate substituent  

Microsoft Academic Search

Carboxylate-alumoxanes are a simple to prepare class of chemically functionalized alumina nanoparticles. The identity of the carboxylate group has a direct effect on the microstructure and temperature of phase conversion for their pyrolysis to alumina bodies. A series of carboxylate-alumoxanes with varying chain length of the organic substituent (organic content) have been investigated: acetic acid alumoxane (A-A), methoxyacetic acid alumoxane

Christopher D. Jones; Andrew R. Barron

2007-01-01

85

Sensing of enantiomeric excess in chiral carboxylic acids.  

PubMed

Cinchona alkaloids (quinine, quinidine, cinchonine, cinchonidine) alkylated at N(1) with chloromethyl anthracene can serve as fluorescent sensors for chiral carboxylic acids. These cinchona ammonium salts are shown to bind chiral carboxylic acids while displaying an increase in fluorescence intensity that can be utilized in determination of enantiomeric excess (ee). Sensor arrays composed of four cinchona ammonium salts are used for quantitative analysis of ee in several non-steroidal anti-inflammatory drugs (NSAIDs), such as enantiomers of ibuprofen, ketoprofen, and naproxen. PMID:25720499

Akdeniz, Ali; Mosca, Lorenzo; Minami, Tsuyoshi; Anzenbacher, Pavel

2015-03-17

86

Carboxylic acids and skeletal muscle chloride channel conductance: effects on the biological activity induced by the introduction of an aryloxyalkyl group alpha to the carboxylic function of 4-chloro-phenoxyacetic acid.  

PubMed

2-(4-Chloro-phenoxy)propanoic and 2-(4-chloro-phenoxy)butanoic acids are compounds known to block chloride membrane conductance in rat striated muscle by interaction with a specific receptor. In the present study, a series of chiral analogues has been prepared and tested to evaluate the influence of a second aryloxy moiety introduced in the side-chain at a variable distance from the stereogenic centre. The results show that this chemical modification is detrimental for biological activity which, however, is increased by lengthening the alkyl chain up to three methylenic groups, then decreases to remain constant in the next analogues of the series. A possible explanation for this is proposed on the basis of steric effects and/or different approach of the molecules to the receptor. PMID:11718267

Carbonara, G; Fracchiolla, G; Loiodice, F; Tortorella, P; Conte-Camerino, D; De Luca, A; Liantonio, A

2001-10-01

87

More on Effects Controlling Carboxylic Acidity.  

ERIC Educational Resources Information Center

Gas phase acidity data shown are offered to writers of elementary organic chemistry texts for replacement of the aqueous phase data that are universally used. Relative acidities in the gas phase are controlled virtually exclusively by enthalpic factors. Structural-energetic explanations of acidic trends can therefore be used. (SK)

Schwartz, Lowell M.

1981-01-01

88

Decarboxylative homocoupling of (hetero)aromatic carboxylic acids.  

PubMed

A variety of hetero(aromatic) carboxylic acids are shown to undergo decarboxylative homocoupling, mediated by a Pd/Ag system. This novel methodology for the synthesis of symmetrical biaryls avoids the use of haloarenes and organometallic compounds as starting materials. PMID:20882244

Cornella, Josep; Lahlali, Hicham; Larrosa, Igor

2010-11-21

89

A Simple Method for the Separation of Triterpene Carboxylic Acids  

Microsoft Academic Search

A polybutadiene-coated alumina column has been found to resolve a closely related mixture of naturally occurring triterpene carbox-ylic acids much more efficiently than conventional octadecylsilyl-bonded (C18) silica columns. Further, this separation could be achieved without ion-pairing, ion-suppression or other buffering techniques.

Mark Tischler; John H. Cardellina II

1993-01-01

90

Direct, High-Yield Esterification of Carboxylic Acids  

Microsoft Academic Search

Mild esterification methods are of considerable interest in the synthesis and manipulation of many natural products. Described herein is a new convenient method for the direct, high-yield conversion from equimolar amounts of carboxylic acids and alcohols into esters under mild conditions.

Sunggak Kim; Sungbong Yang

1981-01-01

91

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.

92

Stable molecular configuration in crystalline carboxylic acids  

NASA Astrophysics Data System (ADS)

The stable (lower enthalpy) molecular configurations of propionic, butyric, Jeric and lauric acids in the crystalline state have been examined via their atom-atom potentials. It was found that the cis configuration is more stable than the trans configuration for propionic, butyric and valeric acids, and that the trans configuration is more stable than the cis configuration for lauric acid, in accord with a previous IR spectral analysis. The potential energy of benzoic acid was recalculated using the positions of atoms given by Speakman, and indicates that the A form is more stable than the B form, in agreement with the results of previous work.

Hayashi, Soichi; Umemura, Junzo; Nakamura, Ryoko

1980-12-01

93

40 CFR 721.4097 - 7-Oxabicyclo[4.1.0]heptane-3-carboxylic acid, methyl ester.  

Code of Federal Regulations, 2010 CFR

...heptane-3-carboxylic acid, methyl ester. 721.4097 Section 721.4097 ...heptane-3-carboxylic acid, methyl ester. (a) Chemical substance and significant...heptane-3-carboxylic acid, methyl ester (PMN P-98-101) is subject to...

2010-07-01

94

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

Code of Federal Regulations, 2011 CFR

40 Protection of Environment 31 2011-07-01 2011-07-01 false Carboxylic acids, (C6-C9) branched and...721.2088 Protection of Environment ENVIRONMENTAL PROTECTION... § 721.2088 Carboxylic acids, (C6-C9) branched...

2011-07-01

95

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

Code of Federal Regulations, 2010 CFR

40 Protection of Environment 30 2010-07-01 2010-07-01 false Carboxylic acids, (C6-C9) branched and...721.2088 Protection of Environment ENVIRONMENTAL PROTECTION... § 721.2088 Carboxylic acids, (C6-C9) branched...

2010-07-01

96

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

97

Esterification of carboxylic acids employing 2-fluoro-2, 2-dinitroethylsulfuric acid  

Microsoft Academic Search

The esterification of carboxylic acids of variable structure was studied employing 2-fluoro-2, 2-dinitroethylsulfuric acid and it was shown that this reaction is a general method for the preparation of 2-fluoro-2, 2-dinitroethanol esters.

L. T. Eremenko; G. F. Oreshko; L. B. Romanova; M. A. Fadeev

1975-01-01

98

Direct conversion of carboxylate salts to carboxylic acids via reactive extraction  

E-print Network

of condensed vapor and liquid from the round-bottom flask were collected for GC analysis. Also, ammonia vapors were trapped by boric acid with methyl red as an indicator in the tail gas trap. The amount of captured ammonia was determined by titration... ammonia was collected by boric acid solution with methyl red indicator (Figure 2-2). All extraction experiments were conducted using 100-mL flasks. Extractant and the aqueous solution with the initial concentration of ammonium carboxylate salts were...

Xu, Xin

2008-10-10

99

Resolution of Carboxylic Acids Using Copper (I)-Promoted Removal of Propargylic Esters Under Neutral Conditions  

PubMed Central

A method for the optical resolution of carboxylic acids is described. Condensation of racemic carboxylic acids with chiral terminal propargyl alcohols gave separable diastereomeric esters. Chromatographic separation followed by heating the individual diastereomers in methanol with catalytic copper (I) halide regenerated the carboxylic acids in good yields and in enantiomeric ratios of ?94%. This method is particularly useful for the resolution of carboxylic acids that are incompatible with conventional ester hydrolysis. PMID:21491889

Ghosh, Partha

2013-01-01

100

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

Code of Federal Regulations, 2014 CFR

...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

101

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

102

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

103

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

104

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

105

A new procedure for preparation of carboxylic acid hydrazides.  

PubMed

The standard method for preparing carboxylic acid hydrazides is hydrazinolysis of esters in alcoholic solutions. However, when applied to alpha,beta-unsaturated esters, the main product typically is the pyrazolidinone resulting from an undesired Michael-type cyclization. Other alternative methodologies reported for direct preparation of hydrazides from acids are inefficient. We developed an efficient and general process, involving preforming activated esters and/or amides followed by reaction with hydrazine, for the preparation of hydrazides including those of alpha,beta-unsaturated acids. This process gives the desired hydrazides in excellent yield and purity under mild conditions. PMID:12492358

Zhang, Xini; Breslav, Michael; Grimm, Jeffrey; Guan, Kailin; Huang, Aihua; Liu, Fuqiang; Maryanoff, Cynthia A; Palmer, David; Patel, Mitul; Qian, Yun; Shaw, Charles; Sorgi, Kirk; Stefanick, Stephen; Xu, Dawei

2002-12-27

106

Carboxylic Acids as Indicators of Parent Body Conditions  

NASA Technical Reports Server (NTRS)

Alpha-hydroxy and alpha-amino carboxylic acids found on the Murchison meteorite are deuterium enriched. It is postulated that they arose from a common interstellar scurce: the reaction of carbonyl compounds in an aqueous mixture containing HCN and NH3. Carbonyl compounds react with HCN to form alpha-hydroxy nitriles, RR'CO + HCN right and left arrow RR'C(OH)CN. If ammonia is also present, the alpha-hydroxy nitriles will exist in equilibrium with the alpha-amino nitriles, RR'C(OH)CN + NH3 right and left arrow - RRCNH2CN + H2O. Both nitrites are hydrolyzed by water to form carboxylic acids: RR'C(OH)CN + H2O yields RR'C(OH)CO2H and RR'C(NH2)CN + H2O yields RR'C(NH2)CO2H.

Lerner N. R.; Chang, Sherwood (Technical Monitor)

1995-01-01

107

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

108

Biocatalytic amidation of carboxylic acids and their antinemic activity  

Microsoft Academic Search

A series of novel N-alkyl substituted amides, synthesized by enzyme catalysis, were evaluated against root-knot nematode, Meloidogyne incognita and found to have potential antinemic activity. The corresponding amides were prepared by the condensation of equimolar amounts of carboxylic acids with different alkyl amines in the presence of Candida antarctica lipase at 60–90°C in 16–20 h. The reactions were carried out

Abinesh Bose; Najam Akhtar Shakil; Pankaj; Jitendra Kumar; Manish K. Singh

2010-01-01

109

Nasal pungency and odor of homologous aldehydes and carboxylic acids  

Microsoft Academic Search

Airborne substances can stimulate both the olfactory and the trigeminal nerve in the nose, giving rise to odor and pungent\\u000a (irritant) sensations, respectively. Nose, eye, and throat irritation constitute common adverse effects in indoor environments.\\u000a We measured odor and nasal pungency thresholds for homologous aliphatic aldehydes (butanal through octanal) and carboxylic\\u000a acids (formic, acetic, butanoic, hexanoic, and octanoic). Nasal pungency

J. Enrique Cometto-MuÊiz; William S. Cain; Michael H. Abraham

1998-01-01

110

A new enzymatic function in the melanogenic pathway. The 5,6-dihydroxyindole-2-carboxylic acid oxidase activity of tyrosinase-related protein-1 (TRP1).  

PubMed

Since the characterization of 5,6-dihydroxyindole-2-carboxylic acid (DHICA) as a major melanogenic intermediate, the fate of this compound and the mechanisms of its incorporation into the melanin polymer have become major issues in the study of melanogenesis. DHICA is a stable dihydroxyindole with a low rate of spontaneous oxidation, suggesting that enzymatic mechanism(s) might contribute to its evolution. The most obvious candidates are the melanosomal tyrosinases. We have recently shown that mouse melanosomes contain two electrophoretically distinct tyrosinase isoenzymes, termed low electrophoretic mobility tyrosinase (LEMT) and high electrophoretic mobility tyrosinase (HEMT), that can be resolved and purified. In this study, we report immunological evidence indicating that LEMT corresponds to the protein encoded by the brown locus (termed tyrosinase-related protein-1, TRP1), while HEMT corresponds to the tyrosinase encoded by the albino locus. We have compared the ability of both isoenzymes to catalyze DHICA evolution as determined by high performance liquid chromatography; although LEMT is a relatively poor tyrosine hydroxylase and DOPA oxidase as compared to HEMT, it was readily able to accelerate DHICA consumption concomitant with the production of a brownish product. However, the DHICA conversion activity of HEMT was barely detectable. The ability of purified LEMT to catalyze DHICA conversion could be almost completely abolished by treatment with heat or trypsin, and was inhibited in a concentration dependent way by the tyrosinase inhibitor 2-phenylthiourea and by L-tyrosine. Moreover, in the presence of low concentration of ascorbate, the DHICA conversion activity of LEMT displayed a lag period which was progressively longer at higher ascorbate concentrations. Based on the relationship between ascorbate added, enzyme activity, and lag period, it is very likely that the DHICA converting activity is indeed a DHICA oxidase activity. This was further proven by the demonstration that the product reacts rapidly and efficiently with the quinone trapping reagent 3-methyl-2-benzothiazolinone hydrazone, yielding a colored adduct similar to the one obtained with DOPAquinone. The DHICA oxidase activity of LEMT displayed a Km for DHICA of about 0.8 mM, as compared to 1.9 mM for L-DOPA and 0.23 nM for L-tyrosine. These results suggest that TRP1, the product of the brown locus, is indeed a tyrosinase with DHICA oxidase activity. However, as opposed to the tyrosinase encoded by the albino locus, TRP1's role in melanogenesis could be more directly related to DHICA metabolism than to the first steps of the pathway. PMID:8027058

Jiménez-Cervantes, C; Solano, F; Kobayashi, T; Urabe, K; Hearing, V J; Lozano, J A; García-Borrón, J C

1994-07-01

111

Approaches for regeneration of amine-carboxylic acid extracts  

SciTech Connect

Extraction processes based on reversible chemical complexation can be useful for separation of polar organics from dilute solution. Tertiary amines are effective extractants for the recovery of carboxylic acids from aqueous solution. The regeneration of aminecarboxylic acid extracts is an important step which strongly influences the economic viability of the separation process. Several regeneration methods are critically reviewed, and the factors that affect swing regeneration processes, including temperature-swing, diluent composition-swing and pH-swing with a volatile base are discussed. Interest in this area comes from interest in treatment of waste streams, particularly in petrochemical and fermentation manufacture.

Dai, Y.; King, C.J.

1995-07-01

112

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

113

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

114

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

115

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

NASA Technical Reports Server (NTRS)

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

Negron-Mendoza, A.; Ponnamperuma, C.

1976-01-01

116

Efficient esterification of carboxylic acids and phosphonic acids with trialkyl orthoacetate in ionic liquid  

Microsoft Academic Search

An operationally simple, inexpensive, efficient, and environmentally friendly esterification of various carboxylic acids, phosphonic acids, and phosphinic acids with triethyl orthoacetate or trimethyl orthoacetate under neutral conditions in a typical room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, was successfully carried out to provide the corresponding ethyl esters or methyl esters in high yields.

Tomonori Yoshino; Satomi Imori; Hideo Togo

2006-01-01

117

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

118

Fluorescent carboxylic and phosphonic acids: comparative photophysics from solution to organic nanoparticles.  

PubMed

Phosphonic and carboxylic fluorescent nanoparticles have been fabricated by direct reprecipitation in water. Their fluorescence properties strongly differ from those of the corresponding esters where strong H-bonding formation is prohibited. Comparative experiments between the two acid derivatives, differing only in their acid functions while keeping the same alkyl chain, have evidenced the peculiar behavior of the phosphonic acid derivative compared to its carboxylic analog. A dramatic emission quenching for the phosphonic acid in aprotic toluene could be observed while a fivefold increase in the fluorescence signal was observed for molecules assembled as nanoparticles. Such properties have been attributed on the theoretical basis to the formation of folded conformers in solution, leading to deactivation of the radiative excited state through intramolecular H-bonding. These studies evidence for the first time through time-resolved fluorescence measurements the stronger H-donating character of phosphonic acids compared to the carboxylic ones, and provide information on the degree of structural heterogeneity within the nanoparticles. They should pave the way for the rational fabrication of chelating acid fluorophores, able to complex metal oxides to yield stiff hybrid magnetofluorescent nanoparticles which are attracting considerable attention in the growing fields of bimodal imaging and vectorization applications. PMID:23799511

Faucon, Adrien; Lenk, Romaric; Hémez, Julie; Gautron, Eric; Jacquemin, Denis; Le Questel, Jean-Yves; Graton, Jérôme; Brosseau, Arnaud; Ishow, Eléna

2013-08-14

119

Sensing Remote Chirality: Stereochemical Determination of ?-, ?-, and ?-Chiral Carboxylic Acids.  

PubMed

Determining the absolute stereochemisty of small molecules bearing remote nonfunctionalizable stereocenters is a challenging task. Presented is a solution in which appropriately substituted bis(porphyrin) tweezers are used. Complexation of a suitably derivatized ?-, ?-, or ?-chiral carboxylic acid to the tweezer induces a predictable helicity of the bis(porphyrin), which is detected as a bisignate Cotton Effect (ECCD). The sign of the ECCD curve is correlated with the absolute stereochemistry of the substrate based on the derived working mnemonics in a predictable manner. PMID:25684753

Tanasova, Marina; Anyika, Mercy; Borhan, Babak

2015-03-27

120

Structural characterization of 1,3-propanedithiols that feature carboxylic acids: Homologues of mercury chelating agents ?  

PubMed Central

The molecular structures of a series of 1,3-propanedithiols that contain carboxylic acid groups, namely rac- and meso-2,4-dimercaptoglutaric acid (H4DMGA) and 2-carboxy-1,3-propanedithiol (H3DMCP), have been determined by X-ray diffraction. Each compound exhibits two centrosymmetric intermolecular hydrogen bonding interactions between pairs of carboxylic acid groups, which result in a dimeric structure for H3DMCP and a polymeric tape-like structure for rac- and meso-H4DMGA. Significantly, the hydrogen bonding motifs observed for rac- and meso-H4DMGA are very different to those observed for the 1,2-dithiol, rac-2,3-dimercaptosuccinic acid (rac-H4DMSA), in which the two oxygen atoms of each carboxylic acid group hydrogen bond to two different carboxylic acid groups, thereby resulting in a hydrogen bonded sheet-like structure rather than a tape. Density functional theory calculations indicate that 1,3-dithiolate coordination to mercury results in larger S–Hg–S bond angles than does 1,2-dithiolate coordination, but these angles are far from linear. As such, ?2-S2 coordination of these dithiolate ligands is expected to be associated with mercury coordination numbers of greater than two. In vivo studies demonstrate that both rac-H4DMGA and H3DMCP reduce the renal burden of mercury in rats, although the compounds are not as effective as either 2,3-dimercaptopropane-1-sulfonic acid (H3DMPS) or meso-H4DMSA. PMID:24187425

Sattler, Wesley; Palmer, Joshua H.; Bridges, Christy C.; Joshee, Lucy; Zalups, Rudolfs K.; Parkin, Gerard

2013-01-01

121

O?Arylation of Carboxylic Acids using (Phenyl)[2?(trimethylsilyl)phenyl]iodonium Triflate as a Precursor of Arynes  

Microsoft Academic Search

Using (phenyl)[2?(trimethylsilyl)phenyl]iodonium triflate as a precursor of arynes, Larock's method for O?arylation of carboxylic acids and arynes was developed. A variety of acids including simple aliphatic carboxylic acids, aromatic carboxylic acids, allenoic acids, and p?toluenesulfonic acid under mild reaction conditions could generate the aryl esters.

Jian Xue; Xian Huang

2007-01-01

122

Thermodynamic properties of furan-2-carboxylic and 3-(2-furyl)-2-propenoic acids  

NASA Astrophysics Data System (ADS)

The standard enthalpies of combustion, formation, fusion, and sublimation of crystalline furan-2-carboxylic and 3-(2-furyl)-2-propenoic acids are determined by experimental methods and recalculated to 298 K. The possibility of using additive calculation schemes based on the principle of group contributions to calculate the standard enthalpies of vaporization and formation of substances with similar combinations of functional fragments in the gas phase is analyzed.

Sobechko, I. B.; Van-Chin-Syan, Yu. Ya.; Kochubei, V. V.; Prokop, R. T.; Velychkivska, N. I.; Gorak, Yu. I.; Dibrivnyi, V. N.; Obushak, M. D.

2014-12-01

123

Development of a high-performance liquid chromatography method for the simultaneous quantification of quinoxaline-2-carboxylic acid and methyl-3-quinoxaline-2-carboxylic acid in animal tissues  

Microsoft Academic Search

A method of high-performance liquid chromatography with UV detection has been established for simultaneous quantitative determination of quinoxaline-2-carboxylic acid (QCA) and methyl-3-quinoxaline-2-carboxylic acid (MQCA), the marker residues for carbadox (CBX) and olaquindox (OLA), respectively, in the muscles and livers of porcine and chicken and in the muscle of fish. Tissue samples were subject to acid hydrolysis followed by liquid–liquid extraction

Yujie Wu; Huan Yu; Yulian Wang; Lingli Huang; Yanfei Tao; Dongmei Chen; Dapeng Peng; Zhengli Liu; Zonghui Yuan

2007-01-01

124

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

125

A novel pyrroline-5-carboxylic acid and acetoacetic acid adduct in hyperprolinaemia type II  

Microsoft Academic Search

Background: From investigations of a child with hyperprolinaemia type II, we demonstrated in vitro that pyridoxal phosphate forms a novel adduct with a proline metabolite, pyrroline-5-carboxylic acid, through Claisen condensation. Studies indicated that this was a previously unsuspected generic reaction of aldehydes and some ketones. We have subsequently found the acetoacetic acid adduct in both plasma and urine from the

Valerie Walker; Graham A Mills; John M Mellor; G. John Langley; R. Duncan Farrant

2003-01-01

126

Azetidine-2-carboxylic acid in the food chain.  

PubMed

Azetidine-2-carboxylic acid (Aze) 1 is a non-protein amino acid present in sugar beets and in table beets (Beta vulgaris). It is readily misincorporated into proteins in place of proline 2 in many species, including humans, and causes numerous toxic effects as well as congenital malformations. Its role in the pathogenesis of disease in humans has remained unexplored. Sugar beet agriculture, especially in the Northern Hemisphere, has become widespread during the past 150 years, and now accounts for nearly 30% of the world's supply of sucrose. Sugar beet byproducts are also used as a dietary supplement for livestock. Therefore, this study was undertaken as an initial survey to identify Aze-containing links in the food chain. Herein, we report the presence of Aze 1 in three sugar beet byproducts that are fed to farm animals: sugar beet molasses, shredded sugar beet pulp, and pelleted sugar beet pulp. PMID:19101705

Rubenstein, Edward; McLaughlin, Theresa; Winant, Richard C; Sanchez, Agustin; Eckart, Michael; Krasinska, Karolina M; Chien, Allis

2009-01-01

127

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

128

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

129

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

130

Chemolithoautotrophy and mixotrophy in the thiophene-2-carboxylic acid-utilizing Xanthobacter tagetidis  

Microsoft Academic Search

Xanthobacter tagetidis grew as a chemolithotrophic autotroph on thiosulfate and other inorganic sulfur compounds, as a heterotroph on thiophene-2-carboxylic\\u000a acid, acetic acid and ?-ketoglutaric acid, and as a mixotroph on thiosulfate in combination with thiophene-2-carboxylic acid\\u000a and\\/or acetic acid. Autotrophic growth on one-carbon organosulfur compounds, and intermediates in their oxidation are also\\u000a reported. Thiosulfate enhanced the growth yields in mixotrophic

A. Nikki Padden; Donovan P. Kelly; A. P. Wood

1998-01-01

131

Solid acid catalysts for converting alkenes and alkanols to carboxylic acids  

Microsoft Academic Search

Tertiary carboxylic acids are presently manufactured by hydrocarboxylation of branched alkenes in the presence of CO, water and a corrosive homogeneous acid. Acidic ion-exchange resins also catalyse the hydrocarboxylation reaction when operated under specific conditions. Critical factors are the use of a moderately polar, non-basic solvent and the maintenance of a very low alkanol or alkene\\/water concentration in the reactor.

J.-P Lange; L Petrus

2001-01-01

132

Reduced receptor binding by a human interferon-. gamma. fragment lacking 11 carboxyl-terminal amino acids  

SciTech Connect

Treatment of recombinant human (/sup 125/I)-labeled interferon-..gamma..(IFN-..gamma..) with either 1) the arginine-specific proteases clostripain or submaxillaris protease or 2) the broadly specific enzyme pronase produced a stable fragment with m.w. of 15,500. Structural analysis showed that the cleavage occurred between residues 129 and 130 and thus produced a fragment lacking only 11 carboxyl-terminal amino acids. The fragmented and untreated molecules showed identical amino-terminal amino acid sequences and were equally reactive with either polyclonal or monoclonal anti-IFN-..gamma... IFN-..gamma.. lacking carboxyl-terminal amino acids displayed a 1000- to 2000-fold reduction in its capacity to bind to cellular IFN-..gamma.. receptors at 4/sup 0/C. Functionally the fragment showed a 50-fold reduction in its ability to induce antiviral activity in fibroblasts and a 10-fold reduction in its ability to induce Fc receptors on the human histiocytic lymphoma cell line U937. These results thus suggest that the carboxyl terminus of human IFN-..gamma.. contributes significantly to the formation of the receptor-binding site of the molecule.

Leinikki, P.O.; Calderon, J.; Luquette, M.H.; Schreiber, R.D.

1987-11-15

133

Regeneration of carboxylic acid-laden basic sorbents by leaching with a volatile base in an organic solvent  

DOEpatents

Carboxylic acids are sorbed from aqueous feedstocks onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with an organic solution of alkylamine thus forming an alkylamine/carboxylic acid complex which is decomposed with improved efficiency to the desired carboxylic acid and the alkylamine. Carbon dioxide addition can be used to improve the adsorption or the carboxylic acids by the solid phase sorbent.

King, C. Judson (Kensington, CA); Husson, Scott M. (Berkeley, CA)

1999-01-01

134

Multiple-acid equilibria in adsorption of carboxylic acids from dilute aqueous solution  

SciTech Connect

Equilibria were measured for adsorption of carboxylic acids from aqueous, binary-acid mixtures of lactic and succinic acids and acetic and formic acids onto basic polymeric sorbents. The experimentally determined adsorption isotherms compared well with model predictions, confirming that simple extensions from adsorption of individual acids apply. Fixed-bed studies were carried out that establish the efficacy of chromatographic fractionation of lactic and succinic acids using basic polymeric sorbents. Finally, sequential thermal and solvent regeneration of lactic and acetic acid-laden sorbents was investigated as a method to fractionate among coadsorbed volatile and nonvolatile acids. Essentially complete removal of the acetic acid from the acid-laden sorbent was achieved by vaporization under the conditions used; a small amount of loss of lactic acid (about 11%) was observed.

Husson, S.M.; King, C.J. [Lawrence Berkeley National Lab., CA (United States)] [Lawrence Berkeley National Lab., CA (United States)

1999-02-01

135

Density functional study of electronic, charge density, and chemical bonding properties of 9-methyl-3-Thiophen-2-YI-Thieno [3,2-e] [1, 2, 4] Thriazolo [4,3-c] pyrimidine-8-Carboxylic acid ethyl ester crystals  

NASA Astrophysics Data System (ADS)

A comprehensive theoretical density functional investigation of the electronic crystal structure, chemical bonding, and the electron charge densities of 9-Methyl-3-Thiophen-2-YI-Thieno [3, 2-e] [1, 2, 4] Thriazolo [4,3-c] Pyrimidine-8-Carboxylic Acid Ethyl Ester (C15H12N4O2S2) is performed. The density of states at Fermi level equal to 5.50 (3.45) states/Ry cell, and the calculated bare electronic specific heat coefficient is found to be 0.95 (0.59) mJ/mole-K2 for the local density approximation (Engel-Vosko generalized gradient approximation). The electronic charge density space distribution contours in (1 0 0) and (1 1 0) planes were calculated. We find that there are two independent molecules (A and B) in the asymmetric unit exhibit intramolecular C-H…O, C-H…N interactions. This intramolecular interaction is different in molecules A and B, where A molecule show C-H…O interaction while B molecule exhibit C-H…N interaction. We should emphasis that there is ?-? interaction between the pyrimidine rings of the two neighbors B molecules gives extra strengths and stabilizations to the superamolecular structure. The calculated distance between the two neighbors pyrimidine rings found to be 3.345 Å, in good agreement with the measured one (3.424(1) Å).

Reshak, A. H.; Kamarudin, H.; Alahmed, Z. A.; Auluck, S.; Chyský, Jan

2014-06-01

136

Carboxylic Acids as Traceless Directing Groups for the Rhodium(III)-Catalyzed Decarboxylative C?H Arylation of Thiophenes.  

PubMed

A rhodium(III)-catalyzed carboxylic acid directed decarboxylative C?H/C?H cross-coupling of carboxylic acids with thiophenes has been developed. With a slight adjustment of the reaction conditions based on the nature of the substrates, aryl carboxylic acids with a variety of substituents could serve as suitable coupling partners, and a broad variety of functional groups were tolerated. This method provides straightforward access to biaryl scaffolds with diverse substitution patterns, many of which have conventionally been synthesized through lengthy synthetic sequences. An illustrative example is the one-step gram-scale synthesis of a biologically active 3,5-substituted 2-arylthiophene by way of the current method. PMID:25631325

Zhang, Yuanfei; Zhao, Huaiqing; Zhang, Min; Su, Weiping

2015-03-16

137

Pancreatic Function in Carboxyl-Ester Lipase Knockout Mice  

Microsoft Academic Search

Background\\/Aims:CEL-MODY is a monogenic form of diabetes and exocrine pancreatic insufficiency due to mutations in the carboxyl-ester lipase (CEL) gene. We aimed to investigate endocrine and exocrine pancreatic function in CEL knockout mice (CELKO). Methods: A knockout mouse model with global targeted deletion of CEL was investigated physiologically and histopathologically, and compared to littermate control CEL+\\/+ mice at 7 and

Mette Vesterhus; Helge Ræder; Amarnath J. Kurpad; Dan Kawamori; Anders Molven; Rohit N. Kulkarni; C. Ronald Kahn; Pål Rasmus Njølstad

2010-01-01

138

Friedel–Crafts acylation reaction using carboxylic acids as acylating agents  

Microsoft Academic Search

Dehydrative Friedel–Crafts acylation reaction of aromatic compounds with carboxylic acids as acylating agents was investigated in the presence of Lewis acid- or Brønsted acid-catalyst. Various metal triflates and bis(trifluoromethanesulfonyl)amides showed catalytic activity at high temperature, among which Eu(NTf2)3 proved to be the most effective and efficiently catalyzed the acylation reaction of alkyl- and alkoxybenzenes with aliphatic and aromatic carboxylic acids

Masato Kawamura; Dong-Mei Cui; Shigeru Shimada

2006-01-01

139

Atomic layer deposition of organic-inorganic hybrid materials based on saturated linear carboxylic acids.  

PubMed

Atomic layer deposition (ALD) has successfully provided thin films of organic-inorganic hybrid materials based on saturated linear carboxylic acids and trimethylaluminium (TMA). Films were grown for seven carboxylic acids: oxalic, malonic, succinic, glutaric, pimelic, suberic and sebacic acid, i.e. ranging from 2 to 10 carbon atoms in the molecular structure. These processes show exceptionally high growth rates; up to 4.3 nm/cycle for the pimelic acid-TMA system. Quartz crystal microbalance measurements of the growth dynamics indicate that all systems are of a self limiting ALD-type. Nevertheless, temperature dependent growth was observed in several systems. The width of the ALD windows shows correlations with the length of the carbon chains. Fourier transform infrared spectroscopy clearly proved that the deposited films are of a hybrid character, where the carboxylic acids primarily form bidentate complexes, though bridging complexes may also form. All films are X-ray amorphous as deposited. The films were further analyzed by atomic force microscopy for surface roughness and topography, UV-Vis spectroscopy and ellipsometry for optical properties, and the goniometer method for measuring sessile drops for surface wetting properties. Apart from the oxalic and malonic acid-TMA systems, the films are stable in contact with water. The films are generally smooth, transparent and have a refractive index close to 1.5. The complete coverage and accurate growth control offered by the ALD technique is here proven to provide surface-functionalized hybrid materials resembling metal-organic frameworks (MOF), probably as rather dense structures, yet with substantial potential for applications. PMID:21442116

Klepper, Karina Barnholt; Nilsen, Ola; Hansen, Per-Anders; Fjellvåg, Helmer

2011-05-01

140

Human ?1-pyrroline-5-carboxylate synthase: Function and regulation  

PubMed Central

Summary Mammalian ?1-pyrroline-5-carboxylate synthase (P5CS) is a bifunctional ATP- and NAD(P)H-dependent mitochondrial enzyme that catalyzes the coupled phosphorylation and reduction-conversion of L-glutamate to P5C, a pivotal step in the biosynthesis of L-proline, L-ornithine and L-arginine. Previously, we reported cloning and characterization of two P5CS transcript variants generated by exon sliding that encode two protein isoforms differing only by a 2 amino acid-insert at the N-terminus of the ?-glutamyl kinase active site. The short form (P5CS.short) is highly expressed in the gut and is inhibited by ornithine. In contrast, the long form (P5CS.long) is expressed ubiquitously and is insensitive to ornithine. Interestingly, we found that all the established human cell lines we have studied expressed P5CS.long but not P5CS.short. In addition, expression of P5CS.long can be modulated by hormones: downregulation by hydrocortisone and dexamethasone and upregulation by estradiol, for example. Using a quantitative proteomic approach, we showed that P5CS.long is upregulated by p53 in p53-induced apoptosis in DLD-1 colorectal cancer cells. Functional genomic analysis confirmed that there are two p53-binding consensus sequences in the promoter region and in the intron 1 of the human P5CS gene. Interestingly, overexpression of P5CS by adenoviruses harboring P5CS.long or P5CS.short in various cell types has no effect on cell growth or survival. It would be of importance to investigate the role of P5CS as a p53 downstream effector and how P5CS.short expression is regulated by hormones and factors of alternative splicing in cells isolated from model animals. PMID:18401542

Khalil, S.; Zhaorigetu, S.; Liu, Z.; Tyler, M.; Wan, G.; Valle, D.

