Yearly trend of dicarboxylic acids in organic aerosols from south of Sweden and source attribution

NASA Astrophysics Data System (ADS)

Hyder, Murtaza; Genberg, Johan; Sandahl, Margareta; Swietlicki, Erik; Jönsson, Jan Åke

2012-09-01

Seven aliphatic dicarboxylic acids (C3-C9) along with phthalic acid, pinic acid and pinonic acid were determined in 35 aerosol (PM10) samples collected over the year at Vavihill sampling station in south of Sweden. Mixture of dichloromethane and methanol (ratio 1:3) was preferred over water for extraction of samples and extraction was assisted by ultrasonic agitation. Analytes were derivatized using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) containing 1% trimethylsilyl chloride and analyzed using gas chromatography/mass spectrometry. Among studied analytes, azelaic acid was found maximum with an average concentration of 6.0 ± 3.6 ng m-3 and minimum concentration was found for pimelic acid (1.06 ± 0.63 ng m-3). A correlation coefficients analysis was used for defining the possible sources of analytes. Higher dicarboxylic acids (C7-C9) showed a strong correlation with each other (correlation coefficients (r) range, 0.96-0.97). Pinic and pinonic acids showed an increase in concentration during summer. Lower carbon number dicarboxylic acids (C3-C6) and phthalic acid were found strongly correlated, but showed a poor correlation with higher carbon number dicarboxylic acids (C7-C9), suggesting a different source for them. Biomass burning, vehicle exhaust, photo-oxidation of volatile organic compounds (natural and anthropogenic emissions) were possible sources for dicarboxylic acids.

Dicarboxylic acid transport in Bradyrhizobium japonicum: use of Rhizobium meliloti dct gene(s) to enhance nitrogen fixation.

PubMed Central

Birkenhead, K; Manian, S S; O'Gara, F

1988-01-01

A recombinant plasmid encoding Rhizobium meliloti sequences involved in dicarboxylic acid transport (plasmid pRK290:4:46) (E. Bolton, B. Higgisson, A. Harrington, and F. O'Gara, Arch. Microbiol. 144:142-146, 1986) was used to study the relationship between dicarboxylic acid transport and nitrogen fixation in Bradyrhizobium japonicum. The expression of the dct sequences on plasmid pRK290:4:46 in B. japonicum CJ1 resulted in increased growth rates in media containing dicarboxylic acids as the sole source of carbon. In addition, strain CJ1(pRK290:4:46) exhibited enhanced succinate uptake activity when grown on dicarboxylic acids under aerobic conditions. Under free-living nitrogen-fixing conditions, strain CJ1(pRK290:4:46) exhibited higher nitrogenase (acetylene reduction) activity compared with that of the wild-type strain. This increase in nitrogenase activity also correlated with an enhanced dicarboxylic acid uptake rate under these microaerobic conditions. The regulation of dicarboxylic acid transport by factors such as metabolic inhibitors and the presence of additional carbon sources was similar in both the wild-type and the engineered strains. The implications of increasing nitrogenase activity through alterations in the dicarboxylic acid transport system are discussed. PMID:3422072

Characterization of dicarboxylic naphthenic acid fraction compounds utilizing amide derivatization: Proof of concept.

PubMed

Kovalchik, Kevin A; MacLennan, Matthew S; Peru, Kerry M; Ajaero, Chukwuemeka; McMartin, Dena W; Headley, John V; Chen, David D Y

