Showing papers on "Carboxylic acid published in 2003"

Effect of Chemical Oxidation on the Structure of Single-Walled Carbon Nanotubes

Abstract: In the present study, we report the systematic investigation of the effect of chemical oxidation on the structure of single-walled carbon nanotubes (SWNTs) by using different oxidants. The oxidation procedure was characterized by using infrared spectroscopy and transmission electron microscopy (TEM). The SWNTs were produced by chemical vapor deposition (CVD) and oxidized with three kinds of oxidants: (1) nitric acid (2.6 M), (2) a mixture of concentrated sulfuric acid (98 wt %) and concentrated nitric acid (16 M) (v/v = 3/1) and (3) KMnO4. The results reveal that the different functional groups can be introduced when the SWNTs are treated with different oxidants. Refluxing in dilute nitric acid can be considered as a mild oxidation for SWNTs, introducing the carboxylic acid groups only at those initial defects that already exist. The abundance of the carboxylic acid groups generated with this oxidant remained constant along with the treating time. In contrast, sonication of SWNTs in H2SO4/HNO3 increased ...

Sidewall carboxylic acid functionalization of single-walled carbon nanotubes.

Abstract: The reactions of single-walled carbon nanotubes (SWNTs) with succinic or glutaric acid acyl peroxides in o-dichlorobenzene at 80−90 °C resulted in the addition of 2-carboxyethyl or 3-carboxypropyl groups, respectively, to the sidewalls of the SWNT. These acid-functionalized SWNTs were converted to acid chlorides by derivatization with SOCl2 and then to amides with terminal diamines such as ethylenediamine, 4,4‘-methylenebis(cyclohexylamine), and diethyltoluenediamine. The acid-functionalized SWNTs and the amide derivatives were characterized by a set of materials characterization methods including attenuated total reflectance (ATR) FTIR, Raman and solid state 13C NMR spectroscopy, transmission electron microscopy (TEM), and thermal gravimetry-mass spectrometry (TG-MS). The degree of SWNT sidewall functionalization with the acid-terminated groups was estimated as 1 in 24 carbons on the basis of TG-MS data. In comparison with the pristine SWNTs, the acid-functionalized SWNTs show an improved solubility in p...

Cocrystals of 1,3,5-Cyclohexanetricarboxylic Acid with 4,4‘-Bipyridine Homologues: Acid···Pyridine Hydrogen Bonding in Neutral and Ionic Complexes

Abstract: cis,cis-1,3,5-Cyclohexanetricarboxylic acid (H3CTA) is crystallized with bipyridine bases 1,2-bis(4-pyridyl)ethane (bipy-eta), 1,4-bis(4-pyridyl-2-ethyl)benzene (bipy-etabz), 1,2-bis(4-pyridyl)ethylene (bipy-ete), and 1,4-bis(2-(4-pyridyl)ethenyl)benzene (bipy-etebz) to afford molecular complexes (H3CTA)·(bipy-eta)1.5 1, (H3CTA)·(bipy-etabz) 2, (H2CTA-)·(bipy-ete2H+)0.5 3, and (H2CTA-)·(bipy-etebz2H+)0.5 4. Cocrystal 1 has a super honeycomb hydrogen bond network stabilized by carboxylic acid-bipyridine O−H···N synthon Va. The hexagonal cavity of 34.1 × 36.7 A is filled by parallel triple interpenetration of independent networks. 2 has zigzag chains of synthon Va connected via O−H···O hydrogen bonds. Carboxylic acid to pyridine proton transfer occurs in 3 and 4. These structures have undulated and flat 2D layers of O−H···O- and O−H···O hydrogen bonds that are connected to bipyridinium via N+−H···O- hydrogen bond Vb. H2CTA- anions in 4 form a porous parquet grid of 14.5 × 7.5 A with the channels accommodati...