2009-01-01

141

Human Delta1-pyrroline-5-carboxylate synthase: function and regulation.  

PubMed

Mammalian Delta(1)-pyrroline-5-carboxylate synthase (P5CS) is a bifunctional ATP- and NAD(P)H-dependent mitochondrial enzyme that catalyzes the coupled phosphorylation and reduction-conversion of L: -glutamate to P5C, a pivotal step in the biosynthesis of L: -proline, L: -ornithine and L: -arginine. Previously, we reported cloning and characterization of two P5CS transcript variants generated by exon sliding that encode two protein isoforms differing only by a two amino acid-insert at the N-terminus of the gamma-glutamyl kinase active site. The short form (P5CS.short) is highly expressed in the gut and is inhibited by ornithine. In contrast, the long form (P5CS.long) is expressed ubiquitously and is insensitive to ornithine. Interestingly, we found that all the established human cell lines we have studied expressed P5CS.long but not P5CS.short. In addition, expression of P5CS.long can be modulated by hormones: downregulation by hydrocortisone and dexamethasone and upregulation by estradiol, for example. Using a quantitative proteomic approach, we showed that P5CS.long is upregulated by p53 in p53-induced apoptosis in DLD-1 colorectal cancer cells. Functional genomic analysis confirmed that there are two p53-binding consensus sequences in the promoter region and in the intron 1 of the human P5CS gene. Interestingly, overexpression of P5CS by adenoviruses harboring P5CS.long or P5CS.short in various cell types has no effect on cell growth or survival. It would be of importance to further investigate the role of P5CS as a p53 downstream effector and how P5CS.short expression is regulated by hormones and factors of alternative splicing in cells isolated from model animals. PMID:18401542

Hu, C-A A; Khalil, S; Zhaorigetu, S; Liu, Z; Tyler, M; Wan, G; Valle, D

2008-11-01

142

Structure and function studies on enzymes with a catalytic carboxyl group(s): from ribonuclease T1 to carboxyl peptidases  

PubMed Central

A group of enzymes, mostly hydrolases or certain transferases, utilize one or a few side-chain carboxyl groups of Asp and/or Glu as part of the catalytic machinery at their active sites. This review follows mainly the trail of studies performed by the author and his colleagues on the structure and function of such enzymes, starting from ribonuclease T1, then extending to three major types of carboxyl peptidases including aspartic peptidases, glutamic peptidases and serine-carboxyl peptidases. PMID:23759941

TAKAHASHI, Kenji

2013-01-01

143

Chiral discrimination of secondary alcohols and carboxylic acids by NMR spectroscopy.  

PubMed

The manuscript reports two novel ternary ion-pair complexes, which serve as chiral solvating agents, for enantiodiscrimination of secondary alcohols and carboxylic acids. The protocol for discrimination of secondary alcohols is designed by using one equivalent mixture each of enantiopure mandelic acid, 4-dimethylaminopyridine (DMAP) and a chiral alcohol. For discrimination of carboxylic acids, the ternary complex is obtained by one equivalent mixture each of enantiopure chiral alcohol, DMAP and a carboxylic acid. The designed protocols also permit accurate measurement of enantiomeric composition. PMID:25332176

Pal, Indrani; Chaudhari, Sachin R; Suryaprakash, Nagaraja Rao

2015-02-01

144

Carboxylic acid production from brewer's spent grain via mixed culture fermentation.  

PubMed

This study aimed at investigating carboxylic acid production from brewer's spent grain (BSG) via mixed culture fermentation. The results showed that the distribution of fermentation products was significantly affected by pH conditions and the addition of electron donors. Lactic acid was the dominant component under acidic and alkaline conditions while volatile fatty acids (VFAs) became dominant under the neutral condition. Furthermore, the neutral condition favored the chain elongation of carboxylic acids, especially with ethanol as the electron donor. Ethanol addition enhanced valeric acid and caproic acid production by 44% and 167%, respectively. Lactic acid addition also had positive effects on VFAs production under the neutral condition but limited to C2-C4 products. As a result, propionic acid and butyric acid production was increased by 109% and 152%, respectively. These findings provide substantial evidence for regulating carboxylic acid production during mixed culture fermentation of BSG by controlling pH and adding electron donors. PMID:25698409

Liang, Shaobo; Wan, Caixia

2015-04-01

145

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

146

Short-chain carboxylic-acid-stimulated, PMN-mediated gingival inflammation.  

PubMed

This communication reviews the effects of short-chain carboxylic acids on human cells of importance to the periodontium. The central hypothesis is that these acids can alter both cell function and gene expression, and thus contribute to the initiation and prolongation of gingival inflammation. Short-chain carboxylic acids [CH3-(CH2)x-COOH, x < 3] are metabolic intermediates with a broad range of apparently paradoxical biological effects. For example, lactic acid (CH3-CHOH-COOH), a 3-carbon alpha-hydroxy-substituted acid, is widely recognized for its cariogenicity. Lactic acid, however, also occurs in tropical fruits, and is the active ingredient in a variety of anti-wrinkle creams developed by dermatologists. In marked contrast, the unsubstituted 3-carbon propionic acid (CH3-CH2-COOH) is used as a food preservative and is the active principle for one class of non-steroidal anti-inflammatory agents. Interestingly, the addition of one carbon to propionic acid dramatically changes the biological effects. The unsubstituted 4-carbon butyric acid (CH3-CH2-CH2-COOH) is used by hematologists as a de-differentiating agent for the treatment of sickle cell anemia, but by oncologists as a differentiating agent for cancer chemotherapy. Finally, acting either individually or in concert, these acids can increase vascular dilation. Clearly, these acids, while metabolically derived, have a number of very divergent activities which are cell-type-specific (Fig. 1). It may be telling that periodontal bacteria produce these acids in millimolar concentrations, and that these bacteria can be characterized by their acid production profiles. It is no less interesting that these acids occur in the gingival crevices of human subjects with severe periodontal disease at millimolar levels which are > 10-fold higher than those found in mildly diseased subjects, and are undetectable in healthy subjects. Further, when applied directly to healthy human gingiva, short-chain carboxylic acids stimulate a gingival inflammatory response and inflammatory cytokine release. At the cellular level, these acids inhibit proliferation of gingival epithelial and endothelial cells, and inhibit leukocyte apoptosis and function, but can stimulate leukocyte cytokine release. At the molecular level, these acids can stimulate neutrophil gene transcription, translation, and protein expression. Thus, the likelihood is high that these acids, in addition to their cariogenic activity, can promote and prolong gingival inflammation. Our challenge will be to identify the cell or cells of the periodontium which respond to short-chain carboxylic acids, to delineate their responses and the molecular mechanism(s) of these effects, and to categorize the aspects of the inflammatory components which damage and those which protect the host. With this information, it may be possible to begin to rationally identify and test pharmaceutical agents which diminish the harmful aspects, while enhancing the beneficial components, of the inflammatory response. PMID:9260044

Niederman, R; Zhang, J; Kashket, S

1997-01-01

147

Carboxylic Acids as A Traceless Activation Group for Conjugate Additions: A Three-Step Synthesis of ()-Pregabalin  

E-print Network

A critical feature of this new Csp 3- arylation reaction is the capacity for aliphatic carboxylic acids carboxylic acids should therefore be suitable and generic precursors for radical conjugate addition reactions electrode (SCE) in CH3CN).9 We assumed that base-promoted deprotonation of a carboxylic acid substrate

MacMillan, David W. C.

148

Flame Retardant Finishing of Cotton Fleece Fabric: Part IV-Bifunctional Carboxylic Acids  

Microsoft Academic Search

Most cotton fleece fabrics are not able to meet the federal flammability standard for general apparel (16 CFR 1610). In this research, we applied three carboxylic acids, i.e., succinic acid (SUA), malic acid (MLA), and tartaric acid (TTA), as flame retardant finishing systems for cotton fleece. We found that all three acids are able to esterify cotton in the presence

Xialing Wu; Charles Q. Yang

2009-01-01

149

Catalytic coupling of carboxylic acids by ketonization as a processing step in biomass conversion  

Microsoft Academic Search

Carboxylic acids, common intermediate products in biomass conversion processes, can be converted into ketones via ketonization reactions over a ceria–zirconia catalyst. Reaction kinetics studies were carried out using hexanoic acid, as a representative carboxylic acid, in the presence of 1-pentanol and 2-butanone, as representative biomass-derived alcohol and ketone species. Studies were carried out at temperatures from 448 to 623K, and

Christian A. Gaertner; Juan Carlos Serrano-Ruiz; Drew J. Braden; James A. Dumesic

2009-01-01

150

Utility of branched chain carboxylic acids in the manufacture of driers  

Microsoft Academic Search

To be useful in the manufacture of driers, a carboxylic acid must yield lead, cobalt, manganese, calcium and zinc soaps which\\u000a are soluble in paint vehicles and petroleum hydrocarbon thinners. The drying metal soaps of a number of saturated branched\\u000a chain carboxylic acids were prepared to determine the relationship of acid structure to metal soap solubility. It was found\\u000a that

Alfred Fischer

1966-01-01

151

An ab initio density functional study of the optical functions of 9-Methyl-3-Thiophen-2-YI-Thieno [3,2e] [1,2,4] Thriazolo [4,3c] Pyrimidine-8-Carboxylic Acid Ethyl Ester crystals  

NASA Astrophysics Data System (ADS)

An ab initio investigation of the optical constants of 9-Methyl-3-Thiophen-2-YI-Thieno [3,2e] [1,2,4] Thriazolo [4,3c] Pyrimidine-8-Carboxylic Acid Ethyl Ester crystal is performed within a framework of local density approximation (LDA), and the Engel-Vosko generalized gradient approximation (EV-GGA) exchange correlation potentials. It is established that there are two independent molecules (A and B) exhibiting different intra-molecular interactions: C-H⋯O (A) and C-H⋯N (B). These intra-molecular interactions favor stabilization of the crystal structure for molecules A and B. It should be emphasized that there exist remarkable ?-? interactions between the pyrimidine rings of the two neighbors B molecules giving extra strengths and stabilizations to the superamolecular structure. These different intra-molecular interactions C-H⋯O (A) and C-H⋯N (B) and the ?-? interaction between the pyrimidine rings of the two neighbors B molecules give principal contribution to dispersion of optical properties. With a view to seek deeper insight into the electronic structure, the optical properties were investigated. Our calculations show that the optical constants are very anisotropic. The EVGGA calculation shows a blue spectral shift of around 0.024 eV with significant changes in the spectra compared to the LDA calculation. The observed spectral shifts are in agreement with the calculated band structure and corresponding electron density of states.

Reshak, Ali H.; Kityk, I. V.; Khenata, R.; Al-Douri, Y.; Auluck, S.

152

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

153

Biocatalytic amidation of carboxylic acids and their antinemic activity.  

PubMed

A series of novel N-alkyl substituted amides, synthesized by enzyme catalysis, were evaluated against root-knot nematode, Meloidogyne incognita and found to have potential antinemic activity. The corresponding amides were prepared by the condensation of equimolar amounts of carboxylic acids with different alkyl amines in the presence of Candida antarctica lipase at 60-90 degrees C in 16-20 h. The reactions were carried out in a non - solvent system without the use of any activating agents. All the products were obtained in appreciable amounts and the yields for different compounds varied between 77.4-82.3%. The synthesized compounds were characterized using spectroscopy techniques namely Infra Red (IR) and Nuclear Magnetic Resonance (NMR) ((1)H and (13)C). Nematicidal activity of synthesized amides was evaluated against J(2)s of Meloidogyne incognita at 500, 250, 125 and 62.5 ppm concentrations after 24 h, 48 h and 72 h of exposure. Among all the tested compounds, N-propyl-butyramide, N-propyl-pentanamide and N-propyl-hexanamide were found to possess significant activity with LC(50) values of 67.46, 83.49 and 96.53 respectively. N-propyl-butyramide with LC(50) value of 67.46 ppm was found to be most active amide against J(2)s of Meloidogyne incognita. The bioactivity study showed that an increase in alkyl chain significantly decreased the activity of amides against root-knot nematode. PMID:20390959

Bose, Abinesh; Shakil, Najam Akhtar; Pankaj; Kumar, Jitendra; Singh, Manish K

2010-04-01

154

Biosynthesis of quinoxaline antibiotics: Purification and characterization of the quinoxaline-2-carboxylic acid activating enzyme from Streptomyces triostinicus  

SciTech Connect

A quinoxaline-2-carboxylic acid activating enzyme was purified to homogeneity from triostin-producing Streptomyces triostinicus. It could also be purified from quinomycin-producing Streptomyces echinatus. Triostins and quinomycins are peptide lactones that contain quinoxaline-2-carboxylic acid as chromophoric moiety. The enzyme catalyzes the ATP-pyrophosphate exchange reaction dependent on quinoxaline-2-carboxylic acid and the formation of the corresponding adenylate. Besides quinoxaline-2-carboxylic acid, the enzyme also catalyzes the formation of adenylates from quinoline-2-carboxylic acid and thieno(3,2-b)pyridine-5-carboxylic acid. No adenylates were seen from quinoline-3-carboxylic acid, quinoline-4-carboxylic acid, pyridine-2-carboxylic acid, and 2-pyrazinecarboxylic acid. Previous work revealed that quinoline-2-carboxylic acid and thieno(3,2-b)pyridine-5-carboxylic acid became efficiently incorporated into the corresponding quinoxaline antibiotic analogues in vivo. Together with the data described here, this suggests that the enzyme is part of the quinoxaline antibiotics synthesizing enzyme system. The enzyme displays a native molecular weight of 42,000, whereas in its denatured form it is a polypeptide of Mr 52,000-53,000. It resembles in its behavior actinomycin synthetase I, the chromophore activating enzyme involved in actinomycin biosynthesis.

Glund, K.; Schlumbohm, W.; Bapat, M.; Keller, U. (Technische Universitaet Berlin (Germany, F.R.))

1990-04-10

155

Lipase-Catalyzed Selective Synthesis and Micellization of Poly(ethylene glycol)-block-poly(?-caprolactone) Copolymer Possessing a Carboxylic Acid Group at the PEG Chain End  

Microsoft Academic Search

A novel poly(ethylene glycol)-block-poly(?-caprolactone) (PEG-b-PCL) copolymer possessing a carboxylic acid group at the PEG chain end was prepared by the one-pot lipase-catalyzed polymerization of ?-CL using an ?-carboxylic acid-?-hydroxy-PEG as a macroinitiator. This synthetic approach is remarkable because it dose not require tedious chemical routes such as end-functional group changing steps and protection-deprotection steps. The PEG-b-PCL copolymer spontaneously forms a

Motoi Oishi; Satoshi Ikeo; Yukio Nagasaki

2007-01-01

156

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

157

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

PubMed

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 a low O/C ratio (0.04-0.06) and high fixed carbon content (~80% dry weight basis) were oxidized using concentrated H(2)SO(4)/HNO(3) and 30% HNO(3). Oxidized and unoxidized biochars were characterized for O/C ratio, total acidity, pH, moisture, ash, volatile matter, and fixed carbon contents, Brunauer-Emmett-Teller surface area, and attenuated total reflectance Fourier transform infrared spectral features. Characterized biochars were amended (2%, 5%, 10%, and 20% in grams of biochar per gram of soil) on a sandy, slightly acidic (pH 6.27) heavy metal contaminated small arms range soil fraction (<250 ?m) having low total organic carbon (0.518%) and low cation exchange capacity (0.95 cmol(c) kg(-1)). Oxidized biochars rich in carboxyl functional groups exhibited significantly greater Pb, Cu, and Zn stabilization ability compared to unoxidized biochars, especially in pH 4.9 acetate buffer (standard solution for the toxicity characteristic leaching procedure). Oppositely, only oxidized biochars caused desorption of Sb, indicating a counteracting impact of carboxyl functional groups on the solubility of anions and cations. The results suggested that appropriate selection of biochar oxidant will produce recalcitrant biochars rich in carboxyl functional groups for a long-term heavy metal stabilization strategy in contaminated soils. PMID:22280497

Uchimiya, Minori; Bannon, Desmond I; Wartelle, Lynda H

2012-02-22

158

Low molecular weight carboxylic acids in oxidizing porphyry copper tailings.  

PubMed

The distribution of low molecular weight carboxylic acids (LMWCA) was investigated in pore water profiles from two porphyry copper tailings impoundments in Chile (Piuquenes at La Andina and Cauquenes at El Teniente mine). The objectives of this study were (1) to determine the distribution of LMWCA, which are interpreted to be the metabolic byproducts of the autotroph microbial community in this low organic carbon system, and (2) to infer the potential role of these acids in cycling of Fe and other elements in the tailings impoundments. The speciation and mobility of iron, and potential for the release of H+ via hydrolysis of the ferric iron, are key factors in the formation of acid mine drainage in sulfidic mine wastes. In the low-pH oxidation zone of the Piuquenes tailings, Fe(III) is the dominant iron species and shows high mobility. LMWCA, which occur mainly between the oxidation front down to 300 cm below the tailings surface at both locations (e.g., max concentrations of 0.12 mmol/L formate, 0.17 mmol/L acetate, and 0.01 mmol/L pyruvate at Piuquenes and 0.14 mmol/L formate, 0.14 mmol/L acetate, and 0.006 mmol/L pyruvate at Cauquenes), are observed at the same location as high Fe concentrations (up to 71.2 mmol/L Fe(II) and 16.1 mmol/L Fe(III), respectively). In this zone, secondary Fe(III) hydroxides are depleted. Our data suggest that LMWCA may influence the mobility of iron in two ways. First, complexation of Fe(III), through formation of bidentate Fe(III)-LMWCA complexes (e.g., pyruvate, oxalate), may enhance the dissolution of Fe(III) (oxy)hydroxides or may prevent precipitation of Fe(III) (oxy)hydroxides. Soluble Fe(III) chelate complexes which may be mobilized downward and convert to Fe(II) by Fe(III) reducing bacteria. Second, monodentate LMWCA (e.g., acetate and formate) can be used by iron-reducing bacteria as electron donors (e.g., Acidophilum spp.), with ferric iron as the electron acceptor. These processes may, in part, explain the low abundances of secondary Fe(III) hydroxide precipitates below the oxidation front and the high concentrations of Fe(II) observed in the pore waters of some low-sulfide systems. The reduction of Fe(III) and the subsequent increase of iron mobility and potential acidity transfer (Fe(II) oxidation can result in the release of H+ in an oxic environment) should be taken in account in mine waste management strategies. PMID:15884343

Dold, Bernhard; Blowes, David W; Dickhout, Ralph; Spangenberg, Jorge E; Pfeifer, Hans-Rudolf

2005-04-15

159

Photophysics of indole-2-carboxylic acid (I2C) and indole-5-carboxylic acid (I5C): Heavy atom effect  

NASA Astrophysics Data System (ADS)

In this study the effect of carboxylic group substitution in the 2 and 5 position of indole ring on the photophysics of the parent indole chromophore has been studied. The photophysical parameters crucial in triplet state decay mechanism of aqueous indole-2-carboxylic acid (I2C) and indole-5-carboxylic acid (I5C) have been determined applying our previously proposed methodology based on the heavy atom effect and fluorescence and phosphorescence decay kinetics [Kowalska-Baron et al., 2012]. The determined time-resolved phosphorescence spectra of I2C and I5C are red-shifted as compared to that of the parent indole. This red-shift was especially evident in the case of I2C and may indicate the possibility of hydrogen bonded complex formation incorporating carbonyl Cdbnd O, the NH group of I2C and, possibly, surrounding water molecules. The possibility of the excited state charge transfer process and the subsequent electronic charge redistribution in such a hydrogen bonded complex may also be postulated. The resulting stabilization of the I2C triplet state is manifested by its relatively long phosphorescence lifetime in aqueous solution (912 ?s). The relatively short phosphorescence lifetime of I5C (56 ?s) may be the consequence of more effective ground-state quenching of I5C triplet state. This hypothesis may be strengthened by the significantly larger value of the determined rate constant of I5C triplet state quenching by its ground-state (4.4 × 108 M-1 s-1) as compared to that for indole (6.8 × 107 M-1 s-1) and I2C (2.3 × 107 M-1 s-1). The determined bimolecular rate constant for triplet state quenching by iodide kqT1 is equal to 1 × 104 M-1 s-1; 6 × 103 M-1 s-1 and 2.7 × 104 M-1 s-1 for indole, I2C and I5C, respectively. In order to obtain a better insight into iodide quenching of I2C and I5C triplet states in aqueous solution, the temperature dependence of the bimolecular rate constants for iodide quenching of the triplet states has been expressed in Arrhenius form. The linearity of the obtained Arrhenius plots clearly indicated the existence of one temperature-dependent non-radiative process for the de-excitation of I2C and I5C triplet state in the presence of iodide. This process may be attributed to the solute-quenching by iodide and, most probably, proceeds via reversibly formed exciplex. The activation energies obtained from linear Arrhenius plots (1.89 kcal/mol for I5C; 2.55 kcal/mol for I2C) are smaller as compared to that for diffusion controlled reactions in aqueous solution (about 4 kcal/mol), which may indicate the great importance of the electrostatic interactions between solute and iodide ions in lowering the energy barrier needed for the formation of the triplet-quencher complex. Based on the theoretical predictions (at the DFT(CAM-B3LYP)/6-31 + G(d,p) level of theory) and careful analysis of the obtained FTIR spectra it may be concluded that in the solid state I2C and I5C molecules form associates by intermolecular NH⋯Odbnd C and OH⋯Odbnd C hydrogen bonding interactions, whereas the existence of intramolecular NH⋯Odbnd C interactions in the solid state of I2C and I5C is highly unlikely.

Kowalska-Baron, Agnieszka; Ga??cki, Krystian; Wysocki, Stanis?aw

2013-12-01

160

Pilot-scale fermentation of office paper and chicken manure to carboxylic acids  

E-print Network

This project focused on scaling up the laboratory fermentation of biomass to carboxylic acids. Four 1050-gallon tanks were used to simulate four-stage countercurrent fermentation. Most laboratory fermentations have been performed with 1-L fermentors...

Moody, Andrew Garret

2006-08-16

161

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

162

Rh(III)-catalyzed decarboxylative coupling of acrylic acids with unsaturated oxime esters: carboxylic acids serve as traceless activators.  

PubMed

?,?-Unsaturated carboxylic acids undergo Rh(III)-catalyzed decarboxylative coupling with ?,?-unsaturated O-pivaloyl oximes to provide substituted pyridines in good yield. The carboxylic acid, which is removed by decarboxylation, serves as a traceless activating group, giving 5-substituted pyridines with very high levels of regioselectivity. Mechanistic studies rule out a picolinic acid intermediate, and an isolable rhodium complex sheds further light on the reaction mechanism. PMID:24512241

Neely, Jamie M; Rovis, Tomislav

2014-02-19

163

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

PubMed

Model systems are critical to our understanding of self-assembly processes. As such, we have studied the surface self-assembly of a small and simple molecule, indole-2-carboxylic acid (I2CA). We combine density functional theory gas-phase (DFT) calculations with scanning tunneling microscopy to reveal details of I2CA assembly in two different solvents at the solution/solid interface, and on Au(111) in ultrahigh vacuum (UHV). In UHV and at the trichlorobenzene/highly oriented pyrolytic graphite (HOPG) interface, I2CA forms epitaxial lamellar structures based on cyclic OH?O carboxylic dimers. The structure formed at the heptanoic acid/HOPG interface is different and can be interpreted in a model where heptanoic acid molecules co-adsorb on the substrate with the I2CA, forming a bicomponent commensurate unit cell. DFT calculations of dimer energetics elucidate the basic building blocks of these structures, whereas calculations of periodic two-dimensional assemblies reveal the epitaxial effects introduced by the different substrates. PMID:25770512

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

2015-03-14

164

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

NASA Astrophysics Data System (ADS)

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

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

2015-03-01

165

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

166

Discovery of novel quinoline carboxylic acid series as DGAT1 inhibitors.  

PubMed

Herein we report the design and synthesis of a series of novel bicyclic DGAT1 inhibitors with a carboxylic acid moiety. The optimization of the initial lead compound 7 based on in vitro and in vivo activity led to the discovery of potent indoline and quinoline classes of DGAT1 inhibitors. The structure-activity relationship studies of these novel series of bicyclic carboxylic acid derivatives as DGAT1 inhibitors are described. PMID:24618302

Zhou, Gang; Ting, Pauline C; Wishart, Grant; Zorn, Nicolas; Aslanian, Robert G; Lin, Mingxiang; Smith, Michelle; Walker, Scott S; Cook, John; Van Heek, Margaret; Lachowicz, Jean

2014-04-01

167

The Effects of Borate Minerals on the Synthesis of Nucleic Acid Bases, Amino Acids and Biogenic Carboxylic Acids from Formamide  

Microsoft Academic Search

The thermal condensation of formamide in the presence of mineral borates is reported. The products afforded are precursors\\u000a of nucleic acids, amino acids derivatives and carboxylic acids. The efficiency and the selectivity of the reaction was studied\\u000a in relation to the elemental composition of the 18 minerals analyzed. The possibility of synthesizing at the same time building\\u000a blocks of both

Raffaele Saladino; Maurizio Barontini; Cristina Cossetti; Ernesto Di Mauro; Claudia Crestini

2011-01-01

168

The conversion of corn stover and pig manure to carboxylic acids with the MixAlco process  

E-print Network

The MixAlco process, developed by Dr. Mark T. Holtzapple, uses anaerobic fermentation to convert waste biomass into carboxylate salts which can then be manipulated into carboxylic acids, ketones and alcohols. This project focuses on the application...

Black, Amanda Spring

2013-02-22

169

On the possibility of using short chain length mono-carboxylic acids for stabilization of magnetic fluids  

NASA Astrophysics Data System (ADS)

Short chain length mono-carboxylic acids (lauric and myristic acids) are used to coat magnetite nanoparticles in non-polar organic liquids, which results in highly stable magnetic fluids. The new fluids are compared with classical organic fluids stabilized by oleic acid (OA). Magnetic granulometry and small-angle neutron scattering (polarized mode) reveal a great difference in the particle size distribution function for the studied magnetic fluids, particularly a decrease in the characteristic particle radius of magnetite when lauric and myristic acids are used instead of OA.

Avdeev, Mikhail V.; Bica, Doina; Vékás, Ladislau; Marinica, Oana; Balasoiu, Maria; Aksenov, Victor L.; Rosta, László; Garamus, Vasil M.; Schreyer, Andreas

2007-04-01

170

Probing the acidity of carboxylic acids in protic ionic liquids, water, and their binary mixtures: activation energy of proton transfer.  

PubMed

Acidity functions were used to express the ability of a solvent/solution to donate/accept a proton to a solute. The present work accounts for the acidity determination of HCOOH, CH3COOH, and CH3CH2COOH in the alkylimidazolium-based protic ionic liquids (PILs), incorporated with carboxylate anion, water, and in a binary mixture of PIL and water using the Hammett acidity function, H0. A reversal in the acidity trend was observed, when organic acids were transferred from water to PIL. It was emphasized that an increased stabilization offered by PIL cation toward the more basic conjugate anion of organic acid was responsible for this anomalous change in acidity order in PILs, which was absent in water. The greater stabilization of a basic organic anion by PIL cation is discussed in terms of the stable hard–soft acid base (HSAB) pairing. A change in the H0 values of these acids was observed with a change in temperature, and a linear correlation between the ln?H0 and 1/T was noted. This relationship points toward the activation energy of proton transfer (E(a,H+)), a barrier provided by the medium during the proton transfer from Brønsted acid to indicator. The H0 function in binary mixtures points to the involvement of pseudosolvent, the behavior of which changes with the nature and concentration of acid. The presence of the maxima/minima in the H0 function is discussed in terms of the synergetic behavior of the pseudosolvent composed of the mixtures of aqueous PILs. PMID:23373464

Shukla, Shashi Kant; Kumar, Anil

2013-02-28

171

Preparation and characterization of carboxyl functionalization of magnetite nanoparticles for oligonucleotide immobilization  

NASA Astrophysics Data System (ADS)

Fe3O4 nanoparticles prepared by the co-precipitation of Fe2+ and Fe3+ with NH4OH were simply modified by the carboxylic acid group of 3-thiopheneacetic acid (3TA) and meso-2,3-dimercaptosuccinic acid (DMSA). These functionalized Fe3O4 nanoparticles when coated with 3TA and DMSA have increased hydrophilic properties, thus causing them to be well dispersed in aqueous solutions. Then oligonucleotides (5'-AGC T-Amine-3') were immobilized on the carboxylic acid group-modified Fe3O4 nanoparticles. They were characterized by using FT-IR, XRD and TEM. The concentration of the oligonucleotide-modified Fe3O4 nanoparticles was investigated using a UV-vis spectrometer and compared to that of Fe3O4 nanoparticles without any surface modification. The Fe3O4 nanoparticles were spherical and the particle sizes were approximately 10 nm. The immobilizing efficiencies of the Fe3O4 nanoparticles modified with 3TA and DMSA were higher than those of the non-functionalized Fe3O4 nanoparticles.

Kim, Min-Jung; Jang, Dae-Hwan; Choa, Yong-Ho

2010-05-01

172

A simple method for the matrix isolation of monomeric and dimeric carboxylic acids  

Microsoft Academic Search

We have used a supersonic jet to matrix isolate either well defined hydrogen bonded aggregates or the monomeric species of carboxylic acids (formic acid or acetic acid, respectively). By varying several parameters of the pulsed deposition we have shown that the pulse duration has the major influence on the aggregation in the gas phase. This allowed us to generate either

M. Halupka; W Sander

1998-01-01

173

Kinetics of esterification of aromatic carboxylic acids over zeolites H? and HZSM5 using dimethyl carbonate  

Microsoft Academic Search

Esterification of benzoic acid and substituted benzoic acids has been carried out efficiently over zeolite H? and HZSM5 in an autoclave using dimethyl carbonate (DMC) as the methylating agent. The wide applicability of this esterification method to esterify a wide range of aromatic carboxylic acids has been demonstrated. This method is a viable and safe alternative to other esterification processes,

Sharath R. Kirumakki; N. Nagaraju; Komandur V. R. Chary; Sankarasubbier Narayanan

2003-01-01

174

Amberlyst 15: A Practical, Mild and Selective Catalyst for Methyl Esterification of Carboxylic Acids  

Microsoft Academic Search

Mild and selective methyl esterification of carboxylic acids are realized using Amberlyst 15 as acid catalyst in methanol. No race mization, epimerization or ketalization products have been observed with this method. Excellent results are obtained in the esterifications of bile acids.

Marino Petrini; Roberto Ballini; Enrico Marcantoni; Goffredo Rosini

1988-01-01

175

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

176

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

E-print Network

Theoretical modeling of the OH stretch infrared spectrum of carboxylic acid dimers based on first, Wisconsin 53706-1396 Received 20 September 2002; accepted 28 October 2002 Carboxylic acid dimers serve, and OH bend internal coordinates for the formic acid and benzoic acid dimers. These are then projected

Zwier, Timothy S.