2017-12-30

The characterization of naphthenic acid fraction compounds (NAFCs) in oil sands process affected water (OSPW) is of interest for both toxicology studies and regulatory reasons. Previous studies utilizing authentic standards have identified dicarboxylic naphthenic acids using two-dimensional gas chromatography hyphenated to time-of-flight mass spectrometry (GC × GC/TOFMS). The selective derivatization of hydroxyl groups has also recently aided in the characterization of oxy-NAFCs, and indirectly the characterization of dicarboxylic NAFCs. However, there has been no previous report of derivatization being used to directly aid in the standard-free characterization of NAFCs with multiple carboxylic acid functional groups. Herein we present proof-of-concept for the characterization of dicarboxylic NAFCs utilizing amide derivatization. Carboxylic acid groups in OSPW extract and in a dicarboxylic acidstandard were derivatized to amides using a previously described method. The derivatized extract and derivatized standard were analyzed by direct-injection positive-mode electrospray ionization ((+)ESI) high-resolution mass spectrometry (HRMS), and the underivatized extract was analyzed by (-)ESI MS. Tandem mass spectrometry (MS/MS) was carried out on selected ions of the derivatized standard and derivatized OSPW. Data analysis was carried out using the Python programming language. The distribution of monocarboxylic NAFCs observed in the amide-derivatized OSPW sample by (+)ESI-MS was generally similar to that seen in underivatized OSPW by (-)ESI-MS. The dicarboxylic acid standard shows evidence of being doubly derivatized, although the second derivatization appears to be inefficient. Furthermore, a spectrum of potential diacid NAFCs is presented, identified by both charge state and derivatization mass. Interference due to the presence of multiple derivatization products is noted, but can be eliminated using on-line separation or an isotopically labelled derivatization

Performance of AA5052 alloy anode in alkaline ethylene glycol electrolyte with dicarboxylic acids additives for aluminium-air batteries

NASA Astrophysics Data System (ADS)

Wang, DaPeng; Zhang, DaQuan; Lee, KangYong; Gao, LiXin

2015-11-01

Dicarboxylic acid compounds, i.e. succinic acid (SUA), adipic acid (ADA) and sebacic acid (SEA), are used as electrolyte additives in the alkaline ethylene glycol solution for AA5052 aluminium-air batteries. It shows that the addition of dicarboxylic acids lowers the hydrogen gas evolution rate of commercial AA5052 aluminium alloy anode. AA5052 aluminium alloy has wide potential window for electrochemical activity and better discharge performance in alkaline ethylene glycol solution containing dicarboxylic acid additives. ADA has the best inhibition effect for the self-corrosion of AA5052 anode among the three dicarboxylic acid additives. Fourier transform infrared spectroscopy (FT-IR) reveals that dicarboxylic acids and aluminium ions can form coordination complexes. Quantum chemical calculations shows that ADA has a smaller energy gap (ΔE, the energy difference between the lowest unoccupied orbital and the highest occupied orbital), indicating that ADA has the strongest interaction with aluminium ions.

40 CFR 721.2270 - Aliphatic dicarboxylic acid salt.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic dicarboxylic acid salt. 721.2270 Section 721.2270 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2270 Aliphatic...

Dicarboxylic acids generated by thermal alteration of kerogen and humic acids

NASA Technical Reports Server (NTRS)

Kawamura, Kimitaka; Kaplan, I. R.

1987-01-01

Significant amounts (up to 2 percent of organic geopolymers) of low-molecular-weight (LMW) dicarboxylic acids (C2-C10) have been detected during thermal alteration (270 C, 2 h) of kerogens and humic acids isolated from young or ancient lithified sediments. Their distribution is characterized by the predominance of oxalic acid followed by succinic, fumaric, and methylsuccinic acids. These acids are probably released by the breakdown of macromolecular structures, which have incorporated biogenic organic compounds, including diacids, during early digenesis in sediments. Because of their reactivity, LMW diacids may play geochemically important roles under natural conditions.

Dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, fatty acids, and benzoic acid in urban aerosols collected during the 2006 Campaign of Air Quality Research in Beijing (CAREBeijing-2006)

NASA Astrophysics Data System (ADS)

Ho, K. F.; Lee, S. C.; Ho, Steven Sai Hang; Kawamura, Kimitaka; Tachibana, Eri; Cheng, Y.; Zhu, Tong