Supported Keggin type heteropolycompounds for ecofriendly reactions

Abstract: New supported Keggin heteropolyacid (HPA) catalysts were prepared in order to make a contribution to the field of catalyzed acid reactions by means of ecofriendly technologies. The esterification of isoamyl alcohol and acetic acid in gaseous phase was studied using tungstophosphoric acid (TPA) supported on different carriers, silica materials, carbon and alumina. These catalysts were characterized by FT-IR, DRS, TPR and their acidity was evaluated through the isopropanol dehydration test reaction. The higher acidic catalysts prepared with silica materials led to the greatest activities due to the higher proton availability which, in turn, was related to the lower interaction and dispersion of the active species. In order to perform this acid reaction in heterogeneous liquid phase and to avoid the tungstophosphoric or molybdophosphoric acid (MPA) solubilization during reaction, functionalized silica and SiMCM-41, and polyvinyl alcohol hydrogel–polyethylenglycol (PVA-PVG) beads were used as new supports. The physical–chemical characterization of the supported catalysts by FT-IR, XRD, 31 P MAS NMR and TG-DTA showed mainly undegraded primary Keggin structure. The solids exhibited low or negligible solubilization and their acidity, measured by potentiometric titration with n-butylamine, was high. The SiMCM-41 and polymeric bead-supported catalysts lead to obtain attractive activity in the isoamyl acetate synthesis through esterification reaction.

Potential inhibitors from wet oxidation of wheat straw and their effect on ethanol production of Saccharomyces cerevisiae: Wet oxidation and fermentation by yeast

Abstract: Alkaline wet oxidation (WO) (using water, 6.5 g/L sodium carbonate and 12 bar oxygen at 195°C) was used as pretreatment method for wheat straw (60 g/L), resulting in a hydrolysate and a cellulosic solid fraction. The hydrolysate consisted of soluble hemicellulose (8 g/L), low-molecular-weight carboxylic acids (3.9 g/L), phenols (0.27 g/L = 1.7 mM) and 2-furoic acid (0.007 g/L). The wet oxidized wheat straw hydrolysate caused no inhibition of ethanol production by Saccharomyces cerevisiae ATCC 96581. Nine phenols and 2-furoic acid, identified to be present in the hydrolysate, were each tested in concentrations of 50–100 times the concentration found in the hydrolysate for their effect on fermentation by yeast. At these high concentrations (10 mM), 4-hydroxybenzaldehyde, vanillin, 4-hydroxyacetophenone and acetovanillone caused a 53–67% decrease in the volumetric ethanol productivity in S. cerevisiae compared to controls with an ethanol productivity of 3.8 g/L. The phenol acids (4-hydroxy, vanillic and syringic acid), 2-furoic acid, syringaldehyde and acetosyringone were less inhibitory, causing a 5–16% decrease in ethanol productivity. By adding the same aromatic compounds to hydrolysate (10 mM), it was shown that syringaldehyde and acetovanillone interacted negatively with hydrolysate components on the ethanol productivity. Fermentation in WO hydrolysate, that had been concentrated 6 times by freeze-drying, lasted 4 hours longer than in regular hydrolysate; however, the ethanol yield was the same. The longer fermentation time could not be explained by an inhibitory action of phenols alone, but was more likely caused by inhibitory interactions of phenols with carboxylic acids, such as acetic and formic acid. © 2003 Wiley Periodicals, Inc. Biotechnol Bioeng 81: 738–747, 2003.

Kinetics study of esterification of acetic acid with isobutanol in the presence of amberlite catalyst

Abstract: Kinetic data on the esterification of acetic acid with isobutanol have been obtained from both the uncatalyzed and heterogeneously catalyzed reactions using a stirred batch reactor in dioxane. The equilibrium constant, which is independent of temperature ranging from 318 to 368 K, was found to be 4. The uncatalyzed reaction was proved to be second-order reversible. In the presence of the catalyst, on the other hand, the reaction has been found to occur between an adsorbed alcohol molecule and a molecule of acid in the bulk fluid (Eley–Rideal model). It has also been observed that the initial reaction rate decreases with alcohol and water concentrations and it linearly increases with that of acid. The temperature dependency of the constants appearing in the rate expression were also determined.