177

Relationship between the malonylation of 1-aminocyclopropane-1-carboxylic acid and D-amino acids in mung-bean hypocotyls  

Microsoft Academic Search

In sections from hypocotyls of dark-grown mung-bean (Vigna radiata L.) seedlings, D-phenylalanine and D-methionine (D-met) inhibited the formation of 1-(malonylamino)cyclopropane-1-carboxylic acid from exogenously administered 1-aminocyclopropane-1-carboxylic acid (ACC), resulting in an increase in free ACC content and stimulation of ethylene production, whereas their L-enantiomers had little or no such effect. When the hypocotyls were administered D-Met, it was mainly metabolized to

Yu Liu; Neil E. Hoffman; Shang Fa Yang

1983-01-01

178

Unnatural Amino Acids. 2. Simple Method of Obtaining Esters of Aziridine2-carboxylic Acids by a Transesterification Reaction  

Microsoft Academic Search

A series of N-unsubstituted esters of aziridine-2-carboxylic acid has been obtained by transesterification in basic medium using primary, secondary, and tertiary alcohols. Methods of transesterification using various bases (K2CO3, ROLi, t-BuOK) have been compared. Transesterification with lithium alcoholates also affords the possibility of obtaining esters of N-substituted aziridine-2-carboxylic acids. Transesterification of chiral esters proceeds with retention of the configuration of

B. Shtrumfs; D. Chernyak; I. Kums; I. Kalvins; P. Trapencieris

2004-01-01

179

Isolation and Molecular Characterization of 1-Aminocyclopropane-1-carboxylic Acid Synthase Genes in Hevea brasiliensis.  

PubMed

Ethylene is an important factor that stimulates Hevea brasiliensis to produce natural rubber. 1-Aminocyclopropane-1-carboxylic acid synthase (ACS) is a rate-limiting enzyme in ethylene biosynthesis. However, knowledge of the ACS gene family of H. brasiliensis is limited. In this study, nine ACS-like genes were identified in H. brasiliensis. Sequence and phylogenetic analysis results confirmed that seven isozymes (HbACS1-7) of these nine ACS-like genes were similar to ACS isozymes with ACS activity in other plants. Expression analysis results showed that seven ACS genes were differentially expressed in roots, barks, flowers, and leaves of H. brasiliensis. However, no or low ACS gene expression was detected in the latex of H. brasiliensis. Moreover, seven genes were differentially up-regulated by ethylene treatment. These results provided relevant information to help determine the functions of the ACS gene in H. brasiliensis, particularly the functions in regulating ethylene stimulation of latex production. PMID:25690030

Zhu, Jia-Hong; Xu, Jing; Chang, Wen-Jun; Zhang, Zhi-Li

2015-01-01

180

Isolation and Molecular Characterization of 1-Aminocyclopropane-1-carboxylic Acid Synthase Genes in Hevea brasiliensis  

PubMed Central

Ethylene is an important factor that stimulates Hevea brasiliensis to produce natural rubber. 1-Aminocyclopropane-1-carboxylic acid synthase (ACS) is a rate-limiting enzyme in ethylene biosynthesis. However, knowledge of the ACS gene family of H. brasiliensis is limited. In this study, nine ACS-like genes were identified in H. brasiliensis. Sequence and phylogenetic analysis results confirmed that seven isozymes (HbACS1–7) of these nine ACS-like genes were similar to ACS isozymes with ACS activity in other plants. Expression analysis results showed that seven ACS genes were differentially expressed in roots, barks, flowers, and leaves of H. brasiliensis. However, no or low ACS gene expression was detected in the latex of H. brasiliensis. Moreover, seven genes were differentially up-regulated by ethylene treatment.These results provided relevant information to help determine the functions of the ACS gene in H. brasiliensis, particularly the functions in regulating ethylene stimulation of latex production. PMID:25690030

Zhu, Jia-Hong; Xu, Jing; Chang, Wen-Jun; Zhang, Zhi-Li

2015-01-01

181

Incorporation of carboxylation multiwalled carbon nanotubes into biodegradable poly(lactic-co-glycolic acid) for bone tissue engineering  

Microsoft Academic Search

Biodegradable poly(lactic-co-glycolic acid) (PLGA)\\/carboxyl-functionalized multi-walled carbon nanotube (c-MWCNT) nanocomposites were successfully prepared via solvent casting technique. Rat bone marrow-derived mesenchymal stem cells (MSCs) were employed to assess the biocompatibility of the nanocomposites in vitro. Scanning electron microscopy (SEM) observations revealed that c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLGA matrix. Surface properties were determined by means of

Cuilin Lin; Yifang Wang; Youqun Lai; Wei Yang; Fei Jiao; Honggang Zhang; Shefang Ye; Qiqing Zhang

2011-01-01

182

Discovery of a Novel Series of CRTH2 (DP2) Receptor Antagonists Devoid of Carboxylic Acids  

PubMed Central

Antagonism of the CRTH2 receptor represents a very attractive target for a variety of allergic diseases. Most CRTH2 antagonists known to date possess a carboxylic acid moiety, which is essential for binding. However, potential acid metabolites O-acyl glucuronides might be linked to idiosynchratic toxicity in humans. In this communication, we describe a new series of compounds that lack the carboxylic acid moiety. Compounds with high affinity (Ki < 10 nM) for the receptor have been identified. Subsequent optimization succeeded in reducing the high metabolic clearance of the first compounds in human and rat liver microsomes. At the same time, inhibition of the CYP isoforms was optimized, giving rise to stable compounds with an acceptable CYP inhibition profile (IC50 CYP2C9 and 2C19 > 1 ?M). Taken together, these data show that compounds devoid of carboxylic acid groups could represent an interesting alternative to current CRTH2 antagonists in development. PMID:24900284

2011-01-01

183

Efficient esterification of carboxylic acids with alkyl halides catalyzed by fluoride ions in ionic liquids  

Microsoft Academic Search

Ionic liquids based on 1,3-dialkylimidazolinium methanesulfonate have been used as efficient reusable reaction media in the esterification of several carboxylic acids with alkyl halides catalyzed by fluoride ions. The method has wide applicability, and it is mild and green; it is useful for the protection of acids, via ester formation, for alkali labile molecules.

L Brinchi; R Germani; G Savelli

2003-01-01

184

JOURNAL OF GEOPHYSICAL RESEARCH, VOL. ???, XXXX, DOI:10.1029/, Carboxylic Acids, Sulfates, and Organosulfates in1  

E-print Network

by a correlation between OM and radon. Sat-16 urated aliphatic C-CH (alkane) composed 41±27% of OM. Carboxylic acid acid epoxide hydrolysis for proposed surrogate compounds (e.g. isoprene22 oxidation products dominated by saturated aliphatic C-CH (alkane) and carboxylic31 acid (together 90% by mass), identified

Russell, Lynn

185

Self-aggregated nanoparticles of carboxylic curdlan-deoxycholic acid conjugates as a carrier of doxorubicin.  

PubMed

In this study, a new non-toxic, biodegradable, biocompatible and water-soluble carboxylic curdlan bearing the dissociable COOH group in 100% purity, which was prepared by 4-acetamido-TEMPO-mediated oxidation, was hydrophobically modified by deoxycholic acid (DOCA) to attain novel amphiphilic curdlan derivatives (CCDs) for the preparation of nano-carriers for antitumor drug doxorubicin (DOX). Under the effect of ultrasonication, the carboxylic curdlan derivatives in water were self-aggregated into spherical nanoparticles with diameters ranging from 214 nm to 380 nm. The critical aggregation concentrations decreased from 0.047 mg/mL to 0.016 mg/mL with increasing DS of DOCA. DOX-loaded CCD nanoparticles were prepared in an aqueous medium with dialysis method. The DOX-CCD nanoparticles exhibited pH- and dose-dependent drug release profiles during in vitro release experiments. Moreover, the drug transport mechanism was Fickian diffusion according to the Ritger-Peppas model. The CCD nanoparticles might be explored as potential carriers for hydrophobic drugs with controlled release and delivery functions. PMID:25193095

Yan, Jing-Kun; Ma, Hai-Le; Chen, Xia; Pei, Juan-Juan; Wang, Zhen-Bin; Wu, Jian-Yong

2015-01-01

186

Rapid, sensitive and specific derivatization methods with 9-(hydroxymethyl)anthracene for the fluorimetric detection of carboxylic acids prior to reversed-phase high-performance liquid chromatographic separation  

Microsoft Academic Search

Three derivatization procedures are described for the pre-column fluorescence labelling of carboxylic acids. The methods are based on esterification with 9-(hydroxymethyl)anthracene. The carboxylic acid function is activated with 2-bromo-l-methylpyridinium iodide, N,N?-carbonyldiimidazole or N-ethyl-N?-(3-dimethylanopropyl)carbodiimide hydrochloride, respectively. Benzoic acid was completely converted into the corresponding ester with all three methods. About 100 fmol of the acid could be detected after high-performance liquid

H. Lingeman; A. Hulshoff; W. J. M. Underberg; F. B. J. M. Offermann

1984-01-01

187

Structures and spectroscopic studies of indolecarboxylic acids. Part III. Diamminetetrakis-?-(O,O?-indole-3-carboxylate)dicopper(II)  

NASA Astrophysics Data System (ADS)

The crystal and molecular structures of the novel compound diamminetetrakis-?-( O, O'-indole-3-carboxylate)dicopper(II), Cu-I3CA, have been determined using single-crystal X-ray diffraction, infrared spectroscopy and EPR methods. The crystals are monoclinic, space group P2 1/c, with a=9.505(2), b=7.469(1), c=23.779(5), V=1669.1(6) Å 3 and Z=2. Complex has a dinuclear molecular structure of C i symmetry in which the carboxyl groups of the indole-3-carboxylic acid ligands act as bridges. The Cu-Cu distance of 2.6387(8) Å, Cu-O distances of 1.961(2) and 1.970(2) Å, and Cu-NH 3 distance of 2.188(2) Å, are typical of such dinuclear complexes. The novel Cu-I3CA complex unit reveals a remarkable similarity in its structural and spectroscopic features to the Cu(II) complexes of the human anti-inflammatory drug, indomethacin (a derivative of indole-3-acetic acid). The EPR and infrared spectroscopic studies of Cu-I3CA in the solid state well support the results from X-ray analysis. The harmonic vibrational frequencies, infrared intensities and Raman scattering activities of the O-deprotonated indole-3-carboxylate ion (I3CA -) have been calculated using density functional (B3LYP) method with the 6-311++G(d,p) basis set. The potential energy distribution (PED) calculated for the ionic ligand (I3CA -) has proved to be of great help in assigning the infrared spectrum of the title complex. The results from natural bond orbital (NBO) analyses for I3CA - and indole-3-carboxylic acid (I3CA) are discussed.

Morzyk-Ociepa, Barbara; Rozycka-Sokolowska, Ewa

2006-02-01

188

Misincorporation of the proline homologue Aze (azetidine-2-carboxylic acid) into recombinant myelin basic protein.  

PubMed

We have evaluated the effects of the proline homologue Aze (1) (azetidine-2-carboxylic acid) on growth of Escherichia coli strains used to over-express recombinant forms of murine myelin basic protein (rmMBP), and on the degree of misincorporation. Addition of Aze to minimal media resulted in severe diminution of growth rate, but rmMBP could still be produced and purified. Mass spectrometry indicated that a detectable proportion of the rmMBP produced had incorporated Aze instead of proline (Pro), to a maximum of three of eleven possible sites. Molecular modelling of a proline-rich region of rmMBP illustrated that the misincorporation of Aze at any site would cause a severe bend in the polypeptide chain, and that multiple Pro-->Aze substitutions would completely disrupt a poly-proline type II structure that has been conjectured to be functionally significant. PMID:20064647

Bessonov, Kyrylo; Bamm, Vladimir V; Harauz, George

2010-04-01

189

Enantioselective kinetic resolution of phenylalkyl carboxylic acids using metagenome?derived esterases  

PubMed Central

Summary Enantiomerically pure ??arylalkyl carboxylic acids are important synthetic intermediates for the preparation of a wide range of compounds with biological and pharmacological activities. A library of 83 enzymes isolated from the metagenome was searched for activity in the hydrolysis of ethyl esters of three racemic phenylalkyl carboxylic acids by a microtiter plate?based screening using a pH?indicator assay. Out of these, 20 enzymes were found to be active and were subjected to analytical scale biocatalysis in order to determine their enantioselectivity. The most enantioselective and also enantiocomplementary biocatalysts were then used for preparative scale reactions. Thus, both enantiomers of each of the three phenylalkyl carboxylic acids studied could be obtained in excellent optical purity and high yields. PMID:21255306

Fernández?Álvaro, Elena; Kourist, Robert; Winter, Julia; Böttcher, Dominique; Liebeton, Klaus; Naumer, Christian; Eck, Jürgen; Leggewie, Christian; Jaeger, Karl?Erich; Streit, Wolfgang; Bornscheuer, Uwe T.

2010-01-01

190

Carboxylic acid effects on the size and catalytic activity of magnetite nanoparticles.  

PubMed

Magnetite nanoparticles (Fe3O4-NPs) were successfully synthesized in diethylene glycol in the presence of carboxylic acids. They were characterized using XRD, SEM and FTIR. Carboxylic acid plays a critical role in determining the morphology, particle size and size distribution of the resulting particles. The results show that as-prepared magnetite nanoparticles are monodisperse and highly crystalline. The nanoparticles can be easily dispersed in aqueous media and other polar solvents due to coated by a layer of hydrophilic polyol and carboxylic acid ligands in situ. Easily prepared Fe3O4-NPs have been shown to be an active, recyclable, and highly selective catalyst for the epoxidation of cyclic olefins with aqueous 30% H2O2. PMID:25302421

Hosseini-Monfared, Hassan; Parchegani, Fatemeh; Alavi, Sohaila

2015-01-01

191

Evidence for 1-(Malonylamino)cyclopropane-1Carboxylic Acid Being the Major Conjugate of Aminocyclopropane-1- Carboxylic Acid in Tomato Fruit1  

Microsoft Academic Search

Tomato (Lycopersicon esculentum Miller) fruit discs fed with (2,3-14C)1-aminocyclopropane-1-carboxylic acid (ACC) formed 1-malonyl-ACC (MACC) as the major conjugate of ACC in fruit throughout all ripening stages, from immature-green through the red-ripe stage. Another conjugate of ACC, g-glutamyl-ACC (GACC), was formed only in mature-green fruit in an amount about 10% of that of MACC; conjugation of ACC into GACC was not

Galen Peiser; Shang Fa Yang

192

The enzymatic malonylation of 1-aminocyclopropane-1-carboxylic acid in homogenates of mung-bean hypocotyls  

Microsoft Academic Search

Homogenates of hypocotyls of light-grown mung-bean (Vigna radiata (L.) Wilczek) seedlings catalyzed the formation of 1-(malonylamino)cyclopropane-1-carboxylic acid (MACC) from the ethylene precursor 1-aminocyclopropane-1-carboxylic acid (ACC) and malonyl-coenzyme A. Apparent Km values for ACC and malonyl-CoA were found to be 0.17 mM and 0.25 mM, respectively. Free coenzyme A was an uncompetitive inhibitor with respect to malonyl-CoA (apparent Ki=0.3 mM). Only

Christine Kionka; Nikolaus Amrhein

1984-01-01

193

Determination of the asphaltene and carboxylic acid content of a heavy oil using a microfluidic device.  

PubMed

Heavy oil utilisation is set to increase over the coming decades as reserves of conventional oil decline. Heavy oil differs from conventional oil in containing relatively large quantities of asphaltene and carboxylic acids. The proportions of these compounds greatly influence how oil behaves during production and its utilisation as a fuel or feedstock. We report the development of a microfluidic technique, based on a H-cell, that can extract the carboxylic acid components of an oil and assess its asphaltene content. Ultimately this technology could yield a field-deployable device capable of performing measurements that facilitate improved resource management at the point of resource-extraction. PMID:19255665

Bowden, Stephen A; Wilson, Rab; Parnell, John; Cooper, Jonathan M

2009-03-21

194

Simple quantification of surface carboxylic acids on chemically oxidized multi-walled carbon nanotubes  

NASA Astrophysics Data System (ADS)

The surface of multi-walled carbon nanotube (MWCNT) was chemically oxidized using nitric acid and sulfuric-nitric acid mixtures. Thermogravimetric analysis, transmission electron microscopy and infrared spectroscopy revealed that the use of acid mixtures led to higher degree of oxidation. More quantitative identification of surface carboxylic acids was carried out using X-ray photoelectron spectroscopy (XPS) and acid-base titration. However, these techniques are costly and require very long analysis times to promptly respond to the extent of the reaction. We propose a much simpler method using pH measurements and pre-determined pKa value in order to estimate the concentration of carboxylic acids on the oxidized MWCNT surfaces. The results from this technique were consistent with those obtained from XPS and titration, and it is expected that this simple quantification method can provide a cheap and fast way to monitor and control the oxidation reaction of MWCNT.

Gong, Hyejin; Kim, Seong-Taek; Lee, Jong Doo; Yim, Sanggyu

2013-02-01

195

Separation of Carboxylic Acids from Waste Water via Reactive Extraction  

Microsoft Academic Search

The separation (or removal) of organic residues from aqueous waste streams released from industries is important and essential from the points of view of pollution control and recovery of useful materials. The disposal of waste waters containing most widely-used industrial organic acids such as acetic acid, formic acid and propionic acid has been recognized as a significant expense to the

Sushil Kumar; B. V. Babu

196

Hydrogen bonds in 1:1 complex of piperidine-3-carboxylic acid with salicylic acid  

NASA Astrophysics Data System (ADS)

The 1:1 complex between the zwitterionic piperidinium-3-carboxylate (P3C) and salicylic acid (SAL), P3C·SAL, has been characterized by single crystal X-ray analysis, FTIR and NMR spectroscopy, and by DFT calculations. The crystals are orthorhombic, space group Pbca, with a = 11.6477(7), b = 9.1754(6), c = 23.5833(12) Å. An O sbnd H⋯O bridge (2.537(1) Å) links the SAL and P3C moieties. The proton in this H bond is located closer to the salicylic carboxylate group. In the P3C moiety, the piperidine ring adopts the chair conformation, and the carboxylate group is in the axial orientation and is stabilized by an intramolecular N +sbnd H⋯O hydrogen bond of 2.847(1) Å. In the crystal packing, two P3C·SAL units form a centrosymmetric dimer through a pair of intermolecular N +sbnd H⋯O bonds of 2.801(1) Å. The dimers form a zigzag chain linked via another N +sbnd H⋯O bond (2.799(1) Å). In the structures of the monomeric [P3C·SAL] and dimeric [(P3C·SAL) 2] species optimized by B3LYP/6-31G(d,p) calculations, both the inter- and intra-molecular hydrogen bonds are shorter than in the crystal. The FTIR spectrum shows a broad absorption in the 3100-2400 cm -1 region attributed to ?NH and ?OH vibrations. The broad absorption in the 1500-600 cm -1 region is attributed to the O sbnd H·O hydrogen bonds. The 1H and 13C NMR spectra have been analyzed to elucidate the structure of the P3C·SAL complex in solution. The GIAO magnetic isotropic shielding tensors have been used to predict the 1H and 13C chemical shifts in DMSO solution.

Bartoszak-Adamska, El?bieta; Dega-Szafran, Zofia; Krociak, Magdalena; Jaskolski, Mariusz; Szafran, Miros?aw

2009-02-01

197

Extraction of aromatic carboxylic acids and phenols by strongly solvating organophosphorus compounds and sulfoxides  

Microsoft Academic Search

Summary This paper contains a systematic comparison of the extracting power and selectivity of tri-n-butylphosphate (TBP), di-n-octylsulfoxide (DOSO) and tri-n-octylphosphinoxide (TOPO) in the extraction of aromatic carboxylic acids and phenols from aqueous perchloric acid solutions of varying pH. Organophosphorus compounds and sulfoxides form hydrogen bonds to proton-donating molecules. This rather specific interaction can be used for solvent extraction of acidic

Peter Markl

1981-01-01

198

Olfactory Sensitivity and Odor StructureActivity Relationships for Aliphatic Carboxylic Acids in CD1 Mice  

Microsoft Academic Search

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

Selçuk Can Güven; Matthias Laska

2012-01-01

199

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

200

Functional and anionic cellulose-interacting polymers by selective chemo-enzymatic carboxylation of galactose-containing polysaccharides.  

PubMed

Carboxylated, anionic polysaccharides were selectively prepared using a combination of enzymatic and chemical reactions. The galactose-containing polysaccharides studied were spruce galactoglucomannan, guar galactomannan, and tamarind galactoxyloglucan. The galactosyl units of the polysaccharides were first oxidized with galactose oxidase (EC 1.1.3.9) and then selectively carboxylated, resulting in the galacturonic acid derivatives with good conversion and yield. The degrees of oxidation (DO) of the products were determined by gas chromatography-mass spectrometry (GC-MS). A novel feasible electrospray ionization-mass spectrometry (ESI-MS) method was also developed for the determination of DO. The solution properties and charge densities of the products were investigated. The interaction of the products with cellulose was studied by two methods, bulk sorption onto bleached birch kraft pulp and adsorption onto nanocellulose ultrathin films by quartz crystal microbalance with dissipation (QCM-D). To study the effect of the location of the carboxylic acid groups on the physicochemical properties, polysaccharides were also oxidized by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated reaction producing polyuronic acids. The chemo-enzymatically oxidized galacturonic polysaccharides with an unmodified backbone had a better ability to interact with cellulose than the TEMPO-oxidized products. The selectively carboxylated polysaccharides can be further exploited, as such, or in the targeted functionalization of cellulose surfaces. PMID:22724576

Parikka, Kirsti; Leppänen, Ann-Sofie; Xu, Chunlin; Pitkänen, Leena; Eronen, Paula; Osterberg, Monika; Brumer, Harry; Willför, Stefan; Tenkanen, Maija

2012-08-13

201

Synthesis of Tryptoline-3-Carboxylic Acid Derivatives A Novel Antidiabetic Agent  

PubMed Central

The compounds, 2-(methylsulfonyl)-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole-3-carboxylic acid (DM3), 2-(phenylsulfonyl)-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole-3-carboxylic acid (DM4), and 2-(p-toluenesulfonyl)-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole-3-carboxylic acid (DM5) were synthesized by coupling of 1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole-3-carboxylic acid (DM2) with methanesulfonyl chloride, benzenesulfonyl chloride, and toluenesulfonyl chloride, which in turn, was synthesized by dissolving dilute aqueous ammonia with 2-(N-hydroxy methyl amino)-indol-3-yl-propanoic acid (DM1) which is the reaction product of l-tryptophan and formalin. All the intermediates and title compounds were characterized by physical, chemical, analytical, and spectral data. All the title compounds have been screened for in vivo antidiabetic activity in streptozotocin-induced diabetic rats, and serum glucose was estimated spectrophotometrically at 505 nm by glucose oxidase/peroxidase method. Compound DM5 showed potent antidiabetic activity. PMID:21731359

Choudhary, AN; Kohli, MS; Kumar, A; Joshi, A

2011-01-01

202

A chiral bisthiourea as a chiral solvating agent for carboxylic acids in the presence of DMAP.  

PubMed

A simple chiral bisthiourea has been used as a highly effective and practical chemical solvating agent (CSA) for diverse ?-carboxylic acids in the presence of DMAP. Excellent enantiodiscrimination based on well-resolved ?-H NMR signals of the enantiomers of carboxylic acids can be obtained without interference from the chiral bisthiourea and DMAP. To check the practicality of the chiral bisthiourea/DMAP for enantiomeric determination, the ee values of mandelic acid (MA) samples over a wide ee range were determined by integration of the ?-H signal of MA in (1)H NMR. A discrimination mechanism is proposed, that the formation of two diasteromeric ternary complexes between the chiral bisthiourea and two in situ formed enantiomeric carboxylate-DMAPH(+) ion pairs discriminates the enantiomers of carboxylic acids. Computational modeling studies show that the chemical shift value of ?-H of (S)-MA is greater than that of (R)-MA in ternary complexes, which is consistent with experimental observation. 1D and 2D NOESY spectra demonstrate the intermolecular noncovalent interactions between the protons on the aromatic rings of chiral bisthiourea and ?-H of the enantiomers of racemic ?-methoxy phenylacetic acids in the complexes. PMID:24050150

Bian, Guangling; Fan, Hongjun; Yang, Shiwei; Yue, Huifeng; Huang, Huayin; Zong, Hua; Song, Ling

2013-09-20

203

Complexation of lanthanides with crown ether carboxylic acids and its applications in analytical chemistry  

SciTech Connect

The extraction characteristics of trivalent lanthanides by three crown ether carboxylic acids of different lipophilicities were investigated. Extraction was found to be independent of anions and strongly dependent on pH. Quantitative extraction of lanthanides was observed in the pH range of 6-8 by all three crown ether carboxylic acids: sym-dibenzo-16-crown-5 oxyacetic acid (I), 2-(sym-dibenzo-16-crown-5-oxy)hexanoic acid (II), and 2-(sym-dibenzo-16-crown-5-oxy)stearic acid (III). Results of competitive experiments indicated that this extraction system was highly selective for lanthanides relative to other major ionic species, such as the alkali metal ions, the alkaline earth metal ions, and transition metal ions. The extraction method has been applied to the determination of low levels of lanthanides in natural waters and in biological materials. Sym-dibenzo-16-crown-5-oxyacetic acid had insufficient lipophilicity to remain in the organic phase when the pH of the aqueous phase was high and the organic to aqueous phase ratio was small. Extraction efficiency increased with the increasing lipophilicity of the crown ether carboxylic acids, which followed the order I < II < III. Using 2-(sym-dibenzo-16-crown-5-oxy)hexanoic acid as an extractant, lanthanides in some natural water and biological samples were determined by neutron activation analysis (NAA). Uranium can also be extracted by the three crown ether carboxylic acids with high efficiency. 2-(Sym-dibenzo-16-crown-5-oxy)hexanoic acid was utilized to extract uranyl ions from seawater and river water samples into chloroform, followed by back-extraction with a pH 2 nitric acid solution prior to NAA. The extraction method combined with NAA provides a sensitive method for the determination of uranium in natural waters.

Tang, Jian.

1989-01-01

204

Low-Molecular Weight Carboxylic Acids in Gas Phase in a Developing Megacity  

NASA Astrophysics Data System (ADS)

Carboxylic acids are amongst the plethora of pollutants that are currently ubiquitous in the environment. Molecular distributions of carboxylic acids have been studied in the atmosphere of the developing mega city Karachi, Pakistan. As a region the city is experiencing industrial and population growth at an unparallel rate. Karachi served as a great focal point to observe the effects of industrial development on a growing city and how it contributes to the progression of environmental pollution. Results indicate that acetic and formic acids are important components of the Karachi atmosphere. The most abundant acids, by a substantial margin, were acetic acid and formic acid, with concentrations of 0.70 - 14.2 ppb and 0.82 - 11.0 ppb, respectively. On the average acetic acid levels exceeded those of formic acid. Concentrations of propionic acid, pyruvic acid, and glyoxalic acid ranged 0.03 - 1.41, 0.01 - 0.28, and 0.02 - 0.14 ppb, respectively. The gaseous acids showed diurnal cycles, with higher mixing ratios during nighttime. Compared with other metropolitans in the world, the level of acetic and formic acid concentration of Karachi is much higher. The ratio of formic to acetic acid was used to distinguish primary sources from secondary sources. A mean ratio of 0.85 was found. A positive correlation (r = 0.65 - 0.94) was observed between the acid concentrations suggesting that they have similar sources. Carboxylic acid concentrations appear to arise both from direct emissions and from atmospheric oxidation of hydrocarbons.

Khwaja, H. A.; Saied, S.; Hussain, M. M.; Siddique, A.; Butts, C.; Kamran, S. S.; Khan, M. K.

2013-12-01

205

RAPID AND EFFICIENT PROTOCOL FOR THE SEMI-QUANTITATIVE ANALYSIS OF C2+ CARBOXYLIC ACIDS IN CRUDE OILS  

Microsoft Academic Search

routinely analysed due to laborious workup procedures, often with low or inaccurate recoveries. The methods often require large amounts of solvent which prevents the analysis of low molecular weigh carboxylic acids due to evaporative losses during sample preparation. Here we present an alternative method for the analysis of carboxylic acids from crude oils. The protocol is based on small-scale column

Christian HALLMANN; Ben VAN AARSSEN

206

The Enolase Superfamily: A General Strategy for Enzyme-Catalyzed Abstraction of the R-Protons of Carboxylic Acids  

E-print Network

-Protons of Carboxylic Acids Patricia C. Babbitt,*, Miriam S. Hasson,§,| Joseph E. Wedekind,,# David R. J. Palmer by their ability to catalyze the abstraction of the R-proton of a carboxylic acid to form an enolic intermediate specialized enzymes: mandelate racemase, galactonate dehydratase, glucarate dehydratase, muconate

Rayment, Ivan

207

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

208

Selective Na(+)/K(+) effects on the formation of ?-cyclodextrin complexes with aromatic carboxylic acids: competition for the guest.  

PubMed

We investigated the effects of K(+) and Na(+) ions on the formation of ?-cyclodextrin complexes with ionized aromatic carboxylic acids. Using solution calorimetry and (1)H NMR, we performed the thermodynamic and structural investigation of ?-cyclodextrin complex formation with benzoic and nicotinic acids in different aqueous solutions containing K(+) and Na(+) ions as well as in pure water. The experiments show that the addition of sodium ions to solution leads to a decrease in the binding constants of the carboxylic acids with ?-cyclodextrin as compared to pure water and solutions containing potassium ions. From another side, the effect of potassium ions on the binding constants is insignificant as compared to pure water solution. We suggest that the selectivity of cation pairing with carboxylates is the origin of the difference between the effects of sodium and potassium ions on complex formation. The strong counterion pairing between the sodium cation and the carboxylate group shifts the equilibrium toward dissociation of the binding complexes. In turn, the weak counterion pairing between the potassium cation and the carboxylate group has no effect on the complex formation. We complemented the experiments with molecular modeling, which shows the molecular scale details of the formation of cation pairs with the carboxylate groups of the carboxylic acids. The fully atomistic molecular simulations show that sodium ions mainly form direct contact pairs with the carboxylate group. At the same time, potassium ions practically do not form direct contact pairs with the carboxylate groups and usually stay in the second solvation shell of carboxylate groups. That confirms our hypotheses that the selective formation of ion pairs is the main cause of the difference in the observed effects of sodium and potassium salts on the guest-host complex formation of ?-cyclodextrin with aromatic carboxylic acids. We propose a molecular mechanism explaining the effects of salts, based on competition between the cations and ?-cyclodextrin for binding with the ionized carboxylic acids. PMID:20843099

Terekhova, Irina V; Romanova, Anastasia O; Kumeev, Roman S; Fedorov, Maxim V

2010-10-01

209

Lewis Acid Promoted Ruthenium(II)-Catalyzed Etherifications by Selective Hydrogenation of Carboxylic Acids/Esters.  

PubMed

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

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

2015-04-20

210

Acute toxicity assessment of perfluorinated carboxylic acids towards the Baltic microalgae  

Microsoft Academic Search

The presence of high-energy carbon–fluorine bonds in perfluoro compounds lends them great stability and causes them to be environmentally persistent. Relatively little is known about the acute toxicity of perfluorinated carboxylic acids (PFCAs) to ecotoxicological markers such as aquatic plants and animals. This study tested the toxicity of these compounds to the green alga Chlorella vulgaris, the diatom Skeletonema marinoi

Adam Lata?a; Marcin N?dzi; Piotr Stepnowski

2009-01-01

211

Selective deuteration of (hetero)aromatic compounds via deutero-decarboxylation of carboxylic acids.  

PubMed

A practical, mild and highly selective protocol for the monodeuteration of a variety of arenes and heteroarenes is presented. Catalytic amounts of Ag(I) salts in DMSO/D(2)O are shown to facilitate the deutero-decarboxylation of ortho-substituted benzoic and heteroaromatic ?-carboxylic acids in high yields with excellent levels of deuterium incorporation. PMID:22418863

Grainger, Rachel; Nikmal, Arif; Cornella, Josep; Larrosa, Igor

2012-04-28

212

Conversion of 1-aminocyclopropane-1-carboxylic acid to ethylene by isolated vacuoles of Pisum sativum L  

Microsoft Academic Search

We compared the distribution of 1-aminocyclopropane-1-carboxylic acid (ACC) between the vacuole of isolated pea (Pisum sativum L.) protoplasts and the remainder of the cell and found that over 80% of the ACC was localized in the vacuole. Isolated protoplasts and vacuoles evolved ethylene. Over 80% of the ethylene production by protoplasts could be accounted for as originating from the vacuole.

Micha Guy; Hans Kende

1984-01-01

213

Simple method for the synthesis of bicyclic pyridine bases from 1-ethynylcycloalkanols and carboxylic acid chlorides  

Microsoft Academic Search

A new, simple and effective method was developed for the synthesis of difficultly obtainable bicyclic pyridine bases by the condensation of cyclic ethynylcarbinols with carboxylic acid anhydrides in the presence of an equimolar ZnCl2-POCl3 mixture followed by treatment with ammonium hydroxide.