2010-10-01

Ground-based studies of PM2.5 were conducted for determination of 30 water-soluble organic species, including dicarboxylic acids, ketocarboxylic acids and dicarbonyls, nine fatty acids, and benzoic acid, during the Campaign of Air Quality Research in Beijing 2006 (CAREBeijing-2006; 21 August to 4 September 2006) at urban (Peking University, PKU) and suburban (Yufa) sites of Beijing. Molecular distributions of dicarboxylic acids demonstrated that oxalic acid (C2) was the most abundant species, followed by phthalic acid (Ph) and succinic acid (C4) at both sites. The sum of three dicarboxylic acids accounted for 71% and 74% of total quantified water-soluble organics (327-1552 and 329-1124 ng m-3) in PKU and Yufa, respectively. Positive correlation was found between total quantified water-soluble species and water-soluble organic compounds (WSOC). On a carbon basis, total quantified dicarboxylic acids and ketocarboxylic acids and dicarbonyls account for up to 14.2% and 30.4% of the WSOC in PKU and Yufa, respectively, suggesting that they are the major WSOC fractions in Beijing. The distributions of fatty acids are characterized by a strong even carbon number predominance with maximum at hexadecanoic acid (C16:0). The ratio of octadecanoic acid (C18:0) to hexadecanoic acid (C16:0) (0.39-0.85, with an average of 0.36) suggests that in addition to vehicular emissions, an input from cooking emissions is important, as is biogenic emission. Benzoic acid that has been proposed as a primary pollutant from vehicular exhaust and a secondary product from photochemical reactions was found to be abundant: 72.2 ± 58.1 ng m-3 in PKU and 78.0 ± 47.3 ng m-3 in Yufa. According to the 72 hour back trajectory analysis, when the air mass passed over the southern or southeastern part of Beijing (24-25 August and 1-2 September), the highest concentrations of organic compounds were observed. On the contrary, when the clean air masses came straight from the north during 3-4 September, the

Carbonaceous aerosol characterization in the Amazon basin, Brazil: novel dicarboxylic acids and related compounds

NASA Astrophysics Data System (ADS)

Kubátová, Alena; Vermeylen, Reinhilde; Claeys, Magda; Cafmeyer, Jan; Maenhaut, Willy; Roberts, Greg; Artaxo, Paulo

High-resolution capillary gas chromatography (GC) and GC/mass spectrometry (MS) were employed for the quantitative determination of dichloromethane-extractable organic compounds in total and size-fractionated aerosol samples which were collected in the Amazon basin, Brazil, during the wet season, as part of the LBA-CLAIRE-98 experiment. Special emphasis was placed on the characterization and identification of several novel unknown dicarboxylic acids and related oxidative degradation products. This class of acidic products was enriched in the fine size fraction, suggesting that they were secondary organic aerosol products formed by gas-to-particle conversion. Some of the unknowns contributed more to the class of dicarboxylic acids than the major known compound, nonadioic acid (azelaic acid). The same unknowns were also observed in urban aerosol samples collected on hot summer days in Gent, Belgium. For the characterization and structure elucidation of the unknowns, various types of derivatizations and fractionation by solid-phase extraction were employed in combination with GC/MS. Four unknowns were identified. The most abundant were two derivatives of glutaric acid, 3-isopropyl pentanedioic acid and 3-acetyl pentanedioic acid. The other two identified unknowns were another oxo homologue, 3-acetyl hexanedioic acid, and, interestingly, 3-carboxy heptanedioic acid. To our knowledge, the occurrence of these four compounds in atmospheric aerosols has not yet been reported. The biogenic precursors of the novel identified compounds could not be pinpointed, but most likely include monoterpenes and fatty acids.

Hydrogen bonded binary molecular adducts derived from exobidentate N-donor ligand with dicarboxylic acids: Acid⋯imidazole hydrogen-bonding interactions in neutral and ionic heterosynthons

NASA Astrophysics Data System (ADS)

Kathalikkattil, Amal Cherian; Damodaran, Subin; Bisht, Kamal Kumar; Suresh, Eringathodi