Atmospheric Pressure Plasma Deposition of Structurally Well-Defined Polyacrylic Acid Films

Abstract: Ultrasonic atomization of acrylic acid monomer into an atmospheric pressure glow discharge (APGD) leads to the deposition of structurally well-defined polymeric films. High retention of the carboxylic acid group has been verified by XPS and FT-IR spectroscopy. These films are found to exhibit low water contact angle values and display good adhesive and gas barrier performance.

Labeling the defects of single-walled carbon nanotubes using titanium dioxide nanoparticles

Abstract: We describe here a new method for labeling the defects of single-walled carbon nanotubes (SWNTs) using TiO2 nanoparticles as markers SWNTs were prepared by chemical vapor deposition, and dilute nitric acid (26M) oxidation was used to introduce carboxylic acid groups at the defect sites Characterization of the SWNTs using ultrastructural and spectroscopic analyses was carried out following introduction of TiO2 nanoparticles The results indicated that TiO2 nanoparticles were chemically absorbed at SWNT defect sites via an ester-type linkage between carboxylic acid groups at the defect sites and hydroxyl groups at the surface of the TiO2 nanoparticles In addition, the adsorption behavior of TiO2 nanoparticles on SWNTs was determined following oxidization of the SWNTs using different processes The results indicated that gas-phase oxidation introduces very few defect sites as evidenced by the low adsorption density of TiO2 nanoparticles Refluxing in dilute nitric acid can be considered as a mild oxidati

Oxide-catalyzed conversion of acetic acid into acetone: an FTIR spectroscopic investigation

Abstract: Adsorptive and catalytic interactions of gas phase acetic acid with surfaces of alumina, titania and ceria were observed by in situ Fourier-transform infrared (FTIR) spectroscopy on heating from room temperature up to 400 °C. The results revealed that, on alumina the acid was irreversibly, non-dissociatively adsorbed in the form of hydrogen-bonded molecules, and dissociatively in the form of bidentate bound acetate species over the full range of temperature scanned. In the gas phase, no chemical change was observed. On titania, the gas phase remained unchanged on heating up to 300 °C, but at 400 °C the acetic acid was largely converted into acetone (as well as CO 2 and H 2 O) and minor products of isobutene and methane. Similar changes to the gas phase were observed on ceria, however, at 300 °C. The acetic acid conversion on ceria was almost complete. The appearance of acetone molecules in the gas phase was pertained by the emergence of IR absorptions implying the formation on the surface of unsaturated carbonyl species. Thus, the formation of these surface species, together with isobutene and CH 4 molecules in the gas phase, was considered consequent to the occurrence of further surface reactions of acetone molecules. Observance of structural and chemical stability of the surface and bulk of TiO 2 and CeO 2 throughout the reaction was taken to emphasize the catalytic nature of the acetic acid conversion into acetone in the gas phase, a process that is evidently more simple and economic than the conventional pyrolytic synthesis of acetone from metal acetate compounds in the solid state. The catalytic sites were suggested to be Lewis acid–base pair sites, with the Lewis acid sites (Ti 4+ or Ce 4+ ) being reducible. Mechanistic pathways were proposed for the observed adsorptive and catalytic interactions of acetic acid molecules on the test oxides.

Orally active, antimalarial, anticancer, artemisinin-derived trioxane dimers with high stability and efficacy.