F. A. Selimov; O. G. Rutman; U. M. Dzhemilev

1988-01-01

214

Direct Esterification of Carboxylic Acid with Alkyl Halide by Cu(I) Oxide  

Microsoft Academic Search

Esterification is one of the most fundamental synthetic reaactions, for which many methods have been known.) The present communication describes a new method of esterification of carboxylic acid with alkyl halide using Cu2o-base system. As the base component, isonitrile and pypridine are suitable. This new method was found in the course of the studies upon the exploration of the catalysis

T. Saegusa; I. Murase

1972-01-01

215

Carboxylic acids, sulfates, and organosulfates in processed continental organic aerosol over the southeast Pacific Ocean  

E-print Network

. This continental source is supported by a correlation between OM and radon. Saturated aliphatic CCH (alkane.g., isoprene oxidation products) or reactive glyoxal uptake mechanisms from laboratory studies aliphatic CCH (alkane) and carboxylic acid (together, 90% by mass), identified as the marine and combustion

216

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

NASA Technical Reports Server (NTRS)

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

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

1981-01-01

217

Reagents and Synthetic Methods 28. Modified Procedures for Anhydrization, Esterification and Thiolesterification of Carboxylic Acids by Means of Available Phosphorus Reagents  

Microsoft Academic Search

Carboxylic acid anhydrides,esters and thiol esters are obtained by a one-pot method from carboxylic acids and alcohols or thiol by means of phosphorus oxychloride or phenyl dichlorophosphoridate reagents.

A. Arrieta; T. García; J. M. Lago; C. Palomo

1983-01-01

218

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...

219

Synthesis of 3,3-dimethylazetidine-2-carboxylic acid and some derivatives  

Microsoft Academic Search

?-Chloro-?-(N-alkylimino)esters were reduced by sodium cyanoborohydride in methanol in the presence of acetic acid with complete selectivity to give rise to either ?-chloro-?-(N-alkylamino)esters (reaction at 0°C) or 1-alkyl-3,3-dimethylazetidine-2-carboxylic esters (reaction at reflux). The isolable ?-chloro-?-(N-alkylamino)esters are suitable sources for 1-(N-alkylamino)-2,2-dimethylcyclopropane-1-carboxylic esters via base-induced 1,3-dehydrochlorination, while the former substrates as transient species undergo 1,4-dehydrochlorination to the corresponding azetidines. The latter process

Dirk Tourwé

1998-01-01

220

Enhanced Production of Carboxylic Acids by Engineering of Rhizopus  

Technology Transfer Automated Retrieval System (TEKTRAN)

The fungus Rhizopus is frequently used to convert, or ferment sugars obtained from agricultural crops to lactic acid. This natural product has long been utilized by the food industry as an additive for preservation, flavor, and acidity. Additionally, it is used for the manufacture of environmental...

221

Emulsion copolymerization of styrene with acrylic or methacrylic acids – distribution of the carboxylic group  

Microsoft Academic Search

Studies on batch emulsion copolymeization of styrene with acrylic acid (AA) or methacrylic acid (MAA) were carried out. The\\u000a effect of AA or MAA on the total conversion of the monomers was studied by a gravimetric method. The distribution of the carboxylic\\u000a group in the copolymer microspheres was investigated by X-ray photoelectron spectroscopy and elemental analysis. The surface\\u000a content of

P. H. Wang; C.-Y. Pan

2001-01-01

222

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 ...

223

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

224

Simple thiol-ene click chemistry modification of SBA-15 silica pores with carboxylic acids.  

PubMed

A straightforward approach for anchoring tailored carboxylic groups in mesoporous SiO2 colloidal materials is presented. The thiol-ene photochemical reaction between vinyltrimethoxysilane precursors and various thiocarboxylic acids which has, click chemistry features (i.e. high conversion yields, insensitivity to oxygen, mild reaction conditions), results in carboxylated silane precursors that can be readily used as surface modifiers. The carboxylic groups of acetic, undecanoic and succinic acid were immobilized on the silica mesopore walls of SBA-15 powders employing the synthesized silane precursors. Post-grafting has been confirmed through infrared spectrometry (FTIR), energy dispersive X-ray spectroscopy (EDS), elemental analysis (EA) and zeta potential measurements. Detailed field-emission gun scanning electron microscopy (FESEM) images and small angle X-ray scattering (SAXS) data revealed parallel mesopores and ordered mesostructures. It is shown that the immobilized COOH groups are chemically accessible for acid-base reactions as well as copper adsorption. Immobilization of easily synthesized tailored carboxylic modified alkoxide precursors within mesoporous systems provides a unique chemical nanoenvironment within these ordered frameworks. PMID:25845883

Bordoni, Andrea V; Lombardo, M Verónica; Regazzoni, Alberto E; Soler-Illia, Galo J A A; Wolosiuk, Alejandro

2015-07-15

225

Role of biologically active inorganic anions Cl- and Br- in inclusion complex formation of ?-cyclodextrin with some aromatic carboxylic acids  

NASA Astrophysics Data System (ADS)

1H NMR spectroscopy was used to evaluate the effects of biologically active anions Cl- and Br- in inclusion complex formation of ?-cyclodextrin with some aromatic carboxylic acids. It was demonstrated that presence of Br- anions induces the decrease in ?-cyclodextrin binding affinity to carboxylic acids, while Cl- has no a noticeable effect. The observed difference was discussed in terms of selective interactions of ?-cyclodextrin with Br- and Cl-. Only Br- anions are able to penetrate into ?-cyclodextrin cavity and compete with carboxylic acid molecule for the macrocyclic cavity. This competition shifts the ?-cyclodextrin/acid equilibrium in the direction of complex dissociation.

Terekhova, Irina; Chibunova, Ekaterina; Kumeev, Roman; Alper, Gennady

2013-02-01

226

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

227

Process for producing peracids from aliphatic hydroxy carboxylic acids  

DOEpatents

A process is described for producing peracids from lactic acid-containing solutions derived from biomass processing systems. It consists of adjusting the pH of the solution to about 8 to 9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids. The solution is oxidized to produce volatile lower aliphatic aldehydes. The aldehydes are removed as they are generated and converted to peracids.

Chum, H.L.; Palasz, P.D.; Ratcliff, M.A.

1984-12-20

228

Process for producing peracids from aliphatic hydroxy carboxylic acids  

DOEpatents

A process for producing peracids from lactic acid-containing solutions derived from biomass processing systems comprising: adjusting the pH of the solution to about 8-9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids; oxidizing the solution to produce volatile lower aliphatic aldehydes; removing said aldehydes as they are generated; and converting said aldehydes to peracids.

Chum, Helena L. (Arvada, CO); Ratcliff, Matthew A. (Lakewood, CO); Palasz, Peter D. (Lakewood, CO)

1986-01-01

229

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, 2010 CFR

...5-oxo-1H-imidazol-2-yl]-3-quinoline carboxylic acid; tolerance for residues...5-oxo-1H -imidazol-2-yl]-3-quinoline carboxylic acid; tolerance for residues...5-oxo-1H -imidazol-2-yl]-3-quinoline carboxylic acid, in or on the raw...

2010-07-01

230

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

231

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...

232

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...

233

Highly efficient esterification of carboxylic acids with alcohols by montmorillonite-enwrapped titanium as a heterogeneous acid catalyst  

Microsoft Academic Search

Montmorillonite-enwrapped titanium catalyst was found to efficiently promote the esterification of carboxylic acids with alcohols. In comparison to other catalysts reported to date, this heterogeneous catalyst offers a remarkably simple workup procedure, and is reusable without any appreciable loss in its activity and selectivity.

Tomonori Kawabata; Tomoo Mizugaki; Kohki Ebitani; Kiyotomi Kaneda

2003-01-01

234

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

235

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

236

A Simple and Efficient Method for Direct Acylation of Acetals with Long Alkyl-Chain Carboxylic Acid Anhydrides  

Microsoft Academic Search

We have developed an efficient and simple method for direct transformation of acetals to carboxylic acid esters. The method consists of treatment of acetals with carboxylic anhydrides in the presence of boron trifluoride etherate as a catalyst and affords the corresponding ester derivatives in high yields with retention of configuration in the alcohol moiety. Some mechanistic aspects of this synthetically

Stephan D. Stamatov; Jacek Stawinski

2000-01-01

237

Stereospecific Biohydroxylations of Protected Carboxylic Acids with Cunninghamella blakesleeana.  

PubMed

Cunninghamella blakesleeana DSM 1906 was found to be an efficient biocatalyst for the biotransformation of cycloalkylcarboxylic acids into hydroxy and oxo derivatives. When cultivated in submerged culture, the fungus grew in pellets. In comparison with malt extract-glucose-peptone-yeast extract medium (medium E), Czapek-Dox medium was found to reduce pellet size. Cycloalkylcarboxylic acids were protected against microbial degradation by chemical transformation into 2-cycloalkyl-1,3-benzoxazoles. The transformations of protected cyclopentyl-, cyclohexyl-, cycloheptyl-, and cyclooctylcarboxylic acids by C. blakesleeana were investigated. The biotransformations were performed in medium E by using an aerated, stirred-tank bioreactor. The transformation of 2-cyclopentyl-1,3-benzoxazole yielded (1S,3S)-3-(benz-1,3-oxazol-2-yl)cyclopentan-1-ol as the main product. The main by-product was (1R)-3-(benz-1,3-oxazol-2-yl)cyclopentan-1-one, and 2-(benz-1,3-oxazol-2-yl)cyclopentan-1-ol was also obtained in small amounts. During the experiment, the enantiomeric excess of the main product increased up to 64%. 2-Cyclohexyl-1,3-benzoxazole was hydroxylated to 4-(benz-1,3-oxazol-2-yl)cyclohexan-1-ol. 2-Cycloheptyl-1,3-benzoxazole and 2-cyclooctyl-1,3-benzoxazole were transformed into several alcohols and ketones, all in low yields (2 to 19%). PMID:16535367

Kreiner, M; Braunegg, G; de Raadt, A; Griengl, H; Kopper, I; Petsch, M; Plachota, P; Schoo, N; Weber, H; Zeiser, A

1996-07-01

238

Stereospecific Biohydroxylations of Protected Carboxylic Acids with Cunninghamella blakesleeana  

PubMed Central

Cunninghamella blakesleeana DSM 1906 was found to be an efficient biocatalyst for the biotransformation of cycloalkylcarboxylic acids into hydroxy and oxo derivatives. When cultivated in submerged culture, the fungus grew in pellets. In comparison with malt extract-glucose-peptone-yeast extract medium (medium E), Czapek-Dox medium was found to reduce pellet size. Cycloalkylcarboxylic acids were protected against microbial degradation by chemical transformation into 2-cycloalkyl-1,3-benzoxazoles. The transformations of protected cyclopentyl-, cyclohexyl-, cycloheptyl-, and cyclooctylcarboxylic acids by C. blakesleeana were investigated. The biotransformations were performed in medium E by using an aerated, stirred-tank bioreactor. The transformation of 2-cyclopentyl-1,3-benzoxazole yielded (1S,3S)-3-(benz-1,3-oxazol-2-yl)cyclopentan-1-ol as the main product. The main by-product was (1R)-3-(benz-1,3-oxazol-2-yl)cyclopentan-1-one, and 2-(benz-1,3-oxazol-2-yl)cyclopentan-1-ol was also obtained in small amounts. During the experiment, the enantiomeric excess of the main product increased up to 64%. 2-Cyclohexyl-1,3-benzoxazole was hydroxylated to 4-(benz-1,3-oxazol-2-yl)cyclohexan-1-ol. 2-Cycloheptyl-1,3-benzoxazole and 2-cyclooctyl-1,3-benzoxazole were transformed into several alcohols and ketones, all in low yields (2 to 19%). PMID:16535367

Kreiner, M.; Braunegg, G.; de Raadt, A.; Griengl, H.; Kopper, I.; Petsch, M.; Plachota, P.; Schoo, N.; Weber, H.; Zeiser, A.

1996-01-01

239

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

240

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

241

Pyrolysis of coal model compounds containing aromatic carboxylic acids: The role of carboxylic acids in cross-linking reactions in low-rank coal  

SciTech Connect

The pyrolysis of 1-(3-carboxyphenyl)-2(4-biphenyl)ethane (1) diluted in 10-fold excess of naphthalene has been studied at 400 {degrees}C to investigate whether decarboxylation of aromatic carboxylic acids can lead to cross-linked products. The dominant mechanism for decarboxylation was found to be an acid-promoted ionic pathway that does not lead to cross-linking. However, a small amount of cross-linked products (i.e. naphthalene grafted onto decarboxylated 1) were formed. The yields of the cross-linked products were found to be decreased in the presence of a hydrogen donor solvent, tetralin, suggesting that these products were formed by a free-radical pathway. The mechanism for the formation of cross-linked products was proposed to occur from the formation and decomposition of anhydrides of 1 during pyrolysis.

Eskay, T.P.; Britt, P.F.; Buchanan, A.C. III

1997-06-01

242

[Determination of the azetidine-2-carboxylic acid from lily of the valley].  

PubMed

This paper reports the separation and determination of the azetidine-2-carboxylic acid in lily of the valley by high performance liquid chromatography (HPLC) with post-column derivatization and fluorescence detection. The operating conditions were cation exchange resin column (30 cm x 0.4 cm i.d.) with buffer solution A [1.96% (mass fraction) sodium citrate solution pH 3.10 +/- 0.02] and B [2.1% (mass fraction) sodium nitrate solution pH 9.60 +/- 0.02] as mobile phase at flow-rate of 0.4 mL/min, gradient elution, column temperature 65 degrees C, detection wavelength lambda ex = 338 nm and lambda em = 425 nm. The retention time of azetidine-2-carboxylic acid was 5.86 minutes. The recovery was 96.4% and coefficient of variation was 0.94%. This method is simple, rapid and sensitive. PMID:12552869

Liu, H

1999-07-01

243

QSAR study of carboxylic acid derivatives as HIV-1 Integrase inhibitors.  

PubMed

QSAR studies have been carried out on carboxylic acid derivatives as HIV-1 Integrase inhibitors using 3D-MoRSE (3D-Molecular Representation of Structure based on Electron diffraction) descriptors. The stepwise multiple linear regression (stepwise-MLR) and replacement method (RM) methods are used to select descriptors which are responsible for the inhibitory activity of these compounds. Mathematical models are obtained by support vector machine (SVM), back-propagation neural networks (BPNN) and multiple linear regression (MLR). Leave-one-out, Leave-many-out (7% and 18%) cross-validation and external validation are carried out with the aim of evaluating the predictive ability of the models. The values of their respective squared correlations coefficients are 0.731, 0.664, 0.523 and 0.766, respectively. Our best QSAR model reveals the polarizability, mass as the most influencing atomic properties in the structures of the carboxylic acid derivatives. PMID:20561721

Cheng, Zhengjun; Zhang, Yuntao; Fu, Weizhong

2010-09-01

244

Growth modification of seeded calcite using carboxylic acids: atomistic simulations.  

PubMed

Molecular dynamics simulations were used to investigate possible explanations for experimentally observed differences in the growth modification of calcite particles by two organic additives, polyacrylic acid (PAA) and polyaspartic acid (p-ASP). The more rigid backbone of p-ASP was found to inhibit the formation of stable complexes with counter-ions in solution, resulting in a higher availability of p-ASP compared to PAA for surface adsorption. Furthermore the presence of nitrogen on the p-ASP backbone yields favorable electrostatic interactions with the surface, resulting in negative adsorption energies, in an upright (brush conformation). This leads to a more rapid binding and longer residence times at calcite surfaces compared to PAA, which adsorbed in a flat (pancake) configuration with positive adsorption energies. The PAA adsorption occurring despite this positive energy difference can be attributed to the disruption of the ordered water layer seen in the simulations and hence a significant entropic contribution to the adsorption free energy. These findings help explain the stronger inhibiting effect on calcite growth observed by p-ASP compared to PAA and can be used as guidelines in the design of additives leading to even more marked growth modifying effects. PMID:20304410

Aschauer, Ulrich; Spagnoli, Dino; Bowen, Paul; Parker, Stephen C

2010-06-01

245

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

246

Cs2CO3-Promoted Carboxylation of N-Tosylhydrazones with Carbon Dioxide toward ?-Arylacrylic Acids.  

PubMed

A Cs2CO3-promoted carboxylation of N-tosylhydrazones and CO2 has been developed. The reaction proceeded efficiently at 80 °C under atmospheric CO2, gave the corresponding ?-arylacrylic acids in moderate to good yields. This method was featured with (1) the employment of Cs2CO3 rather than (n)BuLi as the base; (2) a reaction temperature of 80 °C rather than -78 °C. PMID:25695856

Sun, Song; Yu, Jin-Tao; Jiang, Yan; Cheng, Jiang

2015-03-01

247

Borate esters as convenient reagents for direct amidation of carboxylic acids and transamidation of primary amides.  

PubMed

Simple borates serve as effective promoters for amide bond formation with a variety of carboxylic acids and amines. With trimethyl or tris(2,2,2-trifluoroethyl) borate, amides are obtained in good to excellent yield and high purity after a simple work-up procedure. Tris(2,2,2-trifluoroethyl) borate can also be used for the straightforward conversion of primary amides to secondary amides via transamidation. PMID:21212879

Starkov, Pavel; Sheppard, Tom D

2011-03-01

248

Dynamics of ground-state reverse proton transfer in the 7-azaindole\\/carboxylic acid systems  

Microsoft Academic Search

Dual-level direct dynamics calculation of the ground-state proton transfer reaction is reported for the 7-azaindole(7AI)\\/carboxylic acid system. The reaction path was calculated and the two-dimensional potential energy surface scan was performed at various levels of theory. Only one transition state geometry was resolved in the ground state from the ab initio calculation. The zero-point corrected barrier for the reverse proton

Wei-Ping Hu; Ru-Min You; Shih-Yao Yen; Fa-Tsai Hung; Po-Hung Chou; Pi-Tai Chou

2003-01-01

249

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

250

Activation of carboxyl group with cyanate: peptide bond formation from dicarboxylic acids  

Microsoft Academic Search

The reaction of cyanate with C-terminal carboxyl groups of peptides in aqueous solution was considered as a potential pathway\\u000a for the abiotic formation of peptide bonds under the condition of the primitive Earth. The catalytic effect of dicarboxylic\\u000a acids on cyanate hydrolysis was definitely attributed to intramolecular nucleophilic catalysis by the observation of the 1H-NMR signal of succinic anhydride when

Grégoire Danger; Solenne Charlot; Laurent Boiteau; Robert Pascal

251

Removal of transition metals from dilute aqueous solution by carboxylic acid group containing absorbent polymers  

Technology Transfer Automated Retrieval System (TEKTRAN)

A new carboxylic acid group containing resin with cation exchange capacity, 12.67 meq/g has been used to remove Cu2+, Co2+ and Ni2+ ions from dilute aqueous solution. The resin has Cu2+, Co2+ and Ni2+ removal capacity, 216 mg/g, 154 mg/g and 180 mg/g, respectively. The selectivity of the resin to ...

252

Carboxylic and Dicarboxylic Acids Extracted from Crushed Magnesium Oxide Single Crystals  

Microsoft Academic Search

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

Friedemann Freund; Alka D. Gupta; Devendra Kumar

1999-01-01

253

Reduction of hydroxy-functionalised carbaboranyl carboxylic acids and ketones by organolithium reagents.  

PubMed

While the reaction of carbaboranyl carboxylic acids and ketones with organolithium reagents generally leads to cleavage of the exo-polyhedral C-C bond, introduction of a hydroxyl group at the second carbon atom of the cluster enables the reduction of the carbonyl compounds to tertiary alcohols. The proposed mechanism involving the formation of dimeric contact ion pairs was supported by X-ray crystallography and theoretical calculations. PMID:25760016

Neumann, W; Hiller, M; Sárosi, M B; Lönnecke, P; Hey-Hawkins, E

2015-03-24

254

Human ? 1 -pyrroline-5-carboxylate synthase: function and regulation  

Microsoft Academic Search

Mammalian ?1-pyrroline-5-carboxylate synthase (P5CS) is a bifunctional ATP- and NAD(P)H-dependent mitochondrial enzyme that catalyzes\\u000a the coupled phosphorylation and reduction-conversion of l-glutamate to P5C, a pivotal step in the biosynthesis of l-proline, l-ornithine and l-arginine. Previously, we reported cloning and characterization of two P5CS transcript variants generated by exon sliding\\u000a that encode two protein isoforms differing only by a two amino

C.-A. A. Hu; S. Khalil; S. Zhaorigetu; Z. Liu; M. Tyler; G. Wan; D. Valle

2008-01-01

255

Investigation of pyridine carboxylic acids in CM2 carbonaceous chondrites: Potential precursor molecules for ancient coenzymes  

NASA Astrophysics Data System (ADS)

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 also 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.

2014-07-01

256

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

257

Antiinflammatory and antiarthritic properties of a substituted quinoline carboxylic acid: CL 306,293.  

PubMed

CL 306,293, a substituted quinoline carboxylic acid at a daily oral dose between 1.5 and 3.0 mg/kg suppressed the inflammation and joint destruction (radiological criteria) associated with both developing and established adjuvant arthritis. When a weekly oral dosing regimen was used, joint destruction was attenuated when this agent was administered at a dose of 50 to 200 mg/kg. Inflammation associated with a delayed type hypersensitivity reaction in dogs was suppressed at a daily dose of 0.25 mg/kg or a weekly dose of 1 mg/kg. At efficacious doses, CL 306,293 had no effects on cyclooxygenase or lipoxygenase activities nor did it have an effect on carrageenin induced paw edema. In acute tests, the compound was not ulcerogenic. The above observations indicate that the antiinflammatory effects of CL 306,293 are distinct from those observed with nonsteroidal antiinflammatory agents. Mechanistic studies conducted and to be published indicate that CL 306,293 down regulates T cell function and this mechanism may account, at least in part, for the antiinflammatory and antiarthritic properties observed in animal models of inflammation and joint destruction. PMID:1895266

Sloboda, A E; Powell, D; Poletto, J F; Pickett, W C; Gibbons, J J; Bell, D H; Oronsky, A L; Kerwar, S S

1991-06-01

258

Synergism between ammonia, lactic acid and carboxylic acids as kairomones in the host-seeking behaviour of the malaria mosquito Anopheles gambiae sensu stricto (Diptera: Culicidae).  

PubMed

Host odours play a major role in the orientation and host location of blood-feeding mosquitoes. Anopheles gambiae Giles sensu stricto, which is the most important malaria vector in Africa, is a highly anthropophilic mosquito species, and the host-seeking behaviour of the females of this mosquito is guided by volatiles of human origin. Ammonia, lactic acid and several carboxylic acids are known to be present in the human odour blend. We investigated the effect of these compounds on naive female mosquitoes using a dual-port olfactometer. Ammonia was an attractant on its own, whereas lactic acid was not attractive. Carboxylic acids, offered as a mixture of 12 compounds, were repellent at the concentration tested. The addition of ammonia to the carboxylic acid mixture overruled the repellent effect of the latter. Combining ammonia with either lactic acid or the carboxylic acids did not enhance the attractiveness of ammonia alone. However, a synergistic effect was found when ammonia, lactic acid and the carboxylic acids were applied as a blend. Our findings indicate that An. gambiae s.s. relies on the combination of ammonia, lactic acid and carboxylic acids in its orientation to human hosts. The role of lactic acid in this tripartite synergism differs from that reported for the yellow fever mosquito Aedes aegypti. PMID:15703334

Smallegange, Renate C; Qiu, Yu Tong; van Loon, Joop J A; Takken, Willem

2005-02-01

259

Synthesis and Structure of a New Trinuclear Copper(II) Complex with 5Phenyl Pyrazole3Carboxylic Acid as Ligand  

Microsoft Academic Search

A new copper(II) complex of general formula Na2(Cu3L4) · 2H2O · 2CH3OH (L = 5-phenyl pyrazole-3-carboxylic acid) has been newly obtained by the reaction of copper chloride with 5-phenyl pyrazole-3-carboxylic acid in methanol in the presence of NaOH at room temperature. X-ray diffraction analysis of the crystal structure reveals that the complex is a trinuclear crystal structure that consists of

Yong-Heng Xing; Guang-Hua Zhou; Yue An; Xiao-Qing Zeng; Mao-Fa Ge

2008-01-01

260

Role of apparent p K a of carboxylic acids in lipase-catalyzed esterifications in biphasic systems  

Microsoft Academic Search

Lipase-catalyzed esterifications in biphasic media (heptane–water, 1:1) were conducted by using Thermomyces lanuginosus lipase (TLL) as biocatalyst. Different carboxylic acids (from acetic to lauric) were thus esterified with 1-butanol at different pH values (2–10). For all carboxylic acids tested, pH optima for the enzymatic esterifications were ca. 3–5, in clear agreement with previous literature, and quite different from optima pH

Pablo Domínguez de María; Elena Fernández-Álvaro; Antoon ten Kate; Gerrald Bargeman

2009-01-01

261

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

262

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

263

Structural studies of aromatic carboxylic acids via computational chemistry and microwave spectroscopy.  

PubMed

The structures of three simple aromatic carboxylic acids: benzoic, isophthalic, and terephthalic have been investigated using a combination of theoretical high-level quantum chemical calculations and experimental millimeter-wave Stark-modulated free-jet absorption spectroscopy. Rotational and centrifugal distortion constants have been measured for one conformer of each of the species and for its -COOD isotopologue, leading to the experimental determination of the coordinates of the carboxyl hydrogen atom. Consideration of the observed inertial defect is consistent with a planar equilibrium structure for each species. Calculated structures, relative energies, and electric dipole moments, using ab initio methods at the MP2/cc-pVTZ level, are reported for all the lower-energy conformers of each species. The theoretical calculations lead to the unambiguous identification of the conformers involved in the observed microwave spectra. The match between theoretical and spectroscopic measurements was used to gauge the reliability of the quantum chemical structure optimization calculations. PMID:23320679

Godfrey, Peter D; McNaughton, Don

2013-01-14

264

Structural studies of aromatic carboxylic acids via computational chemistry and microwave spectroscopy  

NASA Astrophysics Data System (ADS)

The structures of three simple aromatic carboxylic acids: benzoic, isophthalic, and terephthalic have been investigated using a combination of theoretical high-level quantum chemical calculations and experimental millimeter-wave Stark-modulated free-jet absorption spectroscopy. Rotational and centrifugal distortion constants have been measured for one conformer of each of the species and for its -COOD isotopologue, leading to the experimental determination of the coordinates of the carboxyl hydrogen atom. Consideration of the observed inertial defect is consistent with a planar equilibrium structure for each species. Calculated structures, relative energies, and electric dipole moments, using ab initio methods at the MP2/cc-pVTZ level, are reported for all the lower-energy conformers of each species. The theoretical calculations lead to the unambiguous identification of the conformers involved in the observed microwave spectra. The match between theoretical and spectroscopic measurements was used to gauge the reliability of the quantum chemical structure optimization calculations.

Godfrey, Peter D.; McNaughton, Don

2013-01-01

265

FT-IR, FT-Raman spectra and quantum mechanical study of piperidine-3-carboxylic acid and its tautomers, isomers  

NASA Astrophysics Data System (ADS)

The mid-IR, far-IR, and Raman spectra of piperidine-3-carboxylic acid were measured and interpreted with support of the MP2 and B3LYP/6-311++G(d, p) calculated harmonic vibrational spectra. 10 stable piperidine-3-carboxylic acid tautomers/isomers were found after B3LYP, calculations. The experimental absorption bands of carboxylate (COO-) group show that the free piperidine-3-carboxylic acid molecule exists in zwitterionic form and the most stable tautomer (NAT-1) can be stabilized by an intramolecular N-H...O hydrogen bond. All vibrational frequencies of NAT-1 assigned in detail with the help of total energy distribution (TED). The experimental vibrational wave numbers were compared with the calculated data.

Yurdakul, ?enay; Ya?ayan, Nefise Çi?dem; Bado?lu, Serdar

2014-06-01

266

Nickel-catalyzed direct carboxylation of olefins with CO2 : one-pot synthesis of ?,?-unsaturated carboxylic acid salts.  

PubMed

The nickel-catalyzed direct carboxylation of alkenes with the cheap and abundantly available C1 building block carbon dioxide (CO2 ) in the presence of a base has been achieved. The one-pot reaction allows for the direct and selective synthesis of a wide range of ?,?-unsaturated carboxylates (TON>100, TOF up to 6?h(-1) , TON=turnover number, TOF=turnover frequency). Thus, it is possible, in one step, to synthesize sodium acrylate from ethylene, CO2 , and a sodium salt. Acrylates are industrially important products, the synthesis of which has hitherto required multiple steps. PMID:25359188

Huguet, Núria; Jevtovikj, Ivana; Gordillo, Alvaro; Lejkowski, Michael L; Lindner, Ronald; Bru, Miriam; Khalimon, Andrey Y; Rominger, Frank; Schunk, Stephan A; Hofmann, Peter; Limbach, Michael

2014-12-15

267

Developmental toxicity of carboxylic acids to Xenopus embryos: a quantitative structure-activity relationship and computer-automated structure evaluation  

Microsoft Academic Search

The developmental toxicity for each of 45 carboxylic acids was determined for Xenopus embryos. Acids tested included 12 unbranched, saturated aliphatics, 12 branched, saturated aliphatics, 12 unsaturated aliphatics, and 9 aromatics. Embryos were collected following hormone-induced breeding and exposed to at least eight concentrations of the acid, along with a control. For each concentration, 25 properly developing embryos were exposed

Douglas A. Dawson; T. Wayne Schultz; Robert S. Hunter

1996-01-01

268

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

269

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

SciTech Connect

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

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

2005-01-01

270

Addition of omega-3 carboxylic acids to statin therapy in patients with persistent hypertriglyceridemia.  

PubMed

The incidence of hypertriglyceridemia has grown alongside that of obesity. Statin therapy has been widely recommended for the treatment of dyslipidemias. Omega-3 (OM3) fatty acid concentrates are commonly prescribed concurrently with statins in patients with persistent hypertriglyceridemia for additional lowering of triglyceride and non-HDL cholesterol. The bioavailability of currently available OM3 ethyl ester drugs is limited by their need for hydrolysis by pancreatic lipases, largely stimulated by dietary fat, prior to intestinal absorption. This review will discuss the chemistry, pharmacokinetics and clinical efficacy of a novel OM3 carboxylic acid drug that provides polyunsaturated docosahexaenoic and eicosapentaenoic acids in the free fatty acid form, which is readily absorbed by the intestine. This drug was approved in May 2014 as an adjunct to diet to reduce triglyceride levels in adults with severe (?500 mg/dl) hypertriglyceridemia. PMID:25089906

Davidson, Michael H; Phillips, Alyssa K; Kling, Douglas; Maki, Kevin C

2014-09-01

271

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

SciTech Connect

This paper reports on solubilities of carboxylic acids in certain organic solvents which increase sharply as the concentration of water in the solvent increases. This phenomenon leads to a method of regeneration for solvent-extraction processes whereby coextracted water is selectively removed from the extract, such as by stripping, thereby precipitating the acid. The removal of a minor constituent to cause precipitation reduces energy consumption, in contrast with bulk removal of solvent. Solubilities of fumaric acid were measured in a number of organic solvents, with varying amounts of water in the organic phase. Cyclohexanone and methylcyclohexanone were chosen as solvents for which detailed solid-liquid and liquid-liquid equilibria were measured for adipic, fumaric, and succinic acids in the presence of varying concentrations of water, at both 25 and 45[degrees]C. Batch precipitation experiments were performed to demonstrate the processing concept and determine the relative volatility of water to solvent in the presence of carbon.

Starr, J.N. (Abbott Labs., North Chicago, IL (United States)); King, C.J. (Lawrence Berkeley Lab., CA (United States))

1992-11-01

272

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

273

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

274

Microwave-assisted melt reaction method for the intercalation of carboxylic acid anions into layered double hydroxides.  

PubMed

Carboxylic acid anions intercalated layered double hydroxides are currently gaining increasing interest due to their potential applications in pharmaceutical field for controlled drug release in novel tunable drug delivery systems. In this work different aliphatic carboxylic acid anions were intercalated into the interlayers of commercial as well as synthetically prepared layered double hydroxides, through a novel microwave mediated melt reaction approach. The volumetric nature of microwave dielectric heating was exploited in order to rapidly heat the intimate mixture of the lamellar inorganic precursor and the appropriate organic acid, at the melting temperature of the particular mono- or dicarboxylic acid used, reaching the intercalation in approximately two hours treatment. PMID:24779132

Rosa, Roberto; Leonelli, Cristina; Villa, Carla; Priarone, Giulia

2013-01-01

275

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

276

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 240 nm. 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

277

Enantiopure synthesis of dihydrobenzo[1,4]-oxazine-3-carboxylic acids and a route to benzoxazinyl oxazolidinones.  