2011-01-01

Four new binary molecular compounds between a flexible exobidentate N-heterocycle and a series of dicarboxylic acids have been synthesized. The N-donor 1,4-bis(imidazol-1-ylmethyl)benzene (bix) was reacted with flexible and rigid dicarboxylic acids viz., cyclohexane-1,4-dicarboxylic acid (H 2chdc), naphthalene-1,4-dicarboxylic acid (H 2npdc) and 1H-pyrazole-3,5-dicarboxylic acid (H 2pzdc), generating four binary molecular complexes. X-ray crystallographic investigation of the molecular adducts revealed the primary intermolecular interactions carboxylic acid⋯amine (via O-H⋯N) as well as carboxylate⋯protonated amine (via N-H +⋯O -) within the binary compounds, generating layered and two-dimensional sheet type H-bonded networks involving secondary weak interactions (C-H⋯O) including the solvent of crystallization. Depending on the differences in p Ka values of the selected base/acid (Δp Ka), diverse H-bonded supramolecular assemblies could be premeditated. This study demonstrates the H-bonding interactions between imidazole/imidazolium cation and carboxylic acid/carboxylate anion in providing sufficient driving force for the directed assembly of binary molecular complexes. In the two-component solid form of hetero synthons involving bix and dicarboxylic acid, only H 2chdc exist as cocrystal with bix, while all the other three compounds crystallized exclusively as salt, in agreement with the Δp Ka values predicted for the formation of salts/cocrystals from the base and acid used in the synthesis of supramolecular solids.

Quantifying hydrogen-deuterium exchange of meteoritic dicarboxylic acids during aqueous extraction

NASA Astrophysics Data System (ADS)

Fuller, M.; Huang, Y.

2003-03-01

Hydrogen isotope ratios of organic compounds in carbonaceous chondrites provide critical information about their origins and evolutionary history. However, because many of these compounds are obtained by aqueous extraction, the degree of hydrogen-deuterium (H/D) exchange that occurs during the process needs to be quantitatively evaluated. This study uses compound- specific hydrogen isotopic analysis to quantify the H/D exchange during aqueous extraction. Three common meteoritic dicarboxylic acids (succinic, glutaric, and 2-methyl glutaric acids) were refluxed under conditions simulating the extraction process. Changes in D values of the dicarboxylic acids were measured following the reflux experiments. A pseudo-first order rate law was used to model the H/D exchange rates which were then used to calculate the isotope exchange resulting from aqueous extraction. The degree of H/D exchange varies as a result of differences in molecular structure, the alkalinity of the extraction solution and presence/absence of meteorite powder. However, our model indicates that succinic, glutaric, and 2-methyl glutaric acids with a D of 1800 would experience isotope changes of 38, 10, and 6, respectively during the extraction process. Therefore, the overall change in D values of the dicarboxylic acids during the aqueous extraction process is negligible. We also demonstrate that H/D exchange occurs on the chiral -carbon in 2-methyl glutaric acid. The results suggest that the racemic mixture of 2-methyl glutaric acid in the Tagish Lake meteorite could result from post-synthesis aqueous alteration. The approach employed in this study can also be used to quantify H/D exchange for other important meteoritic compounds such as amino acids.

Fine and coarse modes of dicarboxylic acids in the Arctic aerosols collected during the Polar Sunrise Experiment 1997

NASA Astrophysics Data System (ADS)

Narukawa, M.; Kawamura, K.; Anlauf, K. G.; Barrie, L. A.

2003-09-01

Fine (<1 μm) and coarse (>1 μm) aerosol particles were collected at Alert, Canada (82°27'N, 62°30'W), during the Arctic spring as part of the Polar Sunrise Experiment 1997 and were analyzed for low molecular weight dicarboxylic acids (C2-C11) using gas chromatography with flame ionization detector (GC-FID) and GC/mass spectrometry (GC/MS). More than 80% of total diacids were detected in the fine fraction, suggesting the production by gas-to-particle conversion in the Arctic. In both fractions, oxalic acid was the dominant diacid species followed by succinic and malonic acids. Shorter chain diacids (C2-C5) showed the concentration maximum on 5-7 April; however, longer chain diacids (dicarboxylic acids in both coarse and fine aerosols during ozone depletion events indicate that heterogeneous reactions are occurring on coarse particle and possibly on fine particles as well. Dicarboxylic acids may be produced by the oxidation of precursor compounds such as glyoxal and glyoxylic and other ω-oxocarboxylic acids that contain aldehyde (hydrated form) group, being involved with ozone and halogen chemistry in the Arctic marine boundary layer.

Adipic acid production catalyzed by a combination of a solid acid and an iodide salt from biomass-derived tetrahydrofuran-2,5-dicarboxylic acid

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

Gilkey, Matthew J.; Balakumar, Rachana; Vlachos, Dionisios G.

We recently reported biomass-derived tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) as a potential renewable feedstock for adipic acid (AA) production by combining HI and molecular H 2 in organic acid solvents.