Abstract: In only two steps and in 70% overall yield, naturally occurring trioxane artemisinin (1) was converted on a gram scale into C-10-carba trioxane dimer 3. This new, very stable dimer was then transformed easily in one additional step into four different dimers 4-7. Alcohol and diol dimers 4 and 5 and ketone dimer 7 are 10 times more antimalarially potent in vitro than artemisinin (1), and alcohol and diol dimers 4 and 5 are strongly growth inhibitory but not cytotoxic toward several human cancer cell lines. Water-soluble carboxylic acid derivatives 8aand 9 were easily prepared in one additional step from dimers 4 and 5. Carboxylic acid dimers 8a and 9 are thermally stable even at 60 degrees C for 24 h, are more orally efficacious as antimalarials in rodents than either artelinic acid or sodium artesunate, and are strongly inhibitory but not cytotoxic toward several human cancer cell lines.

Electrochemical oxidation of several chlorophenols on diamond electrodes Part I. Reaction mechanism

Abstract: The electrochemical oxidation of 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol aqueous wastes using boron-doped diamond electrodes was studied. This treatment led to complete mineralization of the wastes regardless of the operating conditions. A simple mechanistic model is consistent with the voltammetric and electrolysis results. According to this model, the electrochemical treatment of chlorophenol aqueous wastes involves the anodic and cathodic release of chlorine followed by the formation of non-chlorinated aromatic intermediates. Subsequent cleavage of the aromatic ring gives rise to non-chlorinated carboxylic acids. Chlorine atoms arising from the hydrodehalogenation of the chlorophenols are converted into more oxidized molecules at the anode. These molecules react with unsaturated C4 carboxylic acid to finally yield trichloroacetic acid through a haloform reaction. The non-chlorinated organic acids are ultimately oxidized to carbon dioxide and the trichloroacetic acid into carbon dioxide and volatile organo-chlorinated molecules. Both direct and mediated electrochemical oxidation processes are involved in the electrochemical treatment of chlorophenols.

Air quality model evaluation data for organics. 6. C3-C24 organic acids.

Abstract: The atmospheric concentrations of 47 carboxylic acids in the semivolatile and particle phases are quantified in the Los Angeles area, as part of a larger study of the vapor-phase, semivolatile, and particle-phase organic compounds. Variations in the spatial and temporal distributions of acid concentrations are analyzed to determine whether atmospheric formation or primary emissions are responsible for the observed levels. Relatively low molecular weight aliphatic dicarboxylic acids (e.g., butanedioic acid, hexanedioic acid, and propanedioic acid) and some n-alkanoic acids (e.g., n-octanoic acid and n-nonanoic acid) are found at an offshore sampling location at levels comparable to urban area concentrations indicating that these compounds or their atmospheric precursors may be derived from long-range transport or natural background sources. Some aromatic carboxylic acids (e.g., benzoic acid and 1,2-benzenedicarboxylic acid) have spatial and temporal distributions suggesting that formation from anthropogenic emissions of gaseous precursors dominates their atmospheric concentrations. Additionally, the distributions of aliphatic carboxylic acid concentrations known to be emitted from primary sources (e.g., hexadecanoic acid and octadecanoic acid) are consistent with direct emissions as the dominant source of these compounds.

Pyrazole Derivatives as Partial Agonists for the Nicotinic Acid Receptor

Abstract: Nicotinic acid as a hypolipidemic agent appears unique due to its potential to increase HDL cholesterol levels to a greater extent than other drugs However, it has some side effects, among which severe skin flushing is the most frequent and often limits patients' compliance In a search for novel agonists for the recently identified and cloned G protein-coupled nicotinic acid receptor, we synthesized a series of substituted pyrazole-3-carboxylic acids that proved to have substantial affinity for this receptor The affinities were measured by inhibition of [3H]nicotinic acid binding to rat spleen membranes Potencies and intrinsic activities relative to nicotinic acid were determined by their effects on [35S]GTPγS binding to rat adipocyte and spleen membranes Interestingly, most compounds were partial agonists In particular, 2-diazabicyclo[3,3,04,8]octa-3,8-diene-3-carboxylic acid (4c) and 5-propylpyrazole-3-carboxylic acid (4f) proved active with Ki values of approximately 015 μM and EC50 values of ap

Fermentation of corn stover to carboxylic acids.