PubMed

A two step protocol is developed for the efficient synthesis of enantiopure N-Boc-dihydrobenzo[b]-1,4-oxazine-3-carboxylic acids from serine derived cyclic sulfamidate via intramolecular arylamination. The RuPhos Palladacycle along with additional RuPhos ligand is found to be an efficient catalyst for the arylamination of ?-(2-bromoaryloxy)amino acids to provide easy and direct access to a variety of dihydrobenzo[b]-1,4-oxazine-3-carboxylic acids with complete retention of enantiopurity in moderate to high yields. Dihydrobenzo[b]-1,4-oxazine-3-carboxylic acids are not only important unnatural amino acids, but are key precursors for the synthesis of important compounds such as benzoxazinyl oxazolidinones. A general approach for the synthesis of benzoxazinyl oxazolidinone is presented. PMID:25645529

Malhotra, Rajesh; Dey, Tushar K; Basu, Sourav; Hajra, Saumen

2015-03-01

278

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

279

Effect of A Long Chain Carboxylate Acid on Sodium Dodecyl Sulfate Micelle Structure: A SANS Study  

NASA Astrophysics Data System (ADS)

The effect of a different hydrocarbon chain length of carboxylate acid, i.e. dodecanoic acid, CH3(CH)10COOH or lauric acid and hexadecanoic acid, CH3(CH2)14COOH or palmitic acid as a co-surfactant in the 0.3 M sodium dedecyl sulfate, SDS micellar solution has been studied using small angle neutron scattering (SANS). The present of lauric acid has induced the SDS structural micelles. The ellipsoid micelles structures changed significantly in length (major axis) from 22.6 Å to 37.1 Å at a fixed minor axis of 16.7 Å in the present of 0.005 M to 0.1 M lauric acid. Nevertheless, this effect did not occur in the present of palmitic acid with the same concentration range. The present of palmitic acid molecules performed insignificant effect on the SDS micelles growth where the major axis of the micelle was elongated from 22.9 Å to 25.3 Å only. It showed that the appropriate hydrocarbon chain length between surfactant and co-surfactant molecules emerged as one of the determining factors in forming a mixed micelles structure.

Patriati, Arum; Giri Rachman Putra, Edy; Seok Seong, Baek

2010-01-01

280

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

281

Orthogonal protecting groups for N(alpha)-amino and C-terminal carboxyl functions in solid-phase peptide synthesis.  

PubMed

For the controlled synthesis of even the simplest dipeptide, the N(alpha)-amino group of one of the amino acids and the C-terminal carboxyl group of the other should both be blocked with suitable protecting groups. Formation of the desired amide bond can now occur upon activation of the free carboxyl group. After coupling, peptide synthesis can be continued by removal of either of the two protecting groups and coupling with the free C-terminus or N(alpha)-amino group of another protected amino acid. When three functional amino acids are present in the sequence, the side chain of these residues also has to be protected. It is important that there is a high degree of compatibility between the different types of protecting groups such that one type may be removed selectively in the presence of the others. At the end of the synthesis, the protecting groups must be removed to give the desired peptide. Thus, it is clear that the protection scheme adopted is of the utmost importance and makes the difference between success and failure in a given synthesis. Since R. B. Merrifield introduced the solid-phase strategy for the synthesis of peptides, this prerequisite has been readily accepted. This strategy is usually carried out using two main protection schemes: the tert-butoxycarbonyl/benzyl and the 9-flourenylmethoxycarbonyl/tert-butyl methods. However, for the solid-phase preparation of complex or fragile peptides, as well as for the construction of libraries of peptides or small molecules using a combinatorial approach, a range of other protecting groups is also needed. This review summarizes other protecting groups for both the N(alpha)-amino and C-terminal carboxyl functions. PMID:11074410

Albericio, F

2000-01-01

282

Transformations of anthraquinone-1-nitro-2-carboxylic acid during reduction by hydrogen on a catalyst  

SciTech Connect

We studied the catalytic reduction of anthraquinone-1-nitro-2-carboxylic acid by hydrogen under a pressure of 0.1-5.5 MPa and at temperatures of 20-100/sup 0/C in different solvents. The concentration of the substrate was varied from 0.05 to 0.3 mole/dm/sub 3/. A 5% palladium on carbon was used in a thermostated ideal mixing reactor. The process was controlled by the rate of absorption of hydrogen; polarographic, spectral and GLC methods of analysis were used to identify the compounds and to evaluate the quantitative composition of the products.

Rogovik, V.M.; Dzvinka, R.I.; Vinyukova, M.V.

1987-11-20

283

Intermediates in photochemistry of Fe(III) complexes with carboxylic acids in aqueous solutions.  

PubMed

The primary processes in the photochemistry of Fe(III) complexes with carboxylic acids (glyoxalic, tartaric, pyruvic and lactic) were studied by means of laser flash photolysis. The inner-sphere electron transfer with the formation of Fe(II) complex and an escape of an organic radical to the solution bulk was shown to be a minor channel of the photolysis. The main channel was proposed to be the formation of a long-lived radical complex [Fe(II)···?OOC-R](2+). Spectral and kinetic parameters of the radical complexes are determined. PMID:21031204

Glebov, Evgeni M; Pozdnyakov, Ivan P; Grivin, Vjacheslav P; Plyusnin, Victor F; Zhang, Xu; Wu, Feng; Deng, Nansheng

2011-03-01

284

Preferential adhesion of silver nanoparticles onto crystal faces of alpha-cyclodextrin/carboxylic acids inclusion compounds.  

PubMed

Alpha-Cyclodextrin (alpha-CD) inclusion compounds containing the carboxylic acids (octanoic, decanoic, lauric or dodecanoic, myristic or tetradecanoic, palmitic or hexadecanoic and stearic or octadecanoic) as guests were synthesized and applied for preferential adhesion of silver nanoparticles (AgNPs). The binding affinity depends of the chain length of the respective guest and is most efficient for octanoic and decanoic acids. The immobilization of nanoparticles is caused by the spatial replacing of the stabilized shell of the nanoparticles by COOH groups of the guests molecules, located at the entrance of cavity of alpha-CD, corresponding to the {001} crystal plane. Crystalline coating with nanoparticles provides a means of storing of AgNPs on solids state without aggregation. The stabilization of the particles on the surface is valid for a given length and ordering of the guest in the cavities of the alpha-CD being the octanoic and decanoic acid the most appropriated. PMID:23447940

Rodríguez-Llamazares, S; Jara, P; Yutronic, N; Noyong, M; Fischler, M; Simon, U

2012-12-01

285

A Seven-Gene Locus for Synthesis of Phenazine-1-Carboxylic Acid by Pseudomonas fluorescens 2-79  

PubMed Central

Pseudomonas fluorescens 2-79 produces the broad-spectrum antibiotic phenazine-1-carboxylic acid (PCA), which is active against a variety of fungal root pathogens. In this study, seven genes designated phzABCDEFG that are sufficient for synthesis of PCA were localized within a 6.8-kb BglII-XbaI fragment from the phenazine biosynthesis locus of strain 2-79. Polypeptides corresponding to all phz genes were identified by analysis of recombinant plasmids in a T7 promoter/polymerase expression system. Products of the phzC, phzD, and phzE genes have similarities to enzymes of shikimic acid and chorismic acid metabolism and, together with PhzF, are absolutely necessary for PCA production. PhzG is similar to pyridoxamine-5?-phosphate oxidases and probably is a source of cofactor for the PCA-synthesizing enzyme(s). Products of the phzA and phzB genes are highly homologous to each other and may be involved in stabilization of a putative PCA-synthesizing multienzyme complex. Two new genes, phzX and phzY, that are homologous to phzA and phzB, respectively, were cloned and sequenced from P. aureofaciens 30-84, which produces PCA, 2-hydroxyphenazine-1-carboxylic acid, and 2-hydroxyphenazine. Based on functional analysis of the phz genes from strains 2-79 and 30-84, we postulate that different species of fluorescent pseudomonads have similar genetic systems that confer the ability to synthesize PCA. PMID:9573209

Mavrodi, Dmitri V.; Ksenzenko, Vladimir N.; Bonsall, Robert F.; Cook, R. James; Boronin, Alexander M.; Thomashow, Linda S.

1998-01-01

286

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...

287

PhI(OAc)2 mediated decarboxylative sulfonylation of ?-aryl-?,?-unsaturated carboxylic acids: a synthesis of (E)-vinyl sulfones.  

PubMed

A highly efficient metal-free decarboxylative sulfonylation protocol for the preparation of (E)-vinyl sulfones from of ?-aryl-?,?-unsaturated carboxylic acids using sodium sulfinates and (diacetoxyiodo)benzene (PhI(OAc)2) was developed. This strategy offers a simple and expedient synthesis of (E)-vinyl sulfones bearing a wide variety of functional groups. A radical-based pathway has been proposed for this decarboxylative sulfonylation reaction. PMID:25811160

Katrun, Praewpan; Hlekhlai, Sornsiri; Meesin, Jatuporn; Pohmakotr, Manat; Reutrakul, Vichai; Jaipetch, Thaworn; Soorukram, Darunee; Kuhakarn, Chutima

2015-04-01

288

Determination of mono-, poly- and hydroxy-carboxylic acid profiles of beverages as their 2-nitrophenylhydrazides by reversed-phase ion-pair chromatography  

Microsoft Academic Search

A simple, rapid and accurate method for the derivatization and quantitative reversed-phase ion-pair chromatographic analysis of mono-, poly- and hydroxy-carboxylic acids in wines, fruit juices, beer and Japanese “sake” is presented. Nine hydrazine derivatives were prepared in high yield by direct derivatization of the carboxylic acids with 2-nitrophenyl-hydrazine hydrochloride in sample matrix. Isocratic separation of the carboxylic acid hydrazides was

Hiroshi Miwa; Magobei Yamamoto

1996-01-01

289

Development and Validation of an Improved LC Method for the Simultaneous Determination of Pirfenidone and Its Carboxylic Acid Metabolite in Human Plasma  

Microsoft Academic Search

A sensitive and specific assay based on liquid chromatography with ultraviolet detection was developed for the simultaneous\\u000a determination of pirfenidone (PFD), a novel antifibrotic agent, and its carboxylic acid metabolite in human plasma. The carboxylic\\u000a acid metabolite was further identified by mass spectrometric analysis. PFD, its carboxylic acid metabolite and the internal\\u000a standard methyl-p-aminobenzoate were extracted from plasma by a

Shaojun Shi; Jianhong Wu; Jun Wu; Fandian Zeng

2009-01-01

290

Synthesis of bio-functionalized copolymer particles bearing carboxyl groups via a microfluidic device  

Microsoft Academic Search

Monodisperse copolymer particles carrying surface carboxyl groups in the range of 50–200 ?m were prepared by in situ UV polymerization\\u000a of ethyleneglycol dimethacrylate (EGDMA) with acrylic acid (AA) via a microfluidic flow-focusing device (MFFD). The design\\u000a of the coaxial orifices in the MFFD enables the confinement of the comonomer liquid thread to the central axis of the microchannel,\\u000a which can avoid

Shih Hao Huang; Hwa Seng Khoo; Shang Yu ChangChien; Fan Gang Tseng

2008-01-01

291

Acid-functionalized nanoparticles for biomass hydrolysis  

NASA Astrophysics Data System (ADS)

Cellulosic ethanol is a renewable source of energy. Lignocellulosic biomass is a complex material composed mainly of cellulose, hemicellulose, and lignin. Biomass pretreatment is a required step to make sugar polymers liable to hydrolysis. Mineral acids are commonly used for biomass pretreatment. Using acid catalysts that can be recovered and reused could make the process economically more attractive. The overall goal of this dissertation is the development of a recyclable nanocatalyst for the hydrolysis of biomass sugars. Cobalt iron oxide nanoparticles (CoFe2O4) were synthesized to provide a magnetic core that could be separated from reaction using a magnetic field and modified to carry acid functional groups. X-ray diffraction (XRD) confirmed the crystal structure was that of cobalt spinel ferrite. CoFe2O4 were covered with silica which served as linker for the acid functions. Silica-coated nanoparticles were functionalized with three different acid functions: perfluoropropyl-sulfonic acid, carboxylic acid, and propyl-sulfonic acid. Transmission electron microscope (TEM) images were analyzed to obtain particle size distributions of the nanoparticles. Total carbon, nitrogen, and sulfur were quantified using an elemental analyzer. Fourier transform infra-red spectra confirmed the presence of sulfonic and carboxylic acid functions and ion-exchange titrations accounted for the total amount of catalytic acid sites per nanoparticle mass. These nanoparticles were evaluated for their performance to hydrolyze the beta-1,4 glycosidic bond of the cellobiose molecule. Propyl-sulfonic (PS) and perfluoropropyl-sulfonic (PFS) acid functionalized nanoparticles catalyzed the hydrolysis of cellobiose significantly better than the control. PS and PFS were also evaluated for their capacity to solubilize wheat straw hemicelluloses and performed better than the control. Although PFS nanoparticles were stronger acid catalysts, the acid functions leached out of the nanoparticle during the catalytic reactions. PS nanoparticles were further evaluated for the pretreatment of corn stover in order to increase digestibility of the biomass. The pretreatment was carried out at three different catalyst load and temperature levels. At 180°C, the total glucose yield was linearly correlated to the catalyst load. A maximum glucose yield of 90% and 58% of the hemicellulose sugars were obtained at this temperature.

Pena Duque, Leidy Eugenia

292

Isomers of various species of 1-hydroxy-2-pyridinone-6-carboxylic acid, their proton dissociation and complexes with Cr(III) and Zn(II)  

NASA Astrophysics Data System (ADS)

Isomers of 1-hydroxy-2-pyridinone-6-carboxylic acid (6-carboxy-1,2-HOPO), their deprotonated species and complexes with chromium and zinc were theoretically investigated by density functional theory calculations. Free energy of activation, energetics, thermodynamic properties and equilibrium constants of interconversion reactions of their isomers were determined. Measured acid-dissociation constants of the 6-carboxy-1,2-HOPO obtained from potentiometric titration method were compared with the computed constants which were derived from the density functional theory method. Two isomers of each 6-carboxy-1,2-HOPO complexes with chromium and with zinc were found.

Thipyapong, Khajadpai; Ruangpornvisuti, Vithaya

2008-11-01

293

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

294

Diazotization of 6-amino-2-phenyl-7-chloro-2 H -benzotriazole-4-carboxylic acid and transformations of the resulting diazo compounds  

Microsoft Academic Search

6-Amino-2-phenyl-7-chloro-2H-benzotriazole-4-carboxylic acid was prepared by oxidation of 2,5-diamino-4-chloro-2-phenylazobenzoic acid, and its diazotization and subsequent transformations of the diazo compounds were studied. 7-Hydroxy-2-phenyl-2H-benzotriazole-4-carboxylic acid was prepared.

G. L. Artamonov; V. P. Perevalov

2004-01-01

295

Synthesis and biological evaluation of pyrazolylthiazole carboxylic acids as potent anti-inflammatory-antimicrobial agents.  

PubMed

Current Letter presents design, synthesis and biological evaluation of a novel series of pyrazolylthiazole carboxylates 1a-1p and corresponding acid derivatives 2a-2p. All 32 novel compounds were tested for their in vivo anti-inflammatory activity by carrageenan-induced rat paw edema method as well as for in vitro antimicrobial activity. All the tested compounds exhibited excellent AI activity profile. Three compounds 1p (R=Cl, R(1)=Cl), 2c (R=H, R(1)=F) and 2n (R=Cl, R(1)=OCH3) were identified as potent anti-inflammatory agents exhibiting edema inhibition of 93.06-89.59% which is comparable to the reference drug indomethacin (91.32%) after 3h of carrageenan injection while most of the other compounds displayed inhibition ?80%. In addition, pyrazolylthiazole carboxylic acids (2a-2p) also showed good antimicrobial profile. Compound 2h (R=OCH3, R(1)=Cl) showed excellent antimicrobial activity (MIC 6.25?g/mL) against both Gram positive bacteria comparable with the reference drug ciprofloxacin (MIC 6.25?g/mL). PMID:25702850

Khloya, Poonam; Kumar, Satish; Kaushik, Pawan; Surain, Parveen; Kaushik, Dhirender; Sharma, Pawan K

2015-03-15

296

Probing the orthosteric binding site of GABAA receptors with heterocyclic GABA carboxylic acid bioisosteres.  

PubMed

The ionotropic GABAA receptors (GABAARs) are widely distributed in the central nervous system where they play essential roles in numerous physiological and pathological processes. A high degree of structural heterogeneity of the GABAAR has been revealed and extensive effort has been made to develop selective and potent GABAAR agonists. This review investigates the use of heterocyclic carboxylic acid bioisosteres within the GABAAR area. Several heterocycles including 3-hydroxyisoxazole, 3-hydroxyisoxazoline, 3-hydroxyisothiazole, and the 1- and 3-hydroxypyrazole rings have been employed in order to map the orthosteric binding site. The physicochemical properties of the heterocyclic moieties making them suitable for bioisosteric replacement of the carboxylic acid in the molecule of GABA are discussed. A variety of synthetic strategies for synthesis of the heterocyclic scaffolds are available. Likewise, methods for introduction of substituents into specific positions of the heterocyclic scaffolds facilitate the investigation of different regions in the orthosteric binding pocket in close vicinity of the core scaffolds of muscimol/GABA. The development of structural models, from pharmacophore models to receptor homology models, has provided more insight into the molecular basis for binding. Similar binding modes are proposed for the heterocyclic GABA analogues covered in this review by use of ligand-receptor docking into the receptor homology model and the presented structure-activity relationships. A network of interactions between the analogues and the binding pocket is leaving no room for substituents and underline the limited space in the GABAAR orthosteric binding site when in the agonist conformation. PMID:24362592

Petersen, Jette G; Bergmann, Rikke; Krogsgaard-Larsen, Povl; Balle, Thomas; Frølund, Bente

2014-06-01

297

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

298

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

299

Kinetic and Thermochemical Studies of Weakly-Bound HO2 Complexes with Carboxylic acids  

NASA Astrophysics Data System (ADS)

Numerous theoretical and experimental studies have suggested that HO2 radicals are able to form strong hydrogen bonds with some closed-shell species, which can potentially influence our understanding of HO2 chemistry in the upper troposphere and lower stratosphere. In this study, a laser flash photolysis-tunable diode laser absorption spectroscopy technique has been employed to study the formation of HO2 complexes with formic and acetic acids. At low temperatures, equilibration kinetics have been observed, allowing adduct formation and dissociation rate coefficients to be obtained and adduct binding enthalpies to be determined. This is the first experimental study of the HO2-carboxylic acid complexes and the binding energies are in good agreement with the most recent theoretical estimates. The potential role of HO2-RC(O)OH adducts in atmospheric chemistry will be discussed.

Zhao, Z.; Nicovich, J. M.; McKee, M. L.; Wine, P. H.

2008-12-01

300

Synthesis and evaluation of novel dental monomer with branched carboxyl acid group  

PubMed Central

To enhance the water miscibility and increase the mechanical properties of dentin adhesives, a new glycerol-based monomer with vinyl and carboxylic acid, 4-((1,3-bis(-methacryloyloxy)propan-2-yl)oxy)-2-methylene-4-oxobutanoic acid (BMPMOB), was synthesized and characterized. Dentin adhesive formulations containing 2-hydroxyethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]propane (BisGMA), and BMPMOB were characterized with regard to real-time photopolymerization behavior, water sorption, dynamic mechanical analysis, and microscale three-dimensional internal morphologies and compared with HEMA/BisGMA controls. The experimental adhesive copolymers showed higher glass transition temperature and rubbery moduli, as well as improved water miscibility compared to the controls. The enhanced properties of the adhesive copolymers indicated that BMPMOB is a promising comonomer for dental restorative materials. PMID:24596134

Song, Linyong; Ye, Qiang; Ge, Xueping; Misra, Anil; Laurence, Jennifer S.; Berrie, Cynthia L.; Spencer, Paulette

2014-01-01

301

Electrochemical properties of polyolefin nonwoven fabric modified with carboxylic acid group for battery separator  

NASA Astrophysics Data System (ADS)

Carboxylic acid group was introduced by radiation-induced grafting of acrylic acid (AAc) onto polyolefine nonwoven fabric (PNF), wherein the PNF comprises at least about 60% of a polyethylene having a melting temperature at ˜132°C and no more than about 40% of a second polypropylene having a lower melting temperature at ˜162°C, for a battery separator. The AAc-grafted PNF was characterized by XPS, SEM, DSC, TGA and porosimeter. The wetting speed, electrolyte retention, electrical resistance, and tensile strength were evaluated after grafting of AAc. It was found that the wetting speed, electrolyte retention, thickness, and ion-exchange capacity increased, whereas the electrical resistance decreased with increasing grafting yield. The tensile strength decreased with increasing grafting yield, whereas the elongation decreased with increasing grafting yield.

Choi, Seong-Ho; Kang, Hae-Jeong; Ryu, Eun-Nyoung; Lee, Kwang-Pill

2001-01-01

302

Evidence for 1-(Malonylamino)cyclopropane-1-Carboxylic Acid Being the Major Conjugate of Aminocyclopropane-1-Carboxylic Acid in Tomato Fruit1  

PubMed Central

Tomato (Lycopersicon esculentum Miller) fruit discs fed with [2,3-14C]1-aminocyclopropane-1-carboxylic acid (ACC) formed 1-malonyl-ACC (MACC) as the major conjugate of ACC in fruit throughout all ripening stages, from immature-green through the red-ripe stage. Another conjugate of ACC, ?-glutamyl-ACC (GACC), was formed only in mature-green fruit in an amount about 10% of that of MACC; conjugation of ACC into GACC was not detected in fruits at other ripening stages. No GACC formation was observed from etiolated mung bean (Vigna radiata [L.] Wilczek) hypocotyls, etiolated common vetch (Vicia sativum L.) epicotyls, or pea (Pisum sativum L.) root tips, etiolated epicotyls, and green stem tissue, where active conversion of ACC into MACC was observed. GACC was, however, formed in vitro in extracts from fruit of all ripening stages. GACC formation in an extract from red fruit at pH 7.15 was only about 3% of that at pH 8.0, the pH at which most assays were run. Our present in vivo data support the previous contention that MACC is the major conjugate of ACC in plant tissues, whereas GACC is a minor, if any, conjugate of ACC. Thus, our data do not support the proposal that GACC formation could be more important than MACC formation in tomato fruit. PMID:9536071

Peiser, Galen; Fa Yang, Shang

1998-01-01

303

Enzymes Involved in a Novel Anaerobic Cyclohexane Carboxylic Acid Degradation Pathway  

PubMed Central

The anaerobic degradation of cyclohexane carboxylic acid (CHC) has so far been studied only in Rhodopseudomonas palustris, in which CHC is activated to cyclohexanoyl coenzyme A (cyclohexanoyl-CoA [CHCoA]) and then dehydrogenated to cyclohex-1-ene-1-carboxyl-CoA (CHeneCoA). This intermediate is further degraded by reactions of the R. palustris-specific benzoyl-CoA degradation pathway of aromatic compounds. However, CHeneCoA is not an intermediate in the degradation of aromatic compounds in all other known anaerobic bacteria; consequently, degradation of CHC was mostly unknown in anaerobic bacteria. We identified a previously unknown CHC degradation pathway in the Fe(III)-reducing Geobacter metallireducens by determining the following CHC-induced in vitro activities: (i) the activation of CHC to CHCoA by a succinyl-CoA:CHC CoA transferase, (ii) the 1,2-dehydrogenation of CHCoA to CHeneCoA by CHCoA dehydrogenase, and (iii) the unusual 1,4-dehydrogenation of CHeneCoA to cyclohex-1,5-diene-1-carboxyl-CoA. This last represents a previously unknown joint intermediate of the CHC and aromatic compound degradation pathway in bacteria other than R. palustris. The enzymes catalyzing the three reactions were purified and characterized as specific enzymes after heterologous expression of the encoding genes. Quantitative reverse transcription-PCR revealed that expression of these genes was highly induced during growth with CHC but not with benzoate. The newly identified CHC degradation pathway is suggested to be present in nearly all CHC-degrading anaerobic bacteria, including denitrifying, Fe(III)-reducing, sulfate-reducing, and fermenting bacteria. Remarkably, all three CHC degradation pathways always link CHC catabolism to the catabolic pathways of aromatic compounds. We propose that the capacity to use CHC as a carbon source evolved from already-existing aromatic compound degradation pathways. PMID:25112478

Kung, Johannes W.; Meier, Anne-Katrin; Mergelsberg, Mario

2014-01-01

304

Enzymes involved in a novel anaerobic cyclohexane carboxylic acid degradation pathway.  

PubMed

The anaerobic degradation of cyclohexane carboxylic acid (CHC) has so far been studied only in Rhodopseudomonas palustris, in which CHC is activated to cyclohexanoyl coenzyme A (cyclohexanoyl-CoA [CHCoA]) and then dehydrogenated to cyclohex-1-ene-1-carboxyl-CoA (CHeneCoA). This intermediate is further degraded by reactions of the R. palustris-specific benzoyl-CoA degradation pathway of aromatic compounds. However, CHeneCoA is not an intermediate in the degradation of aromatic compounds in all other known anaerobic bacteria; consequently, degradation of CHC was mostly unknown in anaerobic bacteria. We identified a previously unknown CHC degradation pathway in the Fe(III)-reducing Geobacter metallireducens by determining the following CHC-induced in vitro activities: (i) the activation of CHC to CHCoA by a succinyl-CoA:CHC CoA transferase, (ii) the 1,2-dehydrogenation of CHCoA to CHeneCoA by CHCoA dehydrogenase, and (iii) the unusual 1,4-dehydrogenation of CHeneCoA to cyclohex-1,5-diene-1-carboxyl-CoA. This last represents a previously unknown joint intermediate of the CHC and aromatic compound degradation pathway in bacteria other than R. palustris. The enzymes catalyzing the three reactions were purified and characterized as specific enzymes after heterologous expression of the encoding genes. Quantitative reverse transcription-PCR revealed that expression of these genes was highly induced during growth with CHC but not with benzoate. The newly identified CHC degradation pathway is suggested to be present in nearly all CHC-degrading anaerobic bacteria, including denitrifying, Fe(III)-reducing, sulfate-reducing, and fermenting bacteria. Remarkably, all three CHC degradation pathways always link CHC catabolism to the catabolic pathways of aromatic compounds. We propose that the capacity to use CHC as a carbon source evolved from already-existing aromatic compound degradation pathways. PMID:25112478

Kung, Johannes W; Meier, Anne-Katrin; Mergelsberg, Mario; Boll, Matthias

2014-10-01

305

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

306

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

PubMed

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

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

2013-12-01

307

Electrochemical fluorination of 1-ethylpiperazine and 4-methyl- and\\/or 4-ethylpiperazinyl substituted carboxylic acid methyl esters  

Microsoft Academic Search

Electrochemical fluorination (ECF) of 1-ethylpiperazine and eight methyl esters of 4-methyl- and\\/or 4-ethylpiperazinyl substituted carboxylic acids were studied. Corresponding perfluoro(4-fluoro-1-ethylpiperazine) was obtained from 1-ethylpiperazine in a small yield along with perfluoro(1-methyl-3-ethylimidazolidine), perfluoro[2-(N?,N?-difluoroaminoethyl)-N,N-diethylamine)] and perfluorotriethylamine. The corresponding mono-basic perfluoroacid fluorides with a perfluoro(4-alkylpiperazinyl) group were obtained in fair to good yields from the fluorination of methyl esters of 4-alkylpiperazinyl-substituted carboxylic acids.

Takashi Abe; Hajime Baba; Irina Soloshonok

2001-01-01

308

Comparison of unimolecular decomposition pathways for carboxylic acids of relevance to biofuels.  

PubMed

Quantum mechanical molecular modeling is used [M06-2X/6-311++G(2df,p)] to compare activation energies and rate constants for unimolecular decomposition pathways of saturated and unsaturated carboxylic acids that are important in the production of biofuels and that are models for plant and algae-derived intermediates. Dehydration and decarboxylation reactions are considered. The barrier heights to decarboxylation and dehydration are similar in magnitude for saturated acids (?71 kcal mol(-1)), with an approximate 1:1 [H2O]/[CO2] branching ratio over the temperature range studied (500-2000 K). ?,?-Unsaturation lowers the barrier to decarboxylation between 2.2 and 12.2 kcal mol(-1) while increasing the barriers to dehydration by ?3 kcal mol(-1). The branching ratio, as a result, is an order of magnitude smaller, [H2O]/[CO2] = 0.07. For some ?,?-unsaturated acids, six-center transition states are available for dehydration, with barrier heights of ?35.0 kcal mol(-1). The branching ratio for these acids can be as high as 370:1. ?,?-Unsaturation results in a small lowering in the barrier height to decarboxylation (?70.0 kcal mol(-1)). ?,?-Unsaturation also leads to a lowering in the dehydration pathway from 1.7 to 5.1 kcal mol(-1). These results are discussed with respect to predicted kinetic values for acids of importance in biofuels production. PMID:24295398

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

2014-01-01

309

Qualitative analysis of some carboxylic acids by ion-exclusion chromatography with atmospheric pressure chemical ionization mass spectrometric detection  

Microsoft Academic Search

A simple, selective and sensitive method for the determination of carboxylic acids has been developed. A mixture of formic, acetic, propionic, valeric, isovaleric, isobutyric, and isocaproic acids has been separated on a polymethacrylate-based weak acidic cation-exchange resin (TSK gel OA pak-A) based on an ion-exclusion chromatographic mechanism with detection using UV-photodiode array, conductivity and atmospheric pressure chemical ionization mass spectrometry

Murad I. H. Helaleh; Kazuhiko Tanaka; Hiroshi Taoda; Wenzhi Hu; Kiyoshi Hasebe; Paul R. Haddad

2002-01-01

310

First-Principles Studies of Covalent Functionalization of Graphene by Carboxyl Groups  

NASA Astrophysics Data System (ADS)

We study the mechanism of covalent functionalization of graphene by the carboxyl (COOH) group in the framework of density functional theory combined with the generalized gradient approximation. The structures and binding energies of the COOH group attached to the surface of graphene are examined in cases of graphene containing no defects, containing a Stone-Wales defect, and containing a vacancy. Our calculations confirm that the binding of the COOH group with graphene is significantly stronger in the presence of surface defects. We also observe substantial changes in the structure of defective graphene after the attachment of the COOH group. These results suggest that surface defects play an important role in the carboxylation of graphene.

Al-Aqtash, Nabil; Vasiliev, Igor

2009-03-01

311

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

312

Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids  

SciTech Connect

Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe3+ in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe2+. The photochemistry in the presence of halide ions (X? = Cl?, Br?) generates ethyl halides via halogen atom abstraction from FeXn3?n by ethyl radicals. Near-quantitative yields of C2H5X are obtained at ?0.05 M X?. Competition experiments with Co(NH3)5Br2+ provided kinetic data for the reaction of ethyl radicals with FeCl2+ (k = (4.0 ± 0.5) × 106 M?1 s?1) and with FeBr2+ (k = (3.0 ± 0.5) × 107 M?1 s?1). Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu+. Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu+ to Cu2+, and removes gaseous olefins to prevent accumulation of Cu+(olefin) complexes and depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

Carraher, Jack; Pestovsky, Oleg; Bakac, Andreja

2012-03-14

313

Synthesis of the 2?,3?- and 2?,3?-isomers of 3-( p-substituted phenyl)tropane-2-carboxylic acid methyl esters  

Microsoft Academic Search

The synthesis of 3-(p-substituted phenyl)trop-2-carboxylic acid methyl ester 8 and its reduction with samarium iodide provide a new synthesis of 3?-(4?-substituted phenyl)tropane-2?-carboxylic acid methyl ester (2) and, in addition, give the first synthesis of the 2?,3?-diastereoisomer 4.

Kathryn I. Keverline; Philip Abraham; Anita H. Lewin; F. Ivy Carroll

1995-01-01

314

A simple and convenient method for preparation of carboxylic acid alkyl esters, phenolic and thioesters using chlorodiphenylphosphine\\/I 2 and imidazole reagent system  

Microsoft Academic Search

Condensation of carboxylic acids with alcohols, phenols and thiols proceeded smoothly to afford carboxylic acid alkyl esters, phenolic esters and thioesters by using the combination of chlorodiphenylphosphine, imidazole and molecular iodine in refluxing acetonitrile. Esterification with this mixed reagent system gave the corresponding products in excellent yields. The phosphorus-containing byproduct was simply removed from the organic phase by basic aqueous

Najmeh Nowrouzi; Abdol Mohammad Mehranpour; Javad Ameri Rad

2010-01-01

315

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

316

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...