Adipic acid production catalyzed by a combination of a solid acid and an iodide salt from biomass-derived tetrahydrofuran-2,5-dicarboxylic acid

DOE PAGES

Gilkey, Matthew J.; Balakumar, Rachana; Vlachos, Dionisios G.; ...

2018-01-01

We recently reported biomass-derived tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) as a potential renewable feedstock for adipic acid (AA) production by combining HI and molecular H 2 in organic acid solvents.

Crystal growth and physical characterization of picolinic acid cocrystallized with dicarboxylic acids

NASA Astrophysics Data System (ADS)

Somphon, Weenawan; Haller, Kenneth J.

2013-01-01

Pharmaceutical cocrystals are multicomponent materials containing an active pharmaceutical ingredient with another component in well-defined stoichiometry within the same unit cell. Such cocrystals are important in drug design, particularly for improving physicochemical properties such as solubility, bioavailability, or chemical stability. Picolinic acid is an endogenous metabolite of tryptophan and is widely used for neuroprotective, immunological, and anti-proliferative effects within the body. In this paper we present cocrystallization experiments of a series of dicarboxylic acids, oxalic acid, succinic acid, DL-tartaric acid, pimelic acid, and phthalic acid, with picolinic acid. Characterization by FT-IR and Raman spectroscopy, DSC and TG/DTG analysis, and X-ray powder diffraction show that new compounds are formed, including a 1:1 picolinium tartrate monohydrate, a 2:1 monohydrate adduct of picolinic acid and oxalic acid, and a 2:1 picolinic acid-succinic acid monohydrate cocrystal.

Thioesterases for ethylmalonyl-CoA pathway derived dicarboxylic acid production in Methylobacterium extorquens AM1.

PubMed

Sonntag, Frank; Buchhaupt, Markus; Schrader, Jens

2014-05-01

The ethylmalonyl-coenzyme A pathway (EMCP) is a recently discovered pathway present in diverse α-proteobacteria such as the well studied methylotroph Methylobacterium extorquens AM1. Its glyoxylate regeneration function is obligatory during growth on C1 carbon sources like methanol. The EMCP contains special CoA esters, of which dicarboxylic acid derivatives are of high interest as building blocks for chemical industry. The possible production of dicarboxylic acids out of the alternative, non-food competing C-source methanol could lead to sustainable and economic processes. In this work we present a testing of functional thioesterases being active towards the EMCP CoA esters including in vitro enzymatic assays and in vivo acid production. Five thioesterases including TesB from Escherichia coli and M. extorquens, YciA from E. coli, Bch from Bacillus subtilis and Acot4 from Mus musculus showed activity towards EMCP CoA esters in vitro at which YciA was most active. Expressing yciA in M. extorquens AM1 led to release of 70 mg/l mesaconic and 60 mg/l methylsuccinic acid into culture supernatant during exponential growth phase. Our data demonstrates the biotechnological applicability of the thioesterase YciA and the possibility of EMCP dicarboxylic acid production from methanol using M. extorquens AM1.

Seasonal and longitudinal distributions of atmospheric water-soluble dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls over the North Pacific

NASA Astrophysics Data System (ADS)

Bikkina, Srinivas; Kawamura, Kimitaka; Imanishi, Katsuya; Boreddy, S. K. R.; Nojiri, Yukihiro

2015-05-01

In order to assess the seasonal variability of atmospheric abundances of dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls over the North Pacific and Sea of Japan, aerosol samples were collected along the longitudinal transacts during six cruises between Canada and Japan. The back trajectory analyses indicate that aerosol samples collected in winter and spring are influenced by the East Asian outflow, whereas summer and fall samples are associated with the pristine maritime air masses. Molecular distributions of water-soluble organics in winter and spring samples show the predominance of oxalic acid (C2) followed by succinic (C4) and malonic acids (C3). In contrast, summer and fall marine aerosols are characterized by the predominance of C3 over C4. Concentrations of dicarboxylic acids were higher over the Sea of Japan than the North Pacific. With a lack of continental outflow, higher concentrations during early summer are ascribed to atmospheric oxidation of organic precursors associated with high biological activity in the North Pacific. This interpretation is further supported by the high abundances of azelaic acid, which is a photochemical oxidation product of biogenic unsaturated fatty acids, over the Bering Sea in early summer when surface waters are characterized by high biological productivity. We found higher ratios of oxalic acid to pyruvic and glyoxylic acids (C2/Pyr and C2/ωC2) and glyoxal and methylglyoxal (C2/Gly and C2/MeGly) in summer and fall than in winter and spring, suggesting a production of C2 from the aqueous-phase oxidation of oceanic isoprene. In this study, dicarboxylic acids account for 0.7-38% of water-soluble organic carbon.