Abstract: This article describes countercurrent fermentation to anaerobically convert corn stover and pig manure to mixed carboxylic acids using a mixed culture of mesophilic microorganisms. Corn stover was pretreated with lime to increase digestibility. The Continuum Particle Distribution Model (CPDM) was used to simulate continuous fermentors based on data collected from batch experiments. This model saves considerable time in determining optimum operating conditions. For 80% corn stover/20% pig manure, the highest total carboxylic acid productivity was 1.81 g/(L of liquid.d) at a concentration of 21.4 g total acid/L. The highest total acid selectivity, yield, and conversion were 0.714 g total acid/g g volatile solids (VS) digested, 0.550 g total acid/g VS fed, and 0.770 g VS digested/g VS fed, respectively, at a concentration of 16.0 g total acid/L. CPDM predicted the acid concentration and conversion within 13.4 and 11.6%, respectively.

Electrochemical Oxidation of Aqueous Carboxylic Acid Wastes Using Diamond Thin-Film Electrodes

Abstract: The electrochemical oxidation of three carboxylic acids (formic, oxalic, and maleic) using diamond thin-film electrodes was studied using voltametric and galvanostatic electrolysis techniques. The voltametric study shows an anodic current peak that indicates the existence of a direct oxidation reaction at the electrode surface. Galvanostatic electrolysis studies confirm the existence of mediated oxidation reactions and indicate almost total mineralization of the waste with a virtually direct transformation of carboxylic acids into carbon dioxide (no intermediates were detected) regardless of the current intensity, initial organic acid concentration, temperature, and supporting media. Experimental results obtained in the galvanostatic electrolysis study can be fitted satisfactorily (CV < 10%) using a simple model that considers both kinetic and mass-transfer processes.

Photoluminescence from Sol−Gel Organic/Inorganic Hybrid Gels Obtained through Carboxylic Acid Solvolysis

Abstract: Hybrid organic/inorganic sol−gel materials have been synthesized by carboxylic acid solvolysis of (aminopropyl)triethoxysilane or ureasil precursors The hybrid nature of these gels is expanded with the introduction of silica esters A main feature of the ensuing materials is the formation of hybrid organic/inorganic nanoclusters, which are founded on silica backbone but they are facilitated and assisted also by forces arising from hydrophilic/hydrophobic balance and hydrogen-bonding interactions The silicious domains of these clusters with attached functional groups, for example, amino groups, are luminescence centers Some precursor compounds bearing amino groups without silicious groups but with a tendency to form clusters in solution also emit luminescence Luminescence is the result of electron−hole recombination on delocalized states so that emission wavelength depends on excitation wavelength Luminescence can thus be emitted in almost the entire visible spectrum and it can be tuned by choosing ex

Antibodies to the quinolones and fluoroquinolones for the development of generic and specific immunoassays for detection of these residues in animal products.

Abstract: Several quinolone and fluoroquinolone haptens have been used to raise polyclonal antibodies exhibiting both specific and generic properties for these classes of antimicrobial compounds. The antisera have been assessed in rapid enzyme immunoassays (ELISAs) designed to exploit the specificities obtained. A direct generic ELISA for both the quinolones and fluoroquinolones has been developed that uses the cross-reactivity of an antibody raised against norfloxacin (1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid) linked to ovalbumin via a secondary amine group on the piperazinyl moiety to detect nine different drugs in these classes. Specific ELISAs to ciprofloxacin (1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid), enrofloxacin (1-cyclopropyl-7-(4-ethyl-1-piperazinyl)-6-fluoro-1,4-dihydro-4-oxo-3-quinoline carboxylic acid), flumequin (9-fluoro-6,7-dihydro-5-methyl-1-oxo-1H,5H-benzo(ij)quinolizine-2-carboxylic acid) and nalidixic acid (1-ethyl-1,4-dihydro-7-methyl-4-oxo-1,8-naphthyridine-3-carboxylic acid) have also been developed with a high degree of specificity to the individual compounds. The assays measure drug residues in bovine milk and ovine kidney with an interassay relative standard deviation (s(r)) of 10.5% or less and intra-assay s(r) of 11.2% or less. Sensitivity is less than 4 microg x kg(-1) for both the generic and specific assays for all but one of the compounds tested. (Pipemidic acid (8-ethyl-5,8-dihydro-5-oxo-2-(1-piperazinyl)pyrido(2,3-d)pyrimidine-6-carboxylic acid) is detectable at 6 microg x kg(-1) in kidney.)