317

Mechanistic aspects of benzylic bromide formation and oxidation during the cobalt acetate bromide catalyzed oxidation of alkylbenzenes in carboxylic acids  

Microsoft Academic Search

The formation and fate of benzylic bromides during the cobalt acetate bromide catalyzed oxidation of toluene and 4-chlorotoluene were investigated in carboxylic acid solvents. The rate of formation of benzylic bromides depends on the substrate and catalyst concentrations while the conversion of ionic bromide to benzylic bromides is strongly influenced by the type of solvent and the presence of nucleophilic

Gary M. Dugmore; Gregory J. Powels; Ben Zeelie

1995-01-01

318

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

319

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

E-print Network

) cleavage plane of calcite. The molecule used is racemic heptahelicene-2-carboxylic acid, which forms structures, well-aligned along the [010] crystallographic direction and stable at room temperature. Precise and are of well-defined width. We use racemic [7]HCA (enantiomeric excess of 0%), an equimolar mixture of (M)- [7

Kühnle, Angelika

320

Subcellular localization of the sites of conversion of 1-aminocyclopropane-1-carboxylic acid into ethylene in plant cells  

Microsoft Academic Search

The subcellular localization of the sites of 1-aminocyclopropane-1-carboxylic acid (ACC) conversion into ethylene was studied by comparing the specific radioactivity of ethylene evolved from the whole cells with that of intra- and extracellular pools of labelled ACC. We demonstrate that some cells cultured in vitro (Vitis vinifera L. cv. Muscat) or leaf tissues (Hordeum vulgare L. and Triticum aestivum L.)

Mondher Bouzayen; Alain Latché; Jean-Claude Pech

1990-01-01

321

Adsorption of a bromine labeled carboxylic acid corrosion inhibitor on iron measured with EQCM, EIS and XPS  

Microsoft Academic Search

Adsorption of bromine labeled aromatic carboxylic acid corrosion inhibitor on iron, polarized in the active region, was studied with the rotating electrochemical quartz crystal microbalance (rEQCM), electrochemical impedance spectroscopy (EIS) and X-ray induced photoelectron spectroscopy (XPS). The EQCM quantifies adsorption via the mass loss resulting from the fact that the inhibitor replaces water molecules in the interfacial volume occupied by

P Kern; D Landolt

2002-01-01

322

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

323

Polymer-Supported Phosphine-Halogen Complexes - 2 A New Facile Way for Esterification of Carboxylic Acids  

Microsoft Academic Search

The easily available complexes of polystyryl diphenyl phosphine with halogens are convenient condensating agents in the esterification of carboxylic acids under very mild conditions. The isolation of the ester by a simple filtration and evaporation process is a further interesting feature of this reaction.

Romualdo Caputo; Elvira Corrado; Carla Ferreri; Giovanni Palumbo

1986-01-01

324

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

325

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

326

Carboxylic acids in gas and PM2.5 particulate phase at a rural mountain site in northeastern United States  

NASA Astrophysics Data System (ADS)

Low molecular weight carboxylic acids are important constituents of the organic fraction of atmospheric particulate matter in rural and polluted regions. The knowledge on their source is sparse, however, and organic aerosols in general need to better characterized. Atmospheric gas- and particle-phase carboxylic acids (formic, acetic, pyruvic, glyoxalic, benzoaic, adipic, succinic, malonic, and oxalic) and related compounds were measured during August 2002 at a rural site, Whiteface Mountain, NY. Formic and acetic acids were present in the PM2.5 fraction and in the gas phase. Other seven carboxylic acids were below the detection limit in all samples. Formic and acetic acid were present in the atmosphere mostly in the gaseous form with less than 10% in the PM2.5 fraction. Concentrations of formic acid and acetic acid were in the 0.5 - 2.4 ppbv and 0.6 - 1.9 ppbv ranges, respectively. Formic-to-acetic acid ratios less than one (0.88) were recorded, likely due to an increase in acetic acid contribution from direct emissions. In the fine particulate mode (PM2.5 ) the concentrations for acetic acid and formic acid were 120 - 400 and 10 - 180 ng/m3 , respectively. Backward trajectory data indicate that air mass originated at midwestern region on August 5th and gradually moved towards north on August 9th. Correlation of formic acid with sulfate was investigated to interpret their possible secondary formation pathways. A strong correlation (0.73) was observed between formic acid and sulfate in PM2.5 particulates. Since the source of sulfate found at Whiteface Mountain widely accepted as anthropogenic, its association with formic acid indicated that the later might have anthropogenic source.

Hussain, M. M.; Khan, A. R.; Khwaja, H. A.

2009-12-01

327

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

328

Crystal and molecular structure of 3-trichloromethyl-4-chloro-5-isopropoxyisothiazole and 4,5-dichloroisothiazole-3-carboxylic acid  

Microsoft Academic Search

X-ray structural data are used to demonstrate that the chlorine in the 5-position of the heterocycle is replaced on reaction of 3-trichloromethyl-4,5-dichloroisothiazole with sodium isopropoxide. The S-N and C-S bond lengths are lengthened in the resulting 3-trichloromethyl-4-chloro-5-isopropoxyisothiazole whereas the C-N and C-C bonds are shortened compared with analogous bonds in 4,5-dichloroisothiazole-3-carboxylic acid. This is explained by conjugation of the carboxylic

A. I. Verenich; A. A. Govorova; N. M. Galitskii; V. I. Potkin; R. V. Kaberdin; Yu. A. Ol'dekop

1992-01-01

329

Tunneling isomerization of small carboxylic acids and their complexes in solid matrixes: a computational insight.  

PubMed

We have studied hydrogen-atom tunneling in the cis-to-trans conformational change of some carboxylic acid monomers and formic acid (FA) complexes and dimers at the MP2(full) and CCSD(T) levels of theory within the Wentzel-Kramers-Brillouin approximation. The barrier for the minimum energy path, where the OH bond length and the COH bending angle are optimized, is found to be a good approximation for providing the highest barrier transparency. The matrix effect on the transmission coefficients of cis-FA monomer, trans-cis FA dimer (tc1), and cis-acetic acid monomer are modeled by the polarizable continuum model (PCM) at the MP2(full) level of theory in different environments. For the cis-FA monomer and trans-cis FA dimer (tc1), the calculated transmission coefficients agree with the experimental lifetimes observed in noble-gas solids. However, this method cannot reproduce the experimental results obtained for cis-acetic acid. Moreover, the long lifetime of cis-FA and cis-acetic acid in the N2 environment cannot be reproduced either, which is most probably due to specific interactions that are not included in the PCM. The calculation for cis-HCOOD shows a strong decrease of the barrier transparency compared to that for cis-HCOOH, which is consistent with the experiments. In general, good agreement is observed between the calculated barrier transparency (including PCM) and experimental tunneling rate. However, some exceptions are found, which shows that additional factors influence the tunneling rate. PMID:25393052

Tsuge, Masashi; Khriachtchev, Leonid

2015-03-19

330

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

PubMed

Functionalization of nanoparticles can significantly influence their properties and potential applications. Although researchers can now functionalize metal, metal oxide, and organic polymer nanoparticles with a high degree of precision, controlled surface functionalization of nanoscale coordination polymer particles (CPPs) has remained a significant challenge. The lack of methodology is perhaps one of the greatest roadblocks to the advancement of CPPs into high added-value drug delivery applications. Here, we report having achieved this goal through a stepwise formation and functionalization protocol. We fabricated robust nanoparticles with enhanced thermal and colloidal stabilities by incorporation of carboxyl groups and these surface carboxyl groups could be subsequently functionalized through well-known peptide coupling reactions. The set of chemistries that we employed as proof-of-concept enabled a plethora of new functional improvements for the application of CPPs as drug delivery carriers, including enhanced colloidal stabilities and the incorporation of additional functional groups such as polyethylene glycol (PEG) or fluorescent dyes that enabled tracking of their cellular uptake. Finally, we ascertained the cytotoxicity of the new CPP nanoparticles loaded with camptothecin to human breast adenocarcinoma (MCF-7). Efflux measurements show that the encapsulation of camptothecin enhances the potency of the drug 6.5-fold and increases the drug retention within the cell. PMID:25284328

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

2014-11-17

331

Selective reduction of carboxylic acids to aldehydes catalyzed by B(C6F5)3.  

PubMed

B(C(6)F(5))(3) efficiently catalyzes hydrosilylation of aliphatic and aromatic carboxylic acids to produce disilyl acetals under mild conditions. Catalyst loadings can be as low as 0.05 mol %, and bulky tertiary silanes are favored to give selectively the acetals. Acidic workup of the disilyl acetals results in the formation of aldehydes in good to excellent yields. PMID:23317512

Bézier, David; Park, Sehoon; Brookhart, Maurice

2013-02-01

332

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

333

Supramolecular assistance for the selective monofunctionalization of a calix[6]arene tris-carboxylic acid-based receptor.  

PubMed

The selective functionalization of macrocyclic receptors remains extremely challenging because it generally requires the transformation of one and only one functional group among several identical groups. Recently, some of us described that the host-guest properties of a calix[6]arene-based Zn complex could be exploited for its selective monofunctionalization. Herein, we report on the extension of this synthetic strategy to a calix[6]arene-based receptor displaying a different recognition pattern with its guest. More precisely, a calix[6]arene tris-carboxylic acid-based receptor bearing three azido groups at the large rim was selectively monofunctionalized through an intramolecular thermal Huisgen reaction with a hexynNH3(+) ion accommodated into the cavity. This work shows that the monofunctionalization methodology can also be performed efficiently with host-guest systems involving ionic/H-bonding interactions, and it is thus not limited only to the use of metal-ligand interactions. In other words, this supramolecular methodology can be used as a general tool for the selective functionalization of molecular receptors. PMID:24219337

Inthasot, Alex; Dang Thy, Minh-Dung; Lejeune, Manuel; Fusaro, Luca; Reinaud, Olivia; Luhmer, Michel; Colasson, Benoit; Jabin, Ivan

2014-03-01

334

MOF Functionalization via Solvent-Assisted Ligand Incorporation: Phosphonates vs Carboxylates.  

PubMed

Solvent-assisted ligand incorporation (SALI) is useful for functionalizing the channels of metal-organic framework (MOF) materials such as NU-1000 that offer substitutionally labile zirconium(IV) coordination sites for nonbridging ligands. Each of the 30 or so previous examples relied upon coordination of a carboxylate ligand to achieve incorporation. Here we show that, with appropriate attention to ligand/node stoichiometry, SALI can also be achieved with phosphonate-terminated ligands. Consistent with stronger M(IV) coordination of phosphonates versus carboxylates, this change extends the pH range for retention of incorporated ligands. The difference in coordination strength can be exploited to achieve stepwise incorporation of pairs of ligands-specifically, phosphonates species followed by carboxylate species-without danger of displacement of the first ligand type by the second. Diffuse reflectance infrared Fourier-transform spectroscopy suggests that the phosphonate ligands are connected to the MOF node as RPO2(OH)¯ species in a moiety that leaves a base-accessible -OH moiety on each bound phosphonate. PMID:25665089

Deria, Pravas; Bury, Wojciech; Hod, Idan; Kung, Chung-Wei; Karagiaridi, Olga; Hupp, Joseph T; Farha, Omar K

2015-03-01

335

Film morphology, orientation and performance of dodecyl/carboxyl functional polysiloxane on cotton substrates  

NASA Astrophysics Data System (ADS)

A novel polysiloxane (RCAS) bearing dodecyl and carboxyl side groups was synthesized by reaction of a dodecyl/amino functionalized polysiloxane with maleic anhydride. Film morphology, molecular orientation and performance of the synthesized polysiloxane on cotton substrates were investigated by field emission scanning electron microscope (FESEM), atomic force microscope (AFM), X-ray photoelectron microscope (XPS) and so on. Affected by the dodecyl and polar carboxyl side groups, RCAS formed a semi hydrophilic, macroscopic smooth but actually uneven siloxane film with many pillar-likes or small humps on the treated substrate surfaces. On the natural cotton surface, RCAS may take such an orientation to form its film that the Si-CH3, Si-C12H25 groups projected outward into air, while the carboxyl groups pointed inward to the substrate, interacting with the hydroxyls of the cotton substrates in ester and hydrogen bonds or twisted away from the negatively charged cotton fiber surface. As a result of such a film-formation, RCAS provided the treated fabric with not only a good wettability of about 22.96 s and a whiteness of 88.44°, but also an improved softness as well as thickening handle.

An, Qiufeng; Wang, Kefeng; Jia, Yun

2011-03-01

336

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

337

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

338

Carboxyl terminal domain basic amino acids of mycobacterial topoisomerase I bind DNA to promote strand passage  

PubMed Central

Bacterial DNA topoisomerase I (topoI) carries out relaxation of negatively supercoiled DNA through a series of orchestrated steps, DNA binding, cleavage, strand passage and religation. The N-terminal domain (NTD) of the type IA topoisomerases harbor DNA cleavage and religation activities, but the carboxyl terminal domain (CTD) is highly diverse. Most of these enzymes contain a varied number of Zn2+ finger motifs in the CTD. The Zn2+ finger motifs were found to be essential in Escherichia coli topoI but dispensable in the Thermotoga maritima enzyme. Although, the CTD of mycobacterial topoI lacks Zn2+ fingers, it is indispensable for the DNA relaxation activity of the enzyme. The divergent CTD harbors three stretches of basic amino acids needed for the strand passage step of the reaction as demonstrated by a new assay. We also show that the basic amino acids constitute an independent DNA-binding site apart from the NTD and assist the simultaneous binding of two molecules of DNA to the enzyme, as required during the catalytic step. Although the NTD binds to DNA in a site-specific fashion to carry out DNA cleavage and religation, the basic residues in CTD bind to non-scissile DNA in a sequence-independent manner to promote the crucial strand passage step during DNA relaxation. The loss of Zn2+ fingers from the mycobacterial topoI could be associated with Zn2+ export and homeostasis. PMID:23771144

Ahmed, Wareed; Bhat, Anuradha Gopal; Leelaram, Majety Naga; Menon, Shruti; Nagaraja, Valakunja

2013-01-01

339

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

340

In vitro toxicological characterization of perfluorinated carboxylic acids with different carbon chain lengths.  

PubMed

Perfluorooctanoic acid (PFOA) is in use for the production of fluoropolymers (PFT). Due to its toxic properties it was proposed to replace the substance in its industrial applications by homologous compounds with shorter carbon chain length that were supposed to be less toxic compared to PFOA, however, the smaller PFOA homologs are poorly characterized so far. In this study we have conducted a comparative analysis of the toxicity of perfluorinated carboxylic acids (PFCA) with a carbon chain length ranging from four to twelve carbon atoms. By using the human hepatocarcinoma cell line HepG2 as an in vitro model for human hepatocytes we could show a positive correlation between the carbon chain length of the respective PFCA and its cytotoxicity. There was, however, no indication of an apoptotic mechanism for cytotoxicity. All PFCA under investigation were negative in two independent genotoxicity assays. As PFOA, being a well-known peroxisome proliferator, the other PFCA tested in this study were also shown to activate human peroxisome proliferator-activated receptor alpha (PPAR?) with PFOA having the highest potential of PPAR? activation. Moreover, the compounds showed weak potential to activate PPAR? and hardly activated PPAR?. Taken together, the in vitro study revealed that PFCA with a shorter carbon chain length seem to be less toxic than PFOA. PMID:23391484

Buhrke, Thorsten; Kibellus, Anja; Lampen, Alfonso

2013-04-12

341

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

342

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

PubMed

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 (C(6)-C(18)) 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 (C(8)-C(16)) or fatty alkanes (C(7)-C(15)) 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 (C(8)-C(18)). 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

343

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

344

Acid Activated Indian Bentonite, an Efficient Catalyst for Esterification of Carboxylic Acids  

Microsoft Academic Search

The preparation, characterization, and catalytic properties of acid activated Indian bentonite (AAIB) are reported. AAIB has\\u000a been characterized by XRD (basal spacing, 15.05 Å), specific surface area (273 m2\\/g), pore volume and pore diameter using BET method, TGA, SEM, and surface acidity by n-butylamine back titration method and infrared spectroscopy using pyridine as a probe molecule. The activity of Montmorillonite\\u000a K10, ZrO2,

B. Vijayakumar; Gopalpur Nagendrappa; B. S. Jai Prakash

2009-01-01

345

Reaction Kinetics for the Biocatalytic Conversion of Phenazine-1-Carboxylic Acid to 2-Hydroxyphenazine  

PubMed Central

The phenazine derivative 2-hydroxyphenazine (2-OH-PHZ) plays an important role in the biocontrol of plant diseases, and exhibits stronger bacteriostatic and fungistatic activity than phenazine-1-carboxylic acid (PCA) toward some pathogens. PhzO has been shown to be responsible for the conversion of PCA to 2-OH-PHZ, however the kinetics of the reaction have not been systematically studied. Further, the yield of 2-OH-PHZ in fermentation culture is quite low and enhancement in our understanding of the reaction kinetics may contribute to improvements in large-scale, high-yield production of 2-OH-PHZ for biological control and other applications. In this study we confirmed previous reports that free PCA is converted to 2-hydroxy-phenazine-1-carboxylic acid (2-OH-PCA) by the action of a single enzyme PhzO, and particularly demonstrate that this reaction is dependent on NADP(H) and Fe3+. Fe3+ enhanced the conversion from PCA to 2-OH-PHZ and 28°C was a optimum temperature for the conversion. However, PCA added in excess to the culture inhibited the production of 2-OH-PHZ. 2-OH-PCA was extracted and purified from the broth, and it was confirmed that the decarboxylation of 2-OH-PCA could occur without the involvement of any enzyme. A kinetic analysis of the conversion of 2-OH-PCA to 2-OH-PHZ in the absence of enzyme and under different temperatures and pHs in vitro, revealed that the conversion followed first-order reaction kinetics. In the fermentation, the concentration of 2-OH-PCA increased to about 90 mg/L within a red precipitate fraction, as compared to 37 mg/L within the supernatant. The results of this study elucidate the reaction kinetics involved in the biosynthesis of 2-OH-PHZ and provide insights into in vitro methods to enhance yields of 2-OH-PHZ. PMID:24905009

Chen, Mingmin; Cao, Hongxia; Peng, Huasong; Hu, Hongbo; Wang, Wei; Zhang, Xuehong

2014-01-01

346

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

347

Carboxyl-functionalized task-specific ionic liquids for solubilizing metal oxides.  

PubMed

Imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium, and quaternary ammonium bis(trifluoromethylsulfonyl)imide salts were functionalized with a carboxyl group. These ionic liquids are useful for the selective dissolution of metal oxides and hydroxides. Although these hydrophobic ionic liquids are immiscible with water at room temperature, several of them form a single phase with water at elevated temperatures. Phase separation occurs upon cooling. This thermomorphic behavior has been investigated by (1)H NMR, and it was found that it can be attributed to the temperature-dependent hydration and hydrogen-bond formation of the ionic liquid components. The crystal structures of four ionic liquids and five metal complexes have been determined. PMID:18841931

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

2008-11-01

348

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

349

Growth inhibition of Clostridium thermocellum by carboxylic acids: A mechanism based on uncoupling by weak acids  

Microsoft Academic Search

The inhibition of Clostridium thermocellum strains by acetate and other organic acids (propionate, butyrate) can be explained by a model based on the chemiosmotic theory and uncoupler action. It is proposed that the charged permeant species in the process of anion exclusion is the dimer HA-2. Evidence for this mechanisms is provided by 31P-NMR studies of whole cells and cell

Alejandro A. Herrero; Reinaldo F. Gomez; Brad Snedecor; Cynthia J. Tolman; Mary F. Roberts

1985-01-01

350

Determination of functionalised carboxylic acids in atmospheric particles and cloud water using capillary electrophoresis/mass spectrometry.  

PubMed

A capillary electrophoresis/electrospray ionisation mass spectrometry (CE/ESI-MS) method was developed for the determination of 38 organic acids in atmospheric particles and cloud water. The target analytes include many functionalised carboxylic acids, such as carboxylic acids with additional oxo-, hydroxy- or nitro-groups. These compounds are of large interest as their determination might give new insights into the atmospheric multiphase chemistry. OASIS HLB sorbent material (Waters) was used to extract and enrich polar carboxylic acids from aqueous solutions with recoveries greater than 80% for most analytes. Relative standard deviations in the range of 4-20% for peak areas (n=5), including the SPE step, and 0.2-0.5% (n=8) for migration times were found. The limits of detection (S/N=3) ranged from 0.005 to 0.6 micromol l(-1) for an ion-trap mass spectrometer and from 0.0004 to 0.08 micromol l(-1) for a time-of-flight mass spectrometer. These detection limits translate into atmospheric concentrations in the low pg m(-3) range based on the experimental conditions in this study. Severe matrix effects were observed for real samples, arising from complex co-extracted organic material. However, using the method of standard addition, most of the analytes could successfully be quantified in samples of ambient particles and cloud water with concentrations in the low ng m(-3) to high pg m(-3) range. These results demonstrate the suitability of the proposed method for the determination of a wide range of polar carboxylic acids at low concentrations in complex samples of different atmospheric phases. PMID:17920610

van Pinxteren, Dominik; Herrmann, Hartmut

2007-11-01

351

Sucrose esters of carboxylic acids in glandular trichomes ofSolanum berthaultii deter settling and probing by green peach aphid.  

PubMed

Removal of type B trichome exudate fromSolanum berthaultii leaflets leads to a decrease in tarsal gumming and mortality and an increase in feeding by the green peach aphid,Myzus persicae. Type B trichome exudate of theS. berthaultii accession PI 473331 is composed of a complex of 3',3,4,6-tetra-O-acyl sucroses containing primarily short-chain branched carboxylic acids. The acyl constituents are primarily derived from 2-methylpropanoic, 2-methylbutyric, and 8-methylnonanoic acids but constituents derived fromn-decanoic and dodecanoic acids are also present. Sucrose esters inhibit settling and probing by aphids in glass feeding cages. PMID:24263505

Neal, J J; Tingey, W M; Steffens, J C

1990-02-01

352

Phenazine carboxylic acid production and rhizome protective effect of endophytic Pseudomonas aeruginosa isolated from Zingiber officinale.  

PubMed

Ginger (Zingiber officinale) is cultivated commercially in most parts of the world especially in India for its culinary and medicinal applications. One of the major challenges that limit the yield of ginger is rhizome rot disease caused by organisms including Pythium myriotylum. A feasible ecofriendly method is yet to be devised to prevent the plant from this threatening disease. Recent studies on plant microbiome show the possibility of having endophytic organisms with plant protective characteristics associated with the plants. Because of the uniquely evolved underground nature of the ginger rhizome and its peculiar survival in soil for a long time, many interesting endophytic microbes with plant protective characters can be well expected from it. In the current study, previously isolated endophytic Pseudomonas aeruginosa from ginger was investigated in detail for its effect on Pythium myriotylum. The rhizome protective effect of the organism was also studied by co-inoculation studies, which confirmed that Pseudomonas aeruginosa has very potent inhibitory effect on Pythium myriotylum. On further studies, the active antifungal compound was identified as phenazine 1-carboxylic acid. PMID:24353040

Jasim, B; Anisha, C; Rohini, Sabu; Kurian, Jacob Manoj; Jyothis, Mathew; Radhakrishnan, E K

2014-05-01

353

Synthesis, antifungal activity and QSAR of some novel carboxylic Acid amides.  

PubMed

A series of novel aromatic carboxylic acid amides were synthesized and tested for their activities against six phytopathogenic fungi by an in vitro mycelia growth inhibition assay. Most of them displayed moderate to good activity. Among them N-(2-(1H-indazol-1-yl)phenyl)-2-(trifluoromethyl)benzamide (3c) exhibited the highest antifungal activity against Pythium aphanidermatum (EC50 = 16.75 µg/mL) and Rhizoctonia solani (EC50 = 19.19 µg/mL), compared to the reference compound boscalid with EC50 values of 10.68 and 14.47 µg/mL, respectively. Comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) were employed to develop a three-dimensional quantitative structure-activity relationship model for the activity of the compounds. In the molecular docking, a fluorine atom and the carbonyl oxygen atom of 3c formed hydrogen bonds toward the hydroxyl hydrogens of TYR58 and TRP173. PMID:25749678

Du, Shijie; Lu, Huizhe; Yang, Dongyan; Li, Hong; Gu, Xilin; Wan, Chuan; Jia, Changqing; Wang, Mian; Li, Xiuyun; Qin, Zhaohai

2015-01-01

354

Acute toxicity assessment of perfluorinated carboxylic acids towards the Baltic microalgae.  

PubMed

The presence of high-energy carbon-fluorine bonds in perfluoro compounds lends them great stability and causes them to be environmentally persistent. Relatively little is known about the acute toxicity of perfluorinated carboxylic acids (PFCAs) to ecotoxicological markers such as aquatic plants and animals. This study tested the toxicity of these compounds to the green alga Chlorella vulgaris, the diatom Skeletonema marinoi and the blue-green alga Geitlerinema amphibium, which are species representative of the algal flora of the Baltic Sea. The EC(50) values obtained range from 0.28 mM to 12.84 mM. A distinct relationship between hydrophobicity and toxicity is demonstrated. For every extra perfluoromethylene group in the alkyl chain, the toxicity increases twofold. LogEC(50) values are very well correlated linearly with both the number of carbon atoms in the perfluoroalkyl chain and the partition coefficients. The results also indicate that there are clear differences between the responses of particular taxonomic groups of algae: blue-green algae and diatoms are far more sensitive to PFCAs than green algae, probably because of differences in cell wall structure. PMID:21783999

Lata?a, Adam; N?dzi, Marcin; Stepnowski, Piotr

2009-09-01

355

Asymmetric synthesis of 2-methyl cyclohexane carboxylic acids by heterogeneous catalysis: mechanistic aspects  

PubMed

The catalytic hydrogenation of (S)-alkyl-N-(2-methylbenzoyl)pyroglutamates was studied over supported rhodium and ruthenium catalysts at room temperature and a pressure of 5 MPa. The reaction was diastereoselective with the predominant formation of (1S,2R)-2-methylcyclohexane carboxylic acid with a diastereomeric excess (de) of up to 96%. The most stable conformation was determined by means of a combination of modelling calculations, NMR spectroscopy and X-ray structural determination. In this conformation, the carbonyl group of the pyroglutamate auxiliary shields one face of the aromatic ring. The observed selectivity may thus be explained by a preferential adsorption at the unshielded face which avoids steric repulsion by the C=O group to result in a cis hydrogenation. The addition of an amine, the nature of the support (alumina or active carbon) or of the metal (Rh or Ru) were shown to give additional stabilisation of the adsorption at the unshielded face to increase the diastereoisomeric excess. PMID:10785815

Besson; Delbecq; Gallezot; Neto; Pinel

2000-03-17

356

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

357

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

358

Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their potential precursors.  

PubMed

Since 2000 there has been an on-going industrial transition to replace long-chain perfluoroalkyl carboxylic acids(PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their precursors. To date, information on these replacements including their chemical identities, however, has not been published or made easily accessible to the public, hampering risk assessment and management of these chemicals. Here we review information on fluorinated alternatives in the public domain. We identify over 20 fluorinated substances that are applied in [i] fluoropolymer manufacture, [ii] surface treatment of textile, leather and carpets, [iii] surface treatment of food contact materials,[iv] metal plating, [v] fire-fighting foams, and [vi] other commercial and consumer products.We summarize current knowledge on their environmental releases, persistence, and exposure of biota and humans. Based on the limited information available, it is unclear whether fluorinated alternatives are safe for humans and the environment.We identify three major data gaps that must be filled to perform meaningful risk assessments and recommend generation of the missing data through cooperation among all stakeholders (industry, regulators, academic scientists and the public). PMID:24660230

Wang, Zhanyun; Cousins, Ian T; Scheringer, Martin; Hungerbühler, Konrad

2013-10-01

359

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

360

Localized surface plasmon resonance interfaces coated with poly[3-(pyrrolyl)carboxylic acid] for histidine-tagged peptide sensing.  

PubMed

The paper reports on a novel localized surface plasmon resonance (LSPR) substrate architecture for the immobilization and detection of histidine-tagged peptides. The LSPR interface consists of an ITO (indium tin oxide) substrate coated with gold nanostructures. The latter are obtained by thermal deposition of a thin (2 nm thick) gold film followed by post-annealing at 500 °C. The LSPR interface was coated with poly[3-(pyrrolyl)carboxylic acid] thin films using electrochemical means. The ability of the LSPR interfaces coated with poly[3-(pyrrolyl)carboxylic acid] to chelate copper ions was investigated. Once loaded with metal ions, the modified LSPR interface was able to bind specifically to histidine-tagged peptides. The binding process was followed using LSPR. PMID:21874203

Tighilt, Fatma-Zohra; Subramanian, Palaniappan; Belhaneche-Bensemra, Naima; Boukherroub, Rabah; Gabouze, Noureddine; Sam, Sabrina; Szunerits, Sabine

2011-10-21

361

Formation of aldehydes and carboxylic acids in ozonated surface water and wastewater: A clear relationship with fluorescence changes.  

PubMed

This study examined the formation of aldehydes and carboxylic acids in ozonated surface water and municipal wastewater secondary effluent and addressed correlations between the generation of these compounds and concurrent changes of the fluorescence of natural/effluent organic matter (NOM/EfOM) substrates. Ozonation was effective in removing fluorophores in all excitation/emission matrix (EEM) regions, with those operationally assigned to humic- and protein-like species showing relatively higher reactivity than fulvic-like species. Examination of HO exposures and attendant changes of fluorescence-based parameters allows establishing strong linear relationships between formation of the aldehydes and carboxylic acids and the relative changes of integrated fluorescence (?IF/IF0). This demonstrates the feasibility of surrogate monitoring of the formation of biodegradable ozonation by-products via online measurements of water/wastewater EEM fluorescence. PMID:25576127

Liu, Chen; Tang, Xiangyu; Kim, Jaeshin; Korshin, Gregory V

2015-04-01

362

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

363

Selective complexation of ?-amino acids and simple peptides via their carboxylate groups.  

PubMed

The complexation of anions of selected ?-amino acids (alanine, valine, proline, tyrosine) and small peptides (L-alanyl-L-alanine, L-alanyl-L-alanyl-L-alanine, and L-alanyl-L-alanyl-L-alanyl-L-alanine) by the dinuclear nickel(II) complex [LNi2(?-Cl)]+ (1), where (L)2? represents a 24-membered binucleating hexamine-dithiophenolato ligand, has been investigated. The following complexes were prepared, isolated as perchlorate or tetraphenylborate salts, and characterized by UV/Vis, IR, and CD spectroscopy: [LNi2(?-L-alaninato)]+ (2), [LNi2(?-L-valinato)]+ (3), [LNi2(?-L-prolinato)]+ (4), [LNi2(?-L-tyrosinato)]+ (5a), [LNi2(?-D-tyrosinato)]+ (5b), [LNi2(?-L,D-tyrosinato)]+ (5c), [LNi2(?-L-alanyl-L-alaninato)]+ (6), [LNi2(?-(L-alanyl)2-L-alaninato)]+ (7), [LNi2(?-(L-alanyl)3-L-alaninato)]+ (8). Compounds 4, 5a and 6 were additionally identified by X-ray crystallography. In contrast to unsupported amino carboxylate complexes which typically contain five membered NO chelate rings, the [LNi2]2+ fragment selectively binds the ?-amino acids and peptides via ?1,3-bridging carboxylato groups. Coordination of the carboxylato coligands in this way confers dissymmetry on the complexes. The CD spectra of the syn,syn-bridged structures are significantly different from those of the NO chelates, and can distinguish between the two coordination modes. The encapsulation of the peptides increases their solubility in the solvent system MeOH–MeCN by up to two orders of magnitude. This is discussed in terms of the absence of intermolecular hydrogen bonding interactions as indicated in the X-ray structure of 6. PMID:25098239

Schnitter, Roland; Gallego, Daniel; Kersting, Berthold

2014-09-28

364

Configuration and conformational equilibrium of (±)- trans-1-oxo-3-thiophen-2-yl-isochroman-4-carboxylic acid methyl ester  

Microsoft Academic Search

The X-ray analysis of 1-oxo-3-thiophen-2-yl-isochroman-4-carboxylic acid methyl ester 1 confirmed its trans-configuration and a conformation with diaxial H-3 and H-4 atoms in solid state. NMR experiments indicated that trans-1 exists in solution in both expected conformers. In CDCl3 and especially in CD3OD or DMSO, the conformational equilibrium is shifted towards the conformer with diequatorial H-3 and H-4, which was also

Milen G. Bogdanov; Iliya S. Todorov; Pavlina G. Manolova; Diana V. Cheshmedzhieva; Mariana D. Palamareva

2004-01-01

365

The kinetics of photocatalytic degradation of aliphatic carboxylic acids in an UV\\/TiO2 suspension system  

Microsoft Academic Search

Kinetic studies on the photocatalytic degradation of aliphatic carboxylic acids were carried out in a slurry photoreactor with in?situ monitoring, employing artificial UV light as the source of energy and nano?TiO2 powder as the catalyst. The influences on the photocatalytic degradation such as the initial concentration of reactant (C0), catalyst dosage (CTiO2), UV intensity (Ia) and pH value have been

Q. Chen; J. M. Song; F. Pan; F. L. Xia; J. Y. Yuan

2009-01-01

366

A Seven-Gene Locus for Synthesis of Phenazine1Carboxylic Acid by Pseudomonas fluorescens 2-79  

Microsoft Academic Search

Pseudomonas fluorescens 2-79 produces the broad-spectrum antibiotic phenazine-1-carboxylic acid (PCA), which is active against a variety of fungal root pathogens. In this study, seven genes designated phzABCDEFG that are sufficient for synthesis of PCA were localized within a 6.8-kb BglII-XbaI fragment from the phenazine biosynthesis locus of strain 2-79. Polypeptides corresponding to all phz genes were identified by analysis of

DMITRI V. MAVRODI; VLADIMIR N. KSENZENKO; ROBERT F. BONSALL; R. JAMES COOK; ALEXANDER M. BORONIN; LINDA S. THOMASHOW

1998-01-01

367

Nutritional factors regulating growth and accumulation of phenazine 1-carboxylic acid by Pseudomonas fluorescens 2-79  

Microsoft Academic Search

Pseudomonas fluorescens strain 2-79 (NRRL B-15 132) is a biocontrol agent of take-all of wheat caused by the fungus Gaeumannomyces graminis var. tritici. Strain 2-79 produces the antibiotic phenazine 1-carboxylic acid, which acts as the primary mechanism of disease suppression. As a first step toward designing efficient methods of mass producing and formulating this biocontrol agent, the regulation of growth

Patricia J. Slininger; Mark A. Jackson

1992-01-01

368

The pKa of the General Acid/Base Carboxyl Group of a Glycosidase Cycles during Catalysis: A 13  

E-print Network

The pKa of the General Acid/Base Carboxyl Group of a Glycosidase Cycles during Catalysis: A 13 C-NMR Study of Bacillus circulans Xylanase Lawrence P. McIntosh,*,,§ Greg Hand, Philip E. Johnson,,§ Manish D obtained from a study of the pH dependence of kcat/Km and demonstrate that, at the enzyme's pH optimum of 5

McIntosh, Lawrence P.