Volatile aromatic hydrocarbons and dicarboxylic acid concentrations in air at an urban site in the Southwestern US

NASA Astrophysics Data System (ADS)

Tran, Ngoc K.; Steinberg, Spencer M.; Johnson, Brian J.

Concentrations of benzene, toluene, ethylbenzene, o-xylene, and m- and p-xylene were measured at an urban sampling site in Las Vegas, NV by sorbent sampling followed by thermal desorption and determination by GC-PID. Simultaneously, measurements of oxalic, malonic, succinic, and adipic acids were made at the same site by collection on quartz filters, extraction, esterification, and determination by GC-FID. For the period from April 7, 1997 to June 11, 1997, 201 sets of hydrocarbon measurements and 99 sets of acid measurements were made. Additional measurements of dicarboxylic acids were made on samples that represented potential direct sources, e.g. green plants and road dust. Correlations between the hydrocarbon and CO concentrations (measured by the Clark County Health District at a nearby site) were highly significant and a strong negative correlation of hydrocarbon concentration with ozone concentration (also from the county site) was observed under quiescent atmospheric conditions. In general, dicarboxylic acid concentrations were well correlated with one another (with the exception of adipic acid) but not well correlated with hydrocarbon, CO, and ozone concentrations. Multiple sources and complex formation processes are indicated for the dicarboxylic acids.

Hygroscopic Behavior of Multicomponent Aerosols Involving NaCl and Dicarboxylic Acids.

PubMed

Peng, Chao; Jing, Bo; Guo, Yu-Cong; Zhang, Yun-Hong; Ge, Mao-Fa

2016-02-25

Atmospheric aerosols are usually complex mixtures of inorganic and organic compounds. The hygroscopicity of mixed particles is closely related to their chemical composition and interactions between components, which is still poorly understood. In this study, the hygroscopic properties of submicron particles composed of NaCl and dicarboxylic acids including oxalic acid (OA), malonic acid (MA), and succinic acid (SA) with various mass ratios are investigated with a hygroscopicity tandem differential mobility analyzer (HTDMA) system. Both the Zdanovskii-Stokes-Robinson (ZSR) method and extended aerosol inorganics model (E-AIM) are applied to predict the water uptake behaviors of sodium chloride/dicarboxylic acid mixtures. For NaCl/OA mixed particles, the measured growth factors were significantly lower than predictions from the model methods, indicating a change in particle composition caused by chloride depletion. The hygroscopic growth of NaCl/MA particles was well described by E-AIM, and that of NaCl/SA particles was dependent upon mixing ratio. Compared with model predictions, it was determined that water uptake of the NaCl/OA mixture could be enhanced and could be closer to the predictions by addition of levoglucosan or malonic acid, which retained water even at low relative humidity (RH), leading to inhibition of HCl evaporation during dehydration. These results demonstrate that the coexisting hygroscopic species have a strong influence on the phase state of particles, thus affecting chemical interactions between inorganic and organic compounds as well as the overall hygroscopicity of mixed particles.

Microbial Transformation of Dicarboxylic Acids by Airborne Bacteria

NASA Astrophysics Data System (ADS)

Cote, V.; Ariya, P.

2004-05-01

Organic aerosols are assumed to be key players in driving climatic changes and can cause health problems for human. Dicarboxylic acids (DCA) include a large fraction of identified important class of organic aerosols. In addition to direct sources, DCA are partly formed as the result of ozonolysis of terpenes and cyclic alkenes. Previous works in our laboratory show that airborne fungi collected from urban and suburban air play an important role in the transformation of severals organic aerosols such as DCA. Our present study focuses on understanding the potential chemical transformation induced by airborne bacteria and on identification of the transformation products. Airborne bacteria have been collected using a biosampler and cultivated on a solid media. Each bacterial colony is being tested by HPLC for their ability to transform DCA in liquid cultures. Also, GC-MS, SPME and NMR are being used to identify the metabolites generated from the transformation. We will present our preliminary results and we will discuss the application of bacterial activities on the chemical transformation of organics in atmosphere.