Biscarbene−Ruthenium Complexes in Catalysis: Novel Stereoselective Synthesis of (1E,3E)-1,4-Disubstituted-1,3-dienes via Head-to-Head Coupling of Terminal Alkynes and Addition of Carboxylic Acids

Abstract: The reaction of a variety of alkynes RC⋮CH with a variety of carboxylic acids R1CO2H, in the presence of 5% of RuCl(COD)C5Me5, selectively leads to the dienylesters (1E,3E)-RCH1CH2−CH3C(R)(O2CR1). The reaction also applies to amino acid and dicarboxylic acid derivatives. It is shown that the first step of the reaction consists of the head-to-head alkyne coupling and of the formation of the metallacyclic biscarbene−ruthenium complex isolated for R = Ph and catalyzing the formation of dienylester. D-labeled reactions show that the alkyne protons remain at the alkyne terminal carbon atoms and carboxylic acid protonates the C1 carbon atom. QM/MM (ONIOM) calculations, supporting a mixed Fischer−Schrock-type biscarbene complex, show that protonation occurs preferentially at the carbene carbon C1 adjacent to Ru, in the relative cis position with respect to the Ru−Cl bond, to give a mixed C(1)alkyl−C(4)carbene complex in which the C4 carbene is conjugated with the noncoordinated C2C3 double bond. This 16-electron...

Gold catalyzed oxidation of aldehydes in liquid phase

Abstract: Gold on carbon oxidizes aldehydes to carboxylic acids in water solution under mild conditions without loss of activity on recycling, as does not occur for platinum on carbon. Also scarcely soluble aldehydes can be oxidized but the reaction rate is slower. Experiments carried out in an organic solvent such as CCl4 show a speed up of the reaction, in this solvent being recyclable both Au/C and Pt/C. Another explored possibility was represented by carrying out the reaction in the absence of solvent. However, for solid aldehydes like p- and o-OH-PhCHO the water solvent represent the unique alternative.

Pharmaceutical co-crystal compositions

Abstract: A pharmaceutical composition comprising a co-crystal of an API and a co-crystal former; wherein the API has at least one functional group selected from ether, thioether, alcohol, thiol, aldehyde, ketone, thioketone, nitrate ester, phosphate ester, thiophosphate ester, ester, thioester, sulfate ester, carboxylic acid, phosphonic acid, phosphinic acid, sulfonic acid, amide, primary amine, secondary amine, ammonia, tertiary amine, sp2 amine, thiocyanate, cyanamide, oxime, nitrile diazo, organohalide, nitro, s-heterocyclic ring, thiophene, n-heterocyclic ring, pyrrole, o-heterocyclic ring, furan, epoxide, peroxide, hydroxamic acid, imidazole, pyridine and the co-crystal former has at least one functional group selected from amine, amide, pyridine, imidazole, indole, pyrrolidine, carbonyl, carboxyl, hydroxyl, phenol, sulfone, sulfonyl, mercapto and methyl thio, such that the API and co-crystal former are capable of co-crystallizing from a solution phase under crystallization conditions.