369

1-Aminocyclopropane-1-carboxylic acid concentrations in shoot-forming and non-shoot-forming tobacco callus cultures  

SciTech Connect

Shoot-forming tobacco (Nicotiana tabacum var. Wisconsin 38) callus tissues contain significantly lower concentrations of the ethylene precursor 1-aminocyclopropane-1-carboxylic acid compared to non-shoot-forming callus tissues. This difference is evident 1 day after subculture to shoot-forming or non-shoot-forming medium, and is maintained through the first week of growth. The lack of auxin in shoot-forming medium is the probable cause for this difference in ACC concentrations.

Grady, K.L.; Bassham, J.A.

1982-09-01

370

The Carboxyl Terminus of the Human Foamy Virus Gag Protein Contains Separable Nucleic Acid Binding and Nuclear Transport Domains  

Microsoft Academic Search

TheGagproteinofhumanfoamyvirus(HFV)lacksCys-Hisboxespresentinthenucleocapsid(NC)domains of other retroviruses; instead it contains three glycine-arginine-rich motifs (GR boxes). We have expressed the carboxyl end of HFV Gag containing the GR boxes (the NC domain equivalent) and analyzed its nucleic acid bindingproperties.OurresultsshowthattheNCdomainofHFVGagbindswithhighaffinitytobothRNAand DNA, in a sequence-independent manner, as determined by filter binding assays. Analysis of a mutant containing a heterologous sequence in place of GR box I

SHUYUARN F. YU; KURT EDELMANN; ROLAND K. STRONG; ASTRID MOEBES; AXEL RETHWILM; ANDMAXINE L. LINIAL

1996-01-01

371

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

372

Thiazolidine4-carboxylic acid and 2-aminothiazoleethanoic acid as ligands. The synthesis, magnetic, e.p.r. and spectral properties of copper(II) complexes  

Microsoft Academic Search

Two complexes formed from CuII acetate and thiazolidine-4-carboxylic acid (4-TCA) and 2-amino-4-thiazoleethanoic acid (ATAA) have been prepared and characterized by magnetic and spectroscopic techniques. The influence of the nature of ligands and solvents upon CuII e.p.r. properties was investigated for these compounds, Spin-Hamiltonian parameters from these data enabled suggestions concerning the structure of these complexes and the binding ability of

Krystyna Gie?zak-Ko?win; Walter Wojciechowski

1996-01-01

373

Localization of the production of 1-aminocyclopropane-1-carboxylic acid and its conversion to ethylene during the rhythmic production of the gas in Sorghum bicolor seedlings  

E-print Network

Studies were conducted to determine where in the plant 1-aminocyclopropane-1-carboxylic acid (ACC) is made and converted to ethylene in Sorghum bicolor seedlings producing the gas in circadian rhythms. For the first time, a natural enzyme was used...

Gohil, Hemantkumar Laxmansinh

2002-01-01

374

Intermolecular C-O Addition of Carboxylic Acids to Arynes: Synthesis of o-Hydroxyaryl Ketones, Xanthones, 4-Chromanones, and Flavones  

PubMed Central

An efficient and simple route to biologically and pharmaceutically important o-hydroxyaryl ketones, xanthones, 4-chromanones, and flavones has been developed utilizing readily available carboxylic acids and commercially available o-(trimethylsilyl)aryl triflates. PMID:23520410

Dubrovskiy, Anton V.

2013-01-01

375

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

376

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

377

Reagents and Synthetic Methods 21. Thionyl Chloride \\/4-(N,N-Dimethylamino) Pyridine Complex. A Simple One-Pot Method for Esterification of Carboxylic Acids  

Microsoft Academic Search

Esters are obtained by a one-pot method, in which the carboxylic acid is first converted into its acyl chloride by means of thionyl chloride\\/4-(N,N-dimethylamino)pyridine complex as a new activating reagent.

A. Arrieta; T. García; C. Palomo

1982-01-01

378

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

379

Separation of aromatic carboxylic acids using quaternary ammonium salts on reversed-phase HPLC. 2. Application for the analysis of Loy Yang coal oxidation products  

SciTech Connect

In order to develop separation processes and analytical methods for aromatic carboxylic acids for the coal oxidation products, the separation behavior of aromatic carboxylic acids on a reversed-phase HPLC using eluent containing quaternary ammonium salt was optimized using the solvent gradient method. This method was applied for the analysis of Loy Yang coal oxidation products. It was confirmed that the analytical data using this method were consistent with those determined using gas chromatography.

Kawamura, K.; Okuwaki, A.; Verheyen, T.V.; Perry, G.J. [Tohoku University, Miyagi (Japan). Graduate School of Environmental Studies

2006-07-01

380

A secondary metabolite, 4,5-dibromopyrrole-2-carboxylic acid, from marine sponges of the genus Agelas alters cellular calcium signals  

Microsoft Academic Search

A secondary metabolite from sponges of the genus Agelas, 4,5-dibromopyrrole-2-carboxylic acid, which is well known as feeding deterrent, was investigated for effects on the cellular calcium homeostasis in PC12 cells. 4,5-Dibromopyrrole-2-carboxylic acid did not change intracellular calcium levels if applied alone without cell depolarization. During depolarization of the cellular membrane using high potassium solution, a dose dependent reduction of intracellular

Ulf Bickmeyer; Michael Assmann; Matthias Köck; Christian Schütt

2005-01-01

381

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

PubMed Central

Imidazoles and their derivatives are compounds with chemotherapeutic applications. In this study, we investigated the chemical functionalization of carboxylated multiwalled carbon nanotubes (MWNT–COOH) by 1,2-phenylendiamine. Multiwalled nanotube (MWNT)–benzimidazole was obtained by an MWNT–amide reaction with POCl3 after 72 hours, which was confirmed by Fourier transform infrared, scanning electron microscopy, thermal gravimetric analysis, and elemental analysis. These functionalizations were chosen due to -NH2 and NHCO active sites in MWNT–amide for future application. Toxicity assays with fibroblast cells and MTT test for measurement of viable cell numbers were also performed. Cellular results did not show any toxicity change in modified samples from that of the reference samples. PMID:21116331

Azizian, Javad; Tahermansouri, Hasan; Biazar, Esmaeil; Heidari, Saeed; Khoei, Davood Chobfrosh

2010-01-01

382

Hydrogen bonding in cyclic imides and amide carboxylic acid derivatives from the facile reaction of cis-cyclohexane-1,2-carboxylic anhydride with o- and p-anisidine and m- and p-aminobenzoic acids.  

PubMed

The structures of the open-chain amide carboxylic acid rac-cis-2-[(2-methoxyphenyl)carbamoyl]cyclohexane-1-carboxylic acid, C(15)H(19)NO(4), (I), and the cyclic imides rac-cis-2-(4-methoxyphenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, C(15)H(17)NO(3), (II), chiral cis-3-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)benzoic acid, C(15)H(15)NO(4), (III), and rac-cis-4-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)benzoic acid monohydrate, C(15)H(15)NO(4)·H(2)O, (IV), are reported. In the amide acid (I), the phenylcarbamoyl group is essentially planar [maximum deviation from the least-squares plane = 0.060 (1) Å for the amide O atom] and the molecules form discrete centrosymmetric dimers through intermolecular cyclic carboxy-carboxy O-H···O hydrogen-bonding interactions [graph-set notation R(2)(2)(8)]. The cyclic imides (II)-(IV) are conformationally similar, with comparable benzene ring rotations about the imide N-C(ar) bond [dihedral angles between the benzene and isoindole rings = 51.55 (7)° in (II), 59.22 (12)° in (III) and 51.99 (14)° in (IV)]. Unlike (II), in which only weak intermolecular C-H···O(imide) hydrogen bonding is present, the crystal packing of imides (III) and (IV) shows strong intermolecular carboxylic acid O-H···O hydrogen-bonding associations. With (III), these involve imide O-atom acceptors, giving one-dimensional zigzag chains [graph-set C(9)], while with the monohydrate (IV), the hydrogen bond involves the partially disordered water molecule which also bridges molecules through both imide and carboxy O-atom acceptors in a cyclic R(4)(4)(12) association, giving a two-dimensional sheet structure. The structures reported here expand the structural database for compounds of this series formed from the facile reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with substituted anilines, in which there is a much larger incidence of cyclic imides compared to amide carboxylic acids. PMID:22935496

Smith, Graham; Wermuth, Urs D

2012-09-01

383

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

384

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

385

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

386

Phenazine-1-Carboxylic Acid Promotes Bacterial Biofilm Development via Ferrous Iron Acquisition?†  

PubMed Central

The opportunistic pathogen Pseudomonas aeruginosa forms biofilms, which render it more resistant to antimicrobial agents. Levels of iron in excess of what is required for planktonic growth have been shown to promote biofilm formation, and therapies that interfere with ferric iron [Fe(III)] uptake combined with antibiotics may help treat P. aeruginosa infections. However, use of these therapies presumes that iron is in the Fe(III) state in the context of infection. Here we report the ability of phenazine-1-carboxylic acid (PCA), a common phenazine made by all phenazine-producing pseudomonads, to help P. aeruginosa alleviate Fe(III) limitation by reducing Fe(III) to ferrous iron [Fe(II)]. In the presence of PCA, a P. aeruginosa mutant lacking the ability to produce the siderophores pyoverdine and pyochelin can still develop into a biofilm. As has been previously reported (P. K. Singh, M. R. Parsek, E. P. Greenberg, and M. J. Welsh, Nature 417:552-555, 2002), biofilm formation by the wild type is blocked by subinhibitory concentrations of the Fe(III)-binding innate-immunity protein conalbumin, but here we show that this blockage can be rescued by PCA. FeoB, an Fe(II) uptake protein, is required for PCA to enable this rescue. Unlike PCA, the phenazine pyocyanin (PYO) can facilitate biofilm formation via an iron-independent pathway. While siderophore-mediated Fe(III) uptake is undoubtedly important at early stages of infection, these results suggest that at later stages of infection, PCA present in infected tissues may shift the redox equilibrium between Fe(III) and Fe(II), thereby making iron more bioavailable. PMID:21602354

Wang, Yun; Wilks, Jessica C.; Danhorn, Thomas; Ramos, Itzel; Croal, Laura; Newman, Dianne K.

2011-01-01

387

Spectral and biological evaluation of a synthetic antimicrobial peptide derived from 1-aminocyclohexane carboxylic acid.  

PubMed

Ac-GF(A6c)G(A6c)K(A6c)G(A6c)F(A6c)G(A6c)GK(A6c)KKKK-amide (A6c=1-aminocyclohexane carboxylic acid) is a synthetic antimicrobial peptide (AMP) that exhibits in vitro inhibitory activity against drug resistant strains of Staphylococcus aureus, Acinetobacter baumannii, Klebsiella pneumoniae, Pseudomonas aeruginosa, Enterobacter aerogenes, and Enterococcus faecium at concentrations ranging from 10.9 to 43?M. Spectroscopic investigations were conducted to determine how this AMP interacts with simple membrane model systems in order to provide insight into possible mechanisms of action. CD and 2D-(1)H NMR experiments indicated this AMP on binding to SDS and DPC micelles adopts conformations with varying percentages of helical and random coil conformers. CD investigations in the presence of three phospholipid SUVs consisting of POPC, 4:1 POPC/POPG, and 60% POPE/21%POPG/19%POPC revealed: (1) The interactions occurring with POPC SUVs have minimal effect on the conformational diversity of the AMP yielding conformations similar to those observed in buffer. (2) The interactions with 4:1 POPC/POPG, and 60% POPE/21%POPG/19%POPC SUVs exhibited a greater influence on the percentage of different conformers contributing to the CD spectra. (3) The presence of a high of percentage of helical conformers was not observed in the presence of SUVs as was the case with micelles. This data indicates that the diversity of surface bound conformations adopted by this AMP are very different from the diversity of conformations adopted by this AMP on insertion into the lipid bilayer. CD spectra of this AMP in the presence of SUVs consisting of LPS isolated from P. aeruginosa, K. pneumoniae and Escherichia coli exhibited characteristics associated with various helical conformations. PMID:25684423

Abercrombie, J J; Leung, Kai P; Chai, Hanbo; Hicks, Rickey P

2015-03-15

388

Chiral amines as reagents for HPLC-MS enantioseparation of chiral carboxylic acids.  

PubMed

Mass spectrometry (MS) has become a popular analytical technique because of its high sensitivity and specificity. Therefore, the use of a chiral derivatization reagent for the MS detection seems to be efficient for the enantiomeric separation of racemates. However, the number of chiral reagents for the liquid chromatography (LC)-tandem mass spectrometry (MS/MS) analysis is very limited. The applicability of commercially available chiral amines as the derivatization reagents for the enantiomeric separation of chiral carboxylic acids is reported in this paper by using non-steroidal anti-inflammatory drugs (NSAIDs), i.e. ibuprofen, flurbiprofen, and loxoprofen. The efficiency of the chiral reagents was evaluated in terms of tagging easiness, separation by reversed-phase chromatography, and detection sensitivity by electrospray ionization (ESI)-MS/MS. Among the tested eight chiral amines, i.e. (R)-(+)-4-(3-aminopyrrolidin-1-yl)-7-(N,N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole (DBD-APy), (S)-(+)-1-(2-pyrrolidinylmethyl)-pyrrolidine (PMP), L-prolinamide, (3R)-(-)-1-benzyl-3-aminopyrrolidine, (S)-(+)-1-cyclohexyl-ethylamine, (3R)-(+)-3-(trifluoroacetamido)-pyrrolidine (TFAP), (R)-(-)-1-aminoindan (AI), and (S)-(+)-tetrahydrofurfuryl-amine, DBD-APy, PMP, AI, and TFAP could be used as the chiral reagents for the enantiomeric separation of the NSAIDs. The Rs values and the detection limits of the derivatives were in the range of 1.29-3.85 and 0.57-0.96 fmol, respectively. These four reagents were applied for the determination of the NSAIDs in rat plasma. PMID:22761132

Tsutsui, Haruhito; Fujii, Shinya; Sakamoto, Tasuku; Min, Jun Zhe; Todoroki, Kenichiro; Toyo'oka, Toshimasa

2012-07-01

389

Efficient synthesis and utilization of phenyl-substituted heteroaromatic carboxylic acids as aryl diketo acid isosteres in the design of novel HIV-1 integrase inhibitors.  

PubMed

Three new types of aryl diketo acid (ADK) isosteres were designed by conversion of the biologically labile 1,3-diketo unit into heteroaromatic motif such as isoxazole, isothiazole, or 1H-pyrazole to improve the physicochemical property of ADK-based HIV-1 integrase (IN) inhibitors. The synthesis of the heteroaromatic carboxylic acids was established by employing phenyl beta-diketoester or benzaldehyde as the starting material and 1,3-dipolar cycloaddition as the key reaction. Of the compounds tested, the 3-benzyloxyphenyl-substituted isoxazole carboxylic acid displayed the best IN inhibitory and antiviral activities, with N-hydroxylamidation enhancing the in vitro and in vivo potency. These findings are important for further optimization of ADK-based IN inhibitors. PMID:18662877

Zeng, Li-Fan; Zhang, Hu-Shan; Wang, Yun-Hua; Sanchez, Tino; Zheng, Yong-Tang; Neamati, Nouri; Long, Ya-Qiu

2008-08-15

390

New Samarium(III), Gadolinium(III), and Dysprosium(III) Complexes of Coumarin-3-Carboxylic Acid as Antiproliferative Agents  

PubMed Central

New complexes of samarium(III), gadolinium(III), and dysprosium(III) with coumarin-3-carboxylic acid (HCCA) were prepared by the reaction of the ligand with respective metal nitrates in ethanol. The structures of the final complexes were determined by means of physicochemical data, elemental analysis, IR and Raman spectra. The metal-ligand binding mode in the new Ln(III) complexes of coumarin-3-carboxylic acid was elucidated. The vibrational study gave evidence for bidentate coordination of CCA? to Ln(III) ions through the carbonylic oxygen and the carboxylic oxygen atoms. The complexes were tested for antiproliferative activitiy on the chronic myeloid leukemia-derived K-562, overexpressing the BCR-ABL fusion protein. Cytotoxicity towards tumor cells was determined for a broad concentration range. The samarium salt exerted a very weak antiproliferative effect on these cells. This is in contrast to the lanthanide complexes, especially samarium complex, which exhibited potent antiproliferative activity. The present study confirms our previous observations that the lanthanide complexes of coumarins exhibit antiproliferative activity towards K-562 cell line. PMID:18274603

Kostova, Irena; Momekov, Georgi; Stancheva, Peya

2007-01-01

391

Carboxylic acids in PM 2.5 over Pinus morrisonicola forest and related photoreaction mechanisms identified via Raman spectroscopy  

NASA Astrophysics Data System (ADS)

The PM 2.5 aerosol from within an area of Pinus morrisonicola Hayata in Taiwan was collected and analyzed for its low molecular weight carboxylic acid (LMWCAs) content. Oxalic acid was the major LMWCA in the aerosol, followed by acetic, tartaric and maleic acids. This differs significantly from the LMWCA composition of PM 2.5 aerosol reported for a southern Taiwan suburban region (oxalic > succinic > malonic) [Atmospheric Environment 42, 6836-6850 (2008)]. P. morrisonicola Hayata emits oxalic, malic and formic acids and yet there was an abundance of maleic and tartaric acids in the PM 2.5 forest aerosol, indicating that tartaric acid is derived from the transformation of other P. morrisonicola Hayata emissions. Raman spectroscopy was applied and 28 species of LMWCAs and inorganic species were identified. The photochemical mechanisms of maleic and tartaric acids were studied and it was found that the abundant tartaric acid in forest aerosol is most probably the photochemical product from reactions of maleic acid. Furthermore, tartaric acid is photochemically transformed into formic acid and ultimately into CO 2.

Kuo, Su-Ching; Tsai, Ying I.; Tsai, Cheng-Hsien; Hsieh, Li-Ying

2011-12-01

392

Simple Formation of C60 and C60-Ferrocene Conjugated Monolayers Anchored onto Silicon Oxide with Five Carboxylic Acids and Their Transistor Applications  

SciTech Connect

C{sub 60} and C{sub 60}-ferrocene conjugated molecule bearing five carboxylic acids successfully anchor onto a silicon oxide surface as a monolayer through a simple method of simply dipping an amino-terminated surface into the solution of the C{sub 60} derivatives. The monolayer structure was characterized by UV-vis spectroscopy, X-ray reflectivity, X-ray photoelectron spectroscopy, and IR spectroscopy to reveal that the molecules are standing presenting its C{sub 60} spherical face at the surface. The electronic effect of the C{sub 60} monolayer and the ferrocene-functionalized C{sub 60} monolayer in OFET devices was investigated. When an n-type OFET was fabricated on the ferrocene functionalized monolayer, we see an enhancement in the mobility. When a p-type OFET was made the ferrocene-functionalized C{sub 60} monolayer showed a lowering of the carrier mobility.

Y Itoh; B Kim; R Gearba; N Tremblay; R Pindak; Y Matsuo; E Nakamura; C Nuckolls

2011-12-31

393

Perfluoroalkyl sulfonic and carboxylic acids: A critical review of physicochemical properties, levels and patterns in waters and wastewaters, and treatment methods  

Microsoft Academic Search

Perfluorinated acids (PFAs) are an emerging class of environmental contaminants present in various environmental and biological matrices. Two major PFA subclasses are the perfluorinated sulfonic acids (PFSAs) and carboxylic acids (PFCAs). The physicochemical properties and partitioning behavior for the linear PFA members are poorly understood and widely debated. Even less is known about the numerous branched congeners with varying perfluoroalkyl

Sierra Rayne; Kaya Forest

2009-01-01

394

Covalent attachments of boron nitride nanotubes through a carboxylic linker: Density functional studies  

NASA Astrophysics Data System (ADS)

Properties of attached boron nitride (BN) nanotubes based on linking two zigzag nanotubes through a carboxylic (-(Cdbnd O)O-) linker were investigated by performing density functional theory (DFT) calculations. The linking boron and nitrogen atoms at the edges of two zigzag BN nanotubes were linked to the -(C]O)O- linker to make possible the attachments of two BN nanotubes together. Total energies, energy gaps, dipole moments, linking bond lengths and angles, and quadrupole coupling constants were obtained for the optimized structures to determine the properties of the attached BN nanotubes. The results indicated that different properties could be seen for the investigated models based on their linking status. For quadrupole coupling constants, the most significant changes of parameters were observed for the linking atoms among the investigated models of attached BN nanotubes.

Mirzaei, Mahmoud; Arshadi, Sattar; Abedini, Saboora; Yousefi, Mohammad; Meskinfam, Masoumeh

2012-06-01

395

Site-Specific Protonation Kinetics of Acidic Side Chains in Proteins Determined by pH-Dependent Carboxyl (13)C NMR Relaxation.  

PubMed

Proton-transfer dynamics plays a critical role in many biochemical processes, such as proton pumping across membranes and enzyme catalysis. The large majority of enzymes utilize acid-base catalysis and proton-transfer mechanisms, where the rates of proton transfer can be rate limiting for the overall reaction. However, measurement of proton-exchange kinetics for individual side-chain carboxyl groups in proteins has been achieved in only a handful of cases, which typically have involved comparative analysis of mutant proteins in the context of reaction network modeling. Here we describe an approach to determine site-specific protonation and deprotonation rate constants (kon and koff, respectively) of carboxyl side chains, based on (13)C NMR relaxation measurements as a function of pH. We validated the method using an extensively studied model system, the B1 domain of protein G, for which we measured rate constants koff in the range (0.1-3) × 10(6) s(-1) and kon in the range (0.6-300) × 10(9) M(-1) s(-1), which correspond to acid-base equilibrium dissociation constants (Ka) in excellent agreement with previous results determined by chemical shift titrations. Our results further reveal a linear free-energy relationship between log kon and pKa, which provides information on the free-energy landscape of the protonation reaction, showing that the variability among residues in these parameters arises primarily from the extent of charge stabilization of the deprotonated state by the protein environment. We find that side-chain carboxyls with extreme values of koff or kon are involved in hydrogen bonding, thus providing a mechanistic explanation for the observed stabilization of the protonated or deprotonated state. PMID:25665463

Wallerstein, Johan; Weininger, Ulrich; Khan, M Ashhar I; Linse, Sara; Akke, Mikael

2015-03-01

396

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....

397

Chromium(III) removal from water and wastewater using a carboxylate-functionalized cation exchanger prepared from a lignocellulosic residue.  

PubMed

This study concerns with the development of a new cation exchanger (SDGPMASPCOOH) carrying spacer (SP) group [CONH(CH(2))(2)NHCO(CH(2))(2)] and carboxylate functional group at the chain end. The preparation process was carried out through graft copolymerization of methacrylic acid onto sawdust, SD (a lignocellulosic residue) using ceric ammonium nitrate as an initiator. The poly(methacrylic acid) grafted SD (SDGPMA) was subsequently treated with thionyl chloride followed by ethylenediamine (transmidation) and succinic anhydride (carboxyfunctionalization) treatments. Infrared spectroscopy and potentiometric titrations were used to confirm graft copolymer formation and carboxylate functionalization. The effectiveness of the SDGPMASPCOOH in removing Cr(III) from water and wastewater was evaluated by the batch technique. The influence of different experimental parameters such as solution pH, contact time, absorbent dose, Cr(III) concentration and temperature on removal process was evaluated. The maximum Cr(III) removal was observed at the initial pH of 7.0. The Cr(III) was removed by SDGPMASPCOOH up to 99.3 and 92.6% from an initial concentration of 10 and 25 mg/L, respectively, at pH 7.0. Equilibrium time was reached within 4 h. Kinetic data were analyzed using the pseudo-first-order, pseudo-second-order and Elovich equations. The data fitted very well to the pseudo-second-order rate expression. The Langmuir, Freundlich and Temkin equations were applied to the experimental isotherm data and the Langmuir model was found to be in better correlation with the experimental data. The monolayer adsorption capacity for Cr(III) removal was found to be 36.63 mg/g. The adsorption efficiency towards Cr(III) removal was tested using simulated tannery wastewater. The adsorbed Cr(III) on SDGPMASPCOOH can be recovered by treating with 0.1 M HCl. Four adsorption/desorption cycles were performed without significant decrease in removal capacity. The results showed that SDGPMASPCOOH developed in this study exhibited considerable adsorption potential for application in removal of Cr(III) from water and wastewaters. PMID:17905262

Anirudhan, T S; Radhakrishnan, P G

2007-12-15

398

10-Iodo-11H-indolo[3,2-c]quinoline-6-carboxylic Acids Are Selective Inhibitors of DYRK1A.  

PubMed

The protein kinase DYRK1A has been suggested to act as one of the intracellular regulators contributing to neurological alterations found in individuals with Down syndrome. For an assessment of the role of DYRK1A, selective synthetic inhibitors are valuable pharmacological tools. However, the DYRK1A inhibitors described in the literature so far either are not sufficiently selective or have not been tested against closely related kinases from the DYRK and the CLK protein kinase families. The aim of this study was the identification of DYRK1A inhibitors exhibiting selectivity versus the structurally and functionally closely related DYRK and CLK isoforms. Structure modification of the screening hit 11H-indolo[3,2-c]quinoline-6-carboxylic acid revealed structure-activity relationships for kinase inhibition and enabled the design of 10-iodo-substituted derivatives as very potent DYRK1A inhibitors with considerable selectivity against CLKs. X-ray structure determination of three 11H-indolo[3,2-c]quinoline-6-carboxylic acids cocrystallized with DYRK1A confirmed the predicted binding mode within the ATP binding site. PMID:25730262

Falke, Hannes; Chaikuad, Apirat; Becker, Anja; Loaëc, Nadège; Lozach, Olivier; Abu Jhaisha, Samira; Becker, Walter; Jones, Peter G; Preu, Lutz; Baumann, Knut; Knapp, Stefan; Meijer, Laurent; Kunick, Conrad

2015-04-01

399

Improved preparation of haloalkyl bridged carboxylic ortho esters  

Technology Transfer Automated Retrieval System (TEKTRAN)

Protection of a carboxylic acid function as a bridged ortho ester derivative enables the use of strong basic conditions in the synthetic strategy. For example, a protected 3-halopropionic acid can behave like an alkyl halide because the protons, alpha to the halide function, are less acidic. Ester...

400

Biosynthetic mechanism of 2-acetyl-1-pyrroline and its relationship with Delta1-pyrroline-5-carboxylic acid and methylglyoxal in aromatic rice (Oryza sativa L.) callus.  

PubMed

2-Acetyl-1-pyrroline (2-AP) was identified as the major flavor compound in aromatic rice varieties Tainung 71 and 72. In order to understand the mechanism of 2-AP biosynthesis in aromatic rice, we studied the formation of putative precursors, Delta(1)-pyrroline-5-carboxylic acid and methylglyoxal. The endogenous Delta(1)-pyrroline-5-carboxylic acid contents of Tainung 71 and 72 calli reached 191 to 276%, compared to nonaromatic rice Tainung 67. In addition, calli of Tainung 71 and 72 contained 1.30- and 1.36-fold, respectively, higher methylglyoxal levels than that of Tainung 67. Specific enzyme activities of Delta(1)-pyrroline-5-carboxylic acid-synthetic enzyme including Delta(1)-pyrolline-5-carboxylic acid synthetase (P5CS) and ornithine aminotransferase (OAT) increased significantly in aromatic rice varieties. The expression levels of P5CS1 and P5CS2 genes were found to be significantly higher in aromatic rice than nonaromatic rice. Results of a tracer experiment with (15)N-labeled glutamic acid revealed that the nitrogen atom of 2-acetyl-1-pyrroline was derived from glutamic acid. Upregulation of P5CS in aromatic rice Tainung 72 may contribute to the increase of Delta(1)-pyrroline-5-carboxylic acid level and thus leads to the accumulation of an extra amount of 2-acetyl-1-pyrroline. PMID:18680302

Huang, Tzou-Chi; Teng, Chia-Shih; Chang, Jia-Lin; Chuang, Hui-Su; Ho, Chi-Tang; Wu, Mei-Li

2008-08-27

401

Acid-base-controlled stereoselective metalation of overhanging carboxylic acid porphyrins: consequences for the formation of heterobimetallic complexes.  

PubMed

Overhanging carboxylic acid porphyrins have revealed promising ditopic ligands offering a new entry in the field of supramolecular coordination chemistry of porphyrinoids. Notably, the adjunction of a so-called hanging-atop (HAT) Pb(II) cation to regular Pb(II) porphyrin complexes allowed a stereoselective incorporation of the N-core bound cation, and an allosterically controlled Newton's cradle-like motion of the two Pb(II) ions also emerged from such bimetallic complexes. In this contribution, we have extended this work to other ligands and metal ions, aiming at understanding the parameters that control the HAT Pb(II) coordination. The nature of the N-core bound metal ion (Zn(II), Cd(II)), the influence of the deprotonation state of the overhanging COOH group and the presence of a neutral ligand on the opposite side (exogenous or intramolecular), have been examined through (1)H NMR spectroscopic experiments with the help of radiocrystallographic structures and DFT calculations. Single and bis-strap ligands have been considered. They all incorporate a COOH group hung over the N-core on one side. For the bis-strap ligands, either an ester or an amide group has been introduced on the other side. In the presence of a base, the mononuclear Zn(II) or Cd(II) complexes incorporate the carbonyl of the overhanging carboxylate as apical ligand, decreasing its availability for the binding of a HAT Pb(II). An allosteric effector (e.g., 4-dimethylaminopyridine (DMAP), in the case of a single-strap ligand) or an intramolecular ligand (e.g., an amide group), strong enough to compete with the carbonyl of the hung COO(-), is required to switch the N-core bound cation to the opposite side with concomitant release of the COO(-), thereby allowing HAT Pb(II) complexation. In the absence of a base, Zn(II) or Cd(II) binds preferentially the carbonyl of the intramolecular ester or amide groups in apical position rather than that of the COOH. This better preorganization, with the overhanging COOH fully available, is responsible for a stronger binding of the HAT Pb(II). Thus, either allosteric or acid-base control is achieved through stereoselective metalation of Zn(II) or Cd(II). In the latter case, according to the deprotonation state of the COOH group, the best electron-donating ligand is located on one or the other side of the porphyrin (COO(-)>CONHR>COOR>COOH): the lower affinity of COOH for Zn(II) and Cd(II), the higher for a HAT Pb(II). These insights provide new opportunities for the elaboration of innovative bimetallic molecular switches. PMID:23813639

Le Gac, Stéphane; Najjari, Btissam; Dorcet, Vincent; Roisnel, Thierry; Fusaro, Luca; Luhmer, Michel; Furet, Eric; Halet, Jean-François; Boitrel, Bernard

2013-08-12

402

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

403

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.