Salt and cocrystals of sildenafil with dicarboxylic acids: solubility and pharmacokinetic advantage of the glutarate salt.

PubMed

Sanphui, Palash; Tothadi, Srinu; Ganguly, Somnath; Desiraju, Gautam R

2013-12-02

Sildenafil is a drug used to treat erectile dysfunction and pulmonary arterial hypertension. Because of poor aqueous solubility of the drug, the citrate salt, with improved solubility and pharmacokinetics, has been marketed. However, the citrate salt requires an hour to reach its peak plasma concentration. Thus, to improve solubility and bioavailability characteristics, cocrystals and salts of the drug have been prepared by treating aliphatic dicarboxylic acids with sildenafil; the N-methylated piperazine of the drug molecule interacts with the carboxyl group of the acid to form a heterosynthon. Salts are formed with oxalic and fumaric acid; salt monoanions are formed with succinic and glutaric acid. Sildenafil forms cocrystals with longer chain dicarboxylic acids such as adipic, pimelic, suberic, and sebacic acids. Auxiliary stabilization via C-H···O interactions is also present in these cocrystals and salts. Solubility experiments of sildenafil cocrystal/salts were carried out in 0.1N HCl aqueous medium and compared with the solubility of the citrate salt. The glutarate salt and pimelic acid cocrystal dissolve faster than the citrate salt in a two hour dissolution experiment. The glutarate salt exhibits improved solubility (3.2-fold) compared to the citrate salt in water. Solubilities of the binary salts follow an inverse correlation with their melting points, while the solubilities of the cocrystals follow solubilities of the coformer. Pharmacokinetic studies on rats showed that the glutarate salt exhibits doubled plasma AUC values in a single dose within an hour compared to the citrate salt. The high solubility of glutaric acid, in part originating from the strained conformation of the molecule and its high permeability, may be the reason for higher plasma levels of the drug.

Synthesis, Properties and Applications of Biodegradable Polymers Derived from Diols and Dicarboxylic Acids: From Polyesters to Poly(ester amide)s

PubMed Central

Díaz, Angélica; Katsarava, Ramaz; Puiggalí, Jordi

2014-01-01

Poly(alkylene dicarboxylate)s constitute a family of biodegradable polymers with increasing interest for both commodity and speciality applications. Most of these polymers can be prepared from biobased diols and dicarboxylic acids such as 1,4-butanediol, succinic acid and carbohydrates. This review provides a current status report concerning synthesis, biodegradation and applications of a series of polymers that cover a wide range of properties, namely, materials from elastomeric to rigid characteristics that are suitable for applications such as hydrogels, soft tissue engineering, drug delivery systems and liquid crystals. Finally, the incorporation of aromatic units and α-amino acids is considered since stiffness of molecular chains and intermolecular interactions can be drastically changed. In fact, poly(ester amide)s derived from naturally occurring amino acids offer great possibilities as biodegradable materials for biomedical applications which are also extensively discussed. PMID:24776758

Molecular and isotopic analyses of the hydroxy acids, dicarboxylic acids, and hydroxydicarboxylic acids of the Murchison meteorite

NASA Astrophysics Data System (ADS)

Cronin, J. R.; Pizzarello, S.; Epstein, S.; Krishnamurthy, R. V.

1993-10-01

The hydroxymonocarboxylic acids, dicarboxylic acids, and hydroxydicarboxylic acids of the Murchison meteorite were analyzed as their tert-butyldimethylsilyl derivatives using combined gas chromatography-mass spectrometry. The hydroxydicarboxylic acids have not been found previously in meteorites. Each class of compounds is numerous with carbon chains up to C8 or C9 and many, if not all, chain and substitution position isomers represented at each carbon number. The alpha-hydroxycarboxylic acids and alpha-hydroxydicarboxylic acids correspond structurally to many of the known meteoritic alpha-aminocarboxylic acids and alpha-aminodicarboxylic acids, a fact that supports the proposal that a Strecker synthesis was involved in the formation of both classes of compounds. Isotopic analyses show these acids to be D-rich relative to terrestrial organic compounds, as expected; however, the hydroxy acids appear to be isotopically lighter than the amino acids with respect to both carbon and hydrogen.