404

Discriminating the carboxylic groups from the total acidic sites in oxidized multi-wall carbon nanotubes by means of acid–base titration  

Microsoft Academic Search

This work reports on the quantitative determination of the carboxylic groups created upon HNO3 treatment at multi-wall carbon nanotube (MWCNT) surface. To this purpose, MWCNTs have been oxidized by refluxing in acid for different periods of time (from 1h to 12h). The main goal of the present study comprises the development of a simple analytical methodology based on Boehm’s titration

Ana Belén González-Guerrero; Ernest Mendoza; Eva Pellicer; Francesc Alsina; César Fernández-Sánchez; Laura M. Lechuga

2008-01-01

405

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

406

Lewis acid-catalyzed intramolecular condensation of ynol ether-acetals. Synthesis of alkoxycycloalkene carboxylates  

PubMed Central

Treatment of ynol ether-tethered dialkyl acetals with catalytic quantities of scandium triflate in CH3CN gives rise to five-, six-, and seven-membered alkoxycycloalkene carboxylates in good to excellent yields. Trisubstituted and tetrasubsituted carbocyclic and heterocyclic alkenes may be formed by this method, and the products obtained may serve as useful intermediates for natural product synthesis. PMID:23170869

Tran, Vincent

2012-01-01

407

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

408

Synthesis of ?-chloro carboxylic acids by addition of chlorine in a formic acid medium to compounds containing a CCl 2 =CH group  

Microsoft Academic Search

1.Reaction of chlorine with compounds containing the CCl2=CH group in a medium of anhydrous formic acid followed by treatment with water gives a -chloro carboyxlic acids in good yields.2.In this way, from 1,1,3-trichloropropene, l,l-dichloro-3-methoxypropene, 3,3-dichloroallyl formate, 1,1,5-trichloro-1-pentene, 5,5-dichloro-4-pentenyl formate, 1,1,7-trichloro-1-heptene, and 1,1,9-trichloro-1-nonene the following a-chloro carboxylic acids were prepared: 2,3-dichloro- and 2-chloro-3-methoxy-propionic acids, 2-chlorohydracrylic acid formic ester, 2,5-dichlorovaleric acid, 2-chloro-5-hydroxyvaleric

V. N. Kost; T. T. Sidorova; R. Kh. Freidlina; A. N. Nesmeyanov

1959-01-01

409

Diastereomeric complex of ( R/ S)-piperidine-3-carboxylic acid with (2 R,3 R)-tartaric acid: Structural, spectroscopic and computational studies  

NASA Astrophysics Data System (ADS)

2:2 Complex of ( R) and ( S)-piperidine-3-carboxylic acids (P3C) with (2 R,3 R) -tartaric acid (TA), 1, has been characterized by single-crystal X-ray analysis, FTIR and NMR spectroscopies, and by DFT calculations. The crystals of 1 are monoclinic, space group P2 1. The crystal structure is formed by two distinct P3CH +·TA - components, A and B, linked by an O-H⋯O hydrogen bond of 2.603(2) Å. The A and B components differ in the absolute configuration of the C(3) atom of P3CH +; ( S) in A and ( R) in B. The piperidinium-3-carboxylic acid and (2 R,3 R)-semi-tartrate anion moieties of the components A and B are linked by O-H⋯O hydrogen bonds of 2.517(1) and 2.535(1) Å, respectively. In A and B the piperidinium rings adopt the chair conformation with the carboxyl group in the equatorial position. The structures of the monomers of P3CH +·TA -, 3A and 3B, as well as of a dimer 2, have been optimized by the B3LYP/6-31G(d,p) approach. The chemical shift assignments were based on two-dimensional 1H- 1H and 1H- 13C experiments.

Bartoszak-Adamska, E.; Dega-Szafran, Z.; Jaskólski, M.; Szafran, M.

2011-07-01

410

Enantioselective redox-neutral rh-catalyzed coupling of terminal alkynes with carboxylic acids toward branched allylic esters.  

PubMed

We report on the first enantioselective variant of the atom-economic and redox-neutral coupling of carboxylic acids with terminal alkynes under rhodium catalysis utilizing the chiral, bidentate (R,R)-Cp-DIOP ligand. This represents the first example of this convenient asymmetric access to valuable branched allylic esters. The utility of this methodology is demonstrated by both a reaction performed on large scale and a short three-step synthesis of two naturally occurring ?-butyrolactones. A stereochemical model explaining the observed absolute configuration of the products based on DFT calculations is given. PMID:25667963

Koschker, Philipp; Kähny, Matthias; Breit, Bernhard

2015-03-01

411

A tandem conjugate addition/cyclization protocol for the asymmetric synthesis of 2-aryl-4-aminotetrahydroquinoline-3-carboxylic acid derivatives.  

PubMed

Condensation of tert-butyl (E)-3-(2'-aminophenyl)propenoate with a range of aromatic and heteroaromatic aldehydes gives the corresponding imines as single diastereoisomers (>98% de). Addition of lithium (R)-N-benzyl-N-(alpha-methylbenzyl)amide initiates a tandem conjugate addition/cyclization reaction to generate 2-aryl-4-aminotetrahydroquinoline-3-carboxylic acid derivatives in >98% de, >98% ee and high isolated yield. Hydrogenolysis of an N(1)-Boc protected derivative allows selective cleavage of the N-benzyl-N-alpha-methylbenzyl protecting groups without compromise of the diastereo- or enantiopurity. PMID:19348467

Davies, Stephen G; Mujtaba, Nadeam; Roberts, Paul M; Smith, Andrew D; Thomson, James E

2009-05-01

412

Targeted LC–MS derivatization for aldehydes and carboxylic acids with a new derivatization agent 4-APEBA  

PubMed Central

Based on the template of a recently introduced derivatization reagent for aldehydes, 4-(2-(trimethylammonio)ethoxy)benzeneaminium dibromide (4-APC), a new derivatization agent was designed with additional features for the analysis and screening of biomarkers of lipid peroxidation. The new derivatization reagent, 4-(2-((4-bromophenethyl)dimethylammonio)ethoxy)benzenaminium dibromide (4-APEBA) contains a bromophenethyl group to incorporate an isotopic signature to the derivatives and to add additional fragmentation identifiers, collectively enhancing the abilities for detection and screening of unknown aldehydes. Derivatization can be achieved under mild conditions (pH 5.7, 10 °C). By changing the secondary reagent (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide instead of sodium cyanoborohydride), 4-APEBA is also applicable to the selective derivatization of carboxylic acids. Synthesis of the new label, exploration of the derivatization conditions, characterization of the fragmentation of the aldehyde and carboxylic acid derivatives in MS/MS, and preliminary applications of the labeling strategy for the analysis of aldehydes in urine and plasma are described. Figure Structure and MS/MS fragmentation spectrum of 4-APEBA reagents derivatized with octanoic acid Electronic supplementary material The online version of this article (doi:10.1007/s00216-010-3575-1) contains supplementary material, which is available to authorized users. PMID:20238107

Eggink, Mark; Wijtmans, Maikel; Kretschmer, Ansgar; Kool, Jeroen; Lingeman, Henk; de Esch, Iwan J. P.; Irth, Hubertus

2010-01-01

413

The iron-isotope fractionation dictated by the carboxylic functional: An ab-initio investigation  

NASA Astrophysics Data System (ADS)

The ground-state geometries, electronic energies and vibrational properties of carboxylic complexes of iron were investigated both in vacuo and under the effect of a reaction field, to determine thermodynamic properties of iron-acetates and the role of the carboxylic functional on the isotopic imprinting of this metal in metalorganic complexation. The electronic energy, zero point corrections and thermal corrections of these substances at variational state were investigated at the DFT/B3LYP level of theory with different basis set expansions and the effect of the reaction field on the variational structures was investigated through the Polarized Continuun Model. Thermochemical cycle calculations, combined with solvation energy calculations and appropriate scaling from absolute to conventional properties allowed to compute the Gibbs free energy of formation from the elements of the investigated aqueous species and to select the best procedure to be applied in the successive vibrational analysis. The best compliance with the few existing thermodynamic data for these substances was obtained by coupling the gas phase calculations at DFT/B3LYP level with the [6-31G(d,p)]-[6-31G+(d,p)] (for cations and neutral molecules - anions; respectively) with solvation calculations adopting atomic radii optimized for the HF/6-31G(d) level of theory (UAHF). A vibrational analysis conducted on 54Fe, 56Fe, 57Fe and 58Fe gaseous isotopomers yielded reduced partition function ratios which increased not only with the nominal valence of the central cation, as expected, but, more importantly, with the extent of the complexation operated by the organic functional. Coupling thermodynamic data with separative effects it was shown that this last is controlled, as expected, by the relative bond strength of the complex in both aggregation states. Through the Integral Equation Formalism of the Polarized Continuum Model (IEFPCM) the effect of the ionic strength of the solution and of a T-dependent permittivity on the energy and separative effects of the solvated metalorganic complexes were analyzed in detail. The solvent effect in the standard state (hypothetical one-molal solution referred to infinite dilution; T = 298.15 K, P = 1 bar) is a limited reduction of the separative effects of all the isotopomeric couples. With an increase in T (and the concomitant decrease in the dielectric constant of the solvent) this effect diminishes progressively.

Ottonello, G.; Vetuschi Zuccolini, M.

2008-12-01

414

Total Acid Value Titration of Hydrotreated Biomass Fast Pyrolysis Oil: Determination of Carboxylic Acids and Phenolics with Multiple End-Point Detection  

SciTech Connect

Total acid value titration has long been used to estimate corrosive potential of petroleum crude oil and fuel oil products. The method commonly used for this measurement, ASTM D664, utilizes KOH in isopropanol as the titrant with potentiometric end point determination by pH sensing electrode and Ag/AgCl reference electrode with LiCl electrolyte. A natural application of the D664 method is titration of pyrolysis-derived bio-oil, which is a candidate for refinery upgrading to produce drop in fuels. Determining the total acid value of pyrolysis derived bio-oil has proven challenging and not necessarily amenable to the methodology employed for petroleum products due to the different nature of acids present. We presented an acid value titration for bio-oil products in our previous publication which also utilizes potentiometry using tetrabutylammonium hydroxide in place of KOH as the titrant and tetraethylammonium bromide in place of LiCl as the reference electrolyte to improve the detection of these types of acids. This method was shown to detect numerous end points in samples of bio-oil that were not detected by D664. These end points were attributed to carboxylic acids and phenolics based on the results of HPLC and GC-MS studies. Additional work has led to refinement of the method and it has been established that both carboxylic acids and phenolics can be determined accurately. Use of pH buffer calibration to determine half-neutralization potentials of acids in conjunction with the analysis of model compounds has allowed us to conclude that this titration method is suitable for the determination of total acid value of pyrolysis oil and can be used to differentiate and quantify weak acid species. The measurement of phenolics in bio-oil is subject to a relatively high limit of detection, which may limit the utility of titrimetric methodology for characterizing the acidic potential of pyrolysis oil and products.

Christensen, E.; Alleman, T. L.; McCormick, R. L.

2013-01-01

415

Surface chemistry of nanostructures: 1) interactions of mixed monolayers of carboxylic acids on titania, 2) synthesis and immobilization of aqueous cadmium selenide quantum dots  

NASA Astrophysics Data System (ADS)

This thesis will focus on (1) characterization of mixed monolayers of thiol-terminated (T) and methyl-terminated (Me) carboxylic acids on nanocrystalline TiO2 thin films, (2) the synthesis of aqueous CdSe quantum dots (QDs), with particular emphasis on the influence of capping-group functionality and reaction conditions on the kinetics and mechanism of particle growth, and (3) attachment of CdSe QDs to TiO2 thin films and their photoelectrochemical performance as a function of surfactant in QD-sensitized solar cells (QDSSCs). Mixed monolayers have been used in many applications, such as chemical sensing, biomolecular recognition, molecular electronics, catalysis, and as building blocks for materials assembly. Mixed monolayers of T and Me on TiO 2 underwent dimerization-induced compositional changes. Me was displaced on the surface by T because of the formation of intermolecular disulfide bonds between thiol groups of T adsorbed to the TiO2 surface. The compositional changes were found to vary as a function of solvent, alkyl chain length of T, steric bulk of adsorbates, and surface-binding and terminal functional groups. The findings illustrate that dimerization and other intermolecular interactions between adsorbates may dramatically influence the composition and terminal functionalization of mixed monolayers. Semiconductor QDs are attractive alternatives to molecular chromophores and bulk semiconductors for light-harvesting applications in photovoltaics and photocatalysis. Aqueous QDs are of particular interest due to their straightforward, cost-effective, and environmentally-benign syntheses. CdSe QDs were synthesized in basic aqueous suspensions at room temperature under ambient conditions by mixing a cadmium precursor, selenide precursor, and one of several carboxylate-functionalized capping groups (cysteinate, mercaptopropionate, and mercaptosuccinate). The photophysical properties of the QDs varied with capping-group functionality, concentration of precursors, and pH of the aqueous reaction mixture. Varying these parameters allowed for systematic control of the kinetics and mechanism of particle growth, as well as the size and size distribution of QDs at equilibrium. Under certain conditions, "magic-sized" clusters (MSCs) of CdSe, rather than regular QDs, were preferentially synthesized. The carboxylated capping groups of aqueous QDs were used as bifunctional linkers, allowing for facile attachment to nanocrystalline TiO2 thin films. Equilibrium binding experiments were performed to quantify the adsorption of regular QDs and MSCs to nanocrystalline TiO2 thin films. Finally, photoelectrochemistry was used to quantify the influence of capping-group functionality on the efficiency of electron injection from adsorbed QDs into TiO2 and the power-conversion efficiency of QDSSCs.

Nevins, Jeremy S.

2011-12-01

416

Effect of charged amino acid side chain length on lateral cross-strand interactions between carboxylate- and guanidinium-containing residues in a ?-hairpin.  

PubMed

?-Sheet is one of the major protein secondary structures. Oppositely charged residues are frequently observed across neighboring strands in antiparallel sheets, suggesting the importance of cross-strand ion pairing interactions. The charged amino acids Asp, Glu, Arg, and Lys have different numbers of hydrophobic methylenes linking the charged functionality to the backbone. To investigate the effect of side chain length of guanidinium- and carboxylate-containing residues on lateral cross-strand ion pairing interactions at non-hydrogen-bonded positions, ?-hairpin peptides containing Zbb-Agx (Zbb = Asp, Glu, Aad in increasing length; Agx = Agh, Arg, Agb, Agp in decreasing length) sequence patterns were studied by NMR methods. The fraction folded population and folding energy were derived from the chemical shift deviation data. Peptides with high fraction folded populations involved charged residue side chain lengths that supported high strand propensity. Double mutant cycle analysis was used to determine the interaction energy for the potential lateral ion pairs. Minimal interaction was observed between residues with short side chains, most likely due to the diffused positive charge on the guanidinium group, which weakened cross-strand electrostatic interactions with the carboxylate side chain. Only the Aad-Arg/Agh interactions with long side chains clearly exhibited stabilizing energetics, possibly relying on hydrophobics. A survey of a non-redundant protein structure database revealed that the statistical sheet pair propensity followed the trend Asp-Arg < Glu-Arg, implying the need for matching long side chains. This suggested the need for long side chains on both guanidinium-bearing and carboxylate-bearing residues to stabilize the ?-hairpin motif. PMID:25646959

Kuo, Hsiou-Ting; Liu, Shing-Lung; Chiu, Wen-Chieh; Fang, Chun-Jen; Chang, Hsien-Chen; Wang, Wei-Ren; Yang, Po-An; Li, Jhe-Hao; Huang, Shing-Jong; Huang, Shou-Ling; Cheng, Richard P

2015-05-01

417

Catalytic, Enantioselective [4 + 2]-Cycloadditions of Ketene Enolates and o-Quinones: Efficient Entry to Chiral, r-Oxygenated Carboxylic Acid  

E-print Network

available acid chlorides and a cinchona alkaloid-based catalyst. Additionally, the chiral cycloadducts can).2 The reasons for the absence of the [4 + 2]-manifold in ketene enolate-based reactions may be due to a number Entry to Chiral, r-Oxygenated Carboxylic Acid Derivatives Tefsit Bekele, Meha H. Shah, Jamison Wolfer

Lectka, Thomas

418

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

419

Targeted LC-MS derivatization for aldehydes and carboxylic acids with a new derivatization agent 4-APEBA.  

PubMed

Based on the template of a recently introduced derivatization reagent for aldehydes, 4-(2-(trimethylammonio)ethoxy)benzeneaminium dibromide (4-APC), a new derivatization agent was designed with additional features for the analysis and screening of biomarkers of lipid peroxidation. The new derivatization reagent, 4-(2-((4-bromophenethyl)dimethylammonio)ethoxy)benzenaminium dibromide (4-APEBA) contains a bromophenethyl group to incorporate an isotopic signature to the derivatives and to add additional fragmentation identifiers, collectively enhancing the abilities for detection and screening of unknown aldehydes. Derivatization can be achieved under mild conditions (pH 5.7, 10 degrees C). By changing the secondary reagent (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide instead of sodium cyanoborohydride), 4-APEBA is also applicable to the selective derivatization of carboxylic acids. Synthesis of the new label, exploration of the derivatization conditions, characterization of the fragmentation of the aldehyde and carboxylic acid derivatives in MS/MS, and preliminary applications of the labeling strategy for the analysis of aldehydes in urine and plasma are described. PMID:20238107

Eggink, Mark; Wijtmans, Maikel; Kretschmer, Ansgar; Kool, Jeroen; Lingeman, Henk; de Esch, Iwan J P; Niessen, Wilfried M A; Irth, Hubertus

2010-05-01

420

Phenazine-1-carboxylic acid mediated anti-oomycete activity of the endophytic Alcaligenes sp. EIL-2 against Phytophthora meadii.  

PubMed

The oomycete pathogen, Phytophthora meadii, causes various diseases in Hevea brasiliensis at different stages of its life cycle. The study reports the structural characterization of the active principle from the culture filtrate of Alcaligenes sp. EIL-2 (GenBank ID: HQ641257) offering antagonistic activity against P. meadii. Gas Chromatography Mass Spectroscopy (GC-MS) analysis showed the similarity of the compound with phenazine derivatives. The specific representations of FT-IR spectrum such as 3200 cm(-1) (OH stretching, NH stretching and presence of aromatic ring), 1737 cm(-1) (carboxylic acid), 2200-2400 cm(-1) (conjugated dienes) and 1467 cm(-1), and 1422 cm(-1) (CN bonds) were an indicative of phenazine-1-carboxylic acid (PCA). The structure of the compound was further confirmed by (1)H NMR/(13)C NMR spectroscopy, DEPT experiments, and two-dimensional NMR spectral studies, including (1)H-(1)H COSY and (1)H-(13)C HSQC as PCA with the molecular formula of C??H?N?O?. P. meadii was sensitive to purified PCA extract from the endophyte and a concentration of 5 ?g/ml completely inhibited the mycelia growth. PCA also showed zoosporicidal activity against P. meadii zoospores. This is the first study of this kind where PCA from an endophyte of H. brasiliensis is being confirmed to carry antagonistic activity against P. meadii. PMID:24985092

Abraham, Amith; Philip, Shaji; Jacob, Manoj Kurian; Narayanan, Sunilkumar Puthenpurackel; Jacob, C Kuruvilla; Kochupurackal, Jayachandran

2015-01-01

421

Synthesis, characterization, theoretical study and biological activities of oxovanadium (IV) complexes with 2-thiophene carboxylic acid hydrazide.  

PubMed

Oxovanadium (IV) complexes (1)-(3) have been synthesized by treating 2-thiophene carboxylic acid hydrazide with VOSO4?xH2O and VCl3(THF)3 in different M/L ratios. These complexes have been characterized by elemental analysis, UV-vis, FT-IR and mass spectrometry. The FT-IR data predicts the bidentate nature of the ligand which is also confirmed by semi-empirical study. Mass spectrometric data shows that molecular ion peak is only observed for 2-thiophene carboxylic acid hydrazide. The ESP map and thermodynamic parameters shows the presence of partial charge on atoms and stability of synthesized oxovanadium complexes, respectively. DNA binding study of complexes (1)-(3) was carried out by UV-vis and cyclic voltammetric methods which suggests the intercalative binding mode of the complexes with DNA. Cytotoxicity was checked by brine shrimp lethality assay and complex (1) showed greater cytotoxicity towards Artemia salina as compared to free ligand. Immuno-modulatory activity data shows that hydrazide ligand was more active as compared to oxovanadium complexes and standard drug. Complex (2) shows significant urease inhibition activity. The ligand and synthesized complexes were found inactive against all tested bacterial and fungal strains. PMID:24844618

Jabeen, Mudassir; Ali, Saqib; Shahzadi, Saira; Sharma, Saroj K; Qanungo, Kushal

2014-07-01

422

Investigation of acid sites in a zeotypic giant pores chromium(III) carboxylate.  

PubMed

A study of the zeotypic giant pores chromium(III) tricarboxylate Cr(III)3OF(x)(OH)(1-x)(H2O)2 x {C6H3-(CO2)3}2 x nH2O (MIL-100) has been performed. First, its thermal behavior, studied by X-ray thermodiffractometry and infrared spectroscopy, indicates that the departure of water occurs without any pore contraction and no loss in crystallinity, which confirms the robustness of the framework. In a second step, IR spectroscopy has shown the presence of three distinct types of hydroxy groups depending on the outgassing conditions; first, at high temperatures (573 K), only Cr-OH groups with a medium Brønsted acidity are present; at lower temperatures, two types of Cr-H2O terminal groups are observed; and at room temperature, their relatively high Brønsted acidity allows them to combine with H-bonded water molecules. Finally, a CO sorption study has revealed that at least three Lewis acid sites are present in MIL-100 and that fluorine atoms are located on a terminal position on the trimers of octahedra. A first result of grafting of methanol molecules acting as basic organic molecules on the chromium sites has also been shown, opening the way for a postsynthesis functionalization of MIL-100. PMID:16522102

Vimont, Alexandre; Goupil, Jean-Michel; Lavalley, Jean-Claude; Daturi, Marco; Surblé, Suzy; Serre, Christian; Millange, Franck; Férey, Gerard; Audebrand, Nathalie

2006-03-15

423

Systematic evaluation and optimization of modification reactions of oligonucleotides with amines and carboxylic acids for the synthesis of DNA-encoded chemical libraries.  

PubMed

DNA-encoded chemical libraries are collections of small molecules, attached to DNA fragments serving as identification barcodes, which can be screened against multiple protein targets, thus facilitating the drug discovery process. The preparation of large DNA-encoded chemical libraries crucially depends on the availability of robust synthetic methods, which enable the efficient conjugation to oligonucleotides of structurally diverse building blocks, sharing a common reactive group. Reactions of DNA derivatives with amines and/or carboxylic acids are particularly attractive for the synthesis of encoded libraries, in view of the very large number of building blocks that are commercially available. However, systematic studies on these reactions in the presence of DNA have not been reported so far. We first investigated conditions for the coupling of primary amines to oligonucleotides, using either a nucleophilic attack on chloroacetamide derivatives or a reductive amination on aldehyde-modified DNA. While both methods could be used for the production of secondary amines, the reductive amination approach was generally associated with higher yields and better purity. In a second endeavor, we optimized conditions for the coupling of a diverse set of 501 carboxylic acids to DNA derivatives, carrying primary and secondary amine functions. The coupling efficiency was generally higher for primary amines, compared to secondary amine substituents, but varied considerably depending on the structure of the acids and on the synthetic methods used. Optimal reaction conditions could be found for certain sets of compounds (with conversions >80%), but multiple reaction schemes are needed when assembling large libraries with highly diverse building blocks. The reactions and experimental conditions presented in this article should facilitate the synthesis of future DNA-encoded chemical libraries, while outlining the synthetic challenges that remain to be overcome. PMID:25061844

Franzini, Raphael M; Samain, Florent; Abd Elrahman, Maaly; Mikutis, Gediminas; Nauer, Angela; Zimmermann, Mauro; Scheuermann, Jörg; Hall, Jonathan; Neri, Dario

2014-08-20

424

Direct synthesis of amides from carboxylic acids and amines using B(OCH2CF3)3.  

PubMed

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

Lanigan, Rachel M; Starkov, Pavel; Sheppard, Tom D

2013-05-01

425

Contamination of aluminium oxide surfaces in ambient air investigated by FTIR MSR and TOF SIMS. Chemisorption of aliphatic carboxylic acids  

NASA Astrophysics Data System (ADS)

Contamination in ambient air of freshly evaporated aluminium surfaces covered with a thin layer of native oxide has been studied using Fourier transform infrared multiple specular reflectance (FTIR MSR) and time-of-flight secondary ion mass spectrometry (TOF SIMS). The FTIR MSR experiments yield vibrational spectra than can be attributed to short-chain aliphatic carboxylic acids. Some reference spectra have been measured by FTIR MSR spectroscopy of samples prepared by chemisorption of formic, acetic, lactic, butyric and palmitic acids on oxidized aluminium and (in some cases) silver surfaces. From these data the major contaminant has to be the acetate ion. Saturation of the spectral intensities is observed within an hour after exposure to air. The TOF SIMS spectra confirm the conclusion with respect to the acetate ion. Mass peaks belonging to the formate, lactate and some inorganic anions are present in the TOF SIMS spectra.

Sondag, A. H. M.; Raas, M. C.; Van Velzen, P. N. T.

1989-03-01

426

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

427

Isolation and Identification of Two l-Azetidine-2-carboxylic Acid-Degrading Soil Microorganisms, Enterobacter agglomerans and Enterobacter amnigenus  

PubMed

Soil samples collected at several times during the growing season and at different locations within Convallaria majalis beds in Ann Arbor, MI, were screened for their ability to grow with the cyclic amino acid, l-azetidine-2-carboxylic acid (l-A-2-C), as their sole nitrogen source (i.e., metabolize l-A-2-C). Two different soil microorganisms were isolated, characterized, and identified using fundamental selection methods, the standard battery of biochemical characterization tests, and scanning electron microscopy. The assignment of the identity of these organisms as Enterobacter agglomerans and Enterobacter amnigenus was further verified by comparison with authentic microbial samples obtained from ATCC that were able to utilize l-A-2-C as their sole nitrogen source. PMID:9548848

Yeung; Lee; Woodard

1998-02-27

428

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

429

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

430

Derivatization of carboxylic acids with 4-APEBA for detection by positive-ion LC-ESI-MS(/MS) applied for the analysis of prostanoids and NSAID in urine.  

PubMed

In order to develop a generic positive ionization ESI LC-MS method for a variety of interesting substance classes, a new derivatization strategy for carboxylic acids was developed. The carboxylic acid group is labeled with the bromine containing 4-APEBA reagent based on carbodiimide chemistry. The derivatization reaction can be carried out under aqueous conditions, thereby greatly simplifying sample preparation. In this paper, the derivatization of carboxylic acids is exemplified for the determination of prostanoids and non-steroidal anti-inflammatory drugs (NSAID). Optimization of the derivatization conditions was studied. In order to prove the applicability of the presented approach, we applied the described protocol to urine samples from complex regional pain syndrome (CRPS) patients and were able to detect several prostanoids not visible in the urine of healthy volunteers. Further, the determination of the non-steroidal anti-inflammatory drug ibuprofen in a urine sample was possible. PMID:21176889

Kretschmer, A; Giera, M; Wijtmans, M; de Vries, L; Lingeman, H; Irth, H; Niessen, W M A

2011-05-15

431

Synthesis of novel N-benzyl substituted piperidine amides of 1H-indole-5-carboxylic acid as potential inhibitors of cholinesterases.  

PubMed

A series of novel N-benzyl substituted amides of 1H-indole-5-carboxylic acid were synthesized and evaluated for their ability to inhibit acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE). The target compounds (6b-6e) displayed moderate potency to inhibit BuChE. One of the compounds tested, i.e., 1-benzylpiperidine amide of 1H-indole-5-carboxylic acid (6a) was a weak, non-selective inhibitor for both enzymes. The highest inhibitory activity towards BuChE (30.06% [10 microM]) was determined for compound (6c) which is 1-(3-chloro)benzylpiperidine amide of 1H-indole-5-carboxylic acid. PMID:22594259

Jakubowska, Anna; Kulig, Katarzyna; Guzior, Natalia; Malawska, Barbara

2012-01-01

432

Origin of the 900 cm(-1) broad double-hump OH vibrational feature of strongly hydrogen-bonded carboxylic acids.  

PubMed

Medium and strong hydrogen bonds are common in biological systems. Here, they provide structural support and can act as proton transfer relays to drive electron and/or energy transfer. Infrared spectroscopy is a sensitive probe of molecular structure and hydrogen bond strength but strongly hydrogen-bonded structures often exhibit very broad and complex vibrational bands. As an example, strong hydrogen bonds between carboxylic acids and nitrogen-containing aromatic bases commonly display a 900 cm(-1) broad feature with a remarkable double-hump structure. Although previous studies have assigned this feature to the OH, the exact origin of the shape and width of this unusual feature is not well understood. In this study, we present ab initio calculations of the contributions of the OH stretch and bend vibrational modes to the vibrational spectrum of strongly hydrogen-bonded heterodimers of carboxylic acids and nitrogen-containing aromatic bases, taking the 7-azaindole-acetic acid and pyridine-acetic acid dimers as examples. Our calculations take into account coupling between the OH stretch and bend modes as well as how both of these modes are affected by lower frequency dimer stretch modes, which modulate the distance between the monomers. Our calculations reproduce the broadness and the double-hump structure of the OH vibrational feature. Where the spectral broadness is primarily caused by the dimer stretch modes strongly modulating the frequency of the OH stretch mode, the double-hump structure results from a Fermi resonance between the out of the plane OH bend and the OH stretch modes. PMID:25770541

Van Hoozen, Brian L; Petersen, Poul B

2015-03-14

433

Origin of the 900 cm-1 broad double-hump OH vibrational feature of strongly hydrogen-bonded carboxylic acids  

NASA Astrophysics Data System (ADS)

Medium and strong hydrogen bonds are common in biological systems. Here, they provide structural support and can act as proton transfer relays to drive electron and/or energy transfer. Infrared spectroscopy is a sensitive probe of molecular structure and hydrogen bond strength but strongly hydrogen-bonded structures often exhibit very broad and complex vibrational bands. As an example, strong hydrogen bonds between carboxylic acids and nitrogen-containing aromatic bases commonly display a 900 cm-1 broad feature with a remarkable double-hump structure. Although previous studies have assigned this feature to the OH, the exact origin of the shape and width of this unusual feature is not well understood. In this study, we present ab initio calculations of the contributions of the OH stretch and bend vibrational modes to the vibrational spectrum of strongly hydrogen-bonded heterodimers of carboxylic acids and nitrogen-containing aromatic bases, taking the 7-azaindole—acetic acid and pyridine—acetic acid dimers as examples. Our calculations take into account coupling between the OH stretch and bend modes as well as how both of these modes are affected by lower frequency dimer stretch modes, which modulate the distance between the monomers. Our calculations reproduce the broadness and the double-hump structure of the OH vibrational feature. Where the spectral broadness is primarily caused by the dimer stretch modes strongly modulating the frequency of the OH stretch mode, the double-hump structure results from a Fermi resonance between the out of the plane OH bend and the OH stretch modes.

Van Hoozen, Brian L.; Petersen, Poul B.

2015-03-01

434

Diphenyl-benzo[1,3]dioxole-4-carboxylic acid pentafluorophenyl ester: a convenient catechol precursor in the synthesis of siderophore vectors suitable for antibiotic Trojan horse strategies.  

PubMed

Catechols are components of many metal-chelating compounds, including siderophores that are naturally occurring iron(III) chelators excreted by microorganisms. Catechol derivatives are poorly soluble in organic media and the synthesis of catechol-containing molecules requires the use of protected catechol precursors with improved organic solubility. We therefore developed 2,2-diphenyl-benzo[1,3]dioxole-4-carboxylic acid pentafluorophenyl ester. This activated ester reacts with an amine functionalized scaffold to generate chelators in which the catechol functions are protected in the form of diphenyl-benzodioxole moieties. The catechol can subsequently be deprotected, at the end of the synthesis, with trifluoroacetic acid (TFA). This strategy was applied to the synthesis of two catechol compounds functionalized with a terminal propargyl extension. These two compounds were shown to promote iron uptake in Escherichia coli and Pseudomonas aeruginosa. These two compounds are suitable for use as vectors in antibiotic Trojan horse approaches, as they could be conjugated with azide-functionalized antibiotics using the Huisgen dipolar 1,3-cycloaddition. PMID:24305839

Baco, Etienne; Hoegy, Françoise; Schalk, Isabelle J; Mislin, Gaëtan L A

2014-02-01

435

The nucleotide sequence of the RAD3 gene of Saccharomyces cerevisiae: a potential adenine nucleotide binding amino acid sequence and a nonessential acidic carboxyl terminal region.  

PubMed Central

The RAD3 gene of Saccharomyces cerevisiae is required for excision of pyrimidine dimers and is essential for viability. We present the nucleotide sequence of the RAD3 protein coding region and its flanking regions, and the deduced primary structure of the RAD3 protein. In addition, we have mapped the 5' end of RAD3 mRNA. The predicted RAD3 protein contains 778 amino acids with a calculated molecular weight of 89,779. A segment of the RAD3 protein shares homology with several adenine nucleotide binding proteins, suggesting that RAD3 protein may react with ATP. The twenty carboxyl terminal amino acids of RAD3 protein are predominantly acid