Determination of low-molecular-weight dicarboxylic acids in atmospheric aerosols by injection-port derivatization and gas chromatography-mass spectrometry.

PubMed

Hsu, Ching-Lin; Ding, Wang-Hsien

2009-12-15

A rapid and environmental-friendly injection-port derivatization with gas chromatography-mass spectrometry (GC-MS) method was developed to determine selected low-molecular weight (LMW) dicarboxylic acids (from C2 to C10) in atmospheric aerosol samples. The parameters related to the derivatization process (i.e., type of ion-pair reagent, injection-port temperature and concentration of ion-pair reagent) were optimized. Tetrabutylammonium hydroxide (TBA-OH) 20 mM in methanol gave excellent yield for di-butyl ester dicarboxylate derivatives at injection-port temperature at 300 degrees C. Solid-phase extraction (SPE) method instead of rotary evaporation was used to concentrate analytes from filter extracts. The recovery from filter extracts ranged from 78 to 95% with relative standard deviation (RSD) less than 12%. Limits of quantitation (LOQs) ranged from 25 to 250 pg/m(3). The concentrations of di-carboxylated C2-C5 and total C6-C10 in particles of atmospheric aerosols ranged from 91.9 to 240, 11.3 to 56.7, 9.2 to 49.2, 8.7 to 35.3 and n.d. to 37.8 ng/m(3), respectively. Oxalic acid (C2) was the dominant LMW-dicarboxylic acids detected in aerosol samples. The quantitative results were comparable to the results obtained by the off-line derivatization.

Source and reaction pathways of dicarboxylic acids, ketoacids and dicarbonyls in arctic aerosols: One year of observations

NASA Astrophysics Data System (ADS)

Kawamura, Kimitaka; Kasukabe, Hideki; Barrie, Leonard A.

Normal saturated (C 2C 11) and unsaturated (C 4C 5, C 8) dicarboxylic acids were measured in arctic aerosol samples collected weekly at Alert, Canada in 1987-1988. In all seasons, oxalic (C 2) acid was usually the dominant diacid species (1.8-70 ng m -3, av. 14 ± 12 ng m -3) followed by malonic (C 3; 0.05-19 ng m -3, av. 2.5 ± 3.3 ng m -3) and succinic (C 4; 0.51-18 ng m -3, av. 3.8 ± 3.5 ng m -3) acids. The total concentrations of dicarboxylic acids showed a seasonal variation (4.3-97 ng m -3, av. 25 ± 20 ng m -3),with two maxima in September to October and in March to April. The autumn peak is characterized by high concentrations of oxalic acid and azelaic (C 9) acids, which were probably caused by enhanced contributions from anthropogenic and biogenic sources, respectively, followed by photochemical reactions. This is consistent with higher concentrations of n-alkanes from terrestrial plant waxes and of soil-derived aluminum in the autumn aerosol samples. On the other hand, during "Arctic Sunrise" in March to April, oxalic, malonic and succinic acids as well as some other (C 5C 6) diacids were 5 to 20 times more abundant than in the preceding dark winter months, suggesting that diacids are produced in situ by secondary photochemical oxidation of organic pollutants carried to the Arctic. ω-Oxocarboxylic acids (C 2C 5, C 9), pyruvic acid and α-dicarbonyls (methylglyoxal and glyoxal) were also detected in the arctic aerosols. Their concentration also showed spring maxima; however, they were observed a few weeks earlier than the spring peak of diacids. The ω-oxoacids are likely intermediates to the production of α,ω-dicarboxylic acids at the polar sunrise.

Sutter's Mill dicarboxylic acids as possible tracers of parent-body alteration processes

NASA Astrophysics Data System (ADS)

Pizzarello, Sandra; Garvie, Laurence A. J.

2014-11-01

Dicarboxylic acids were searched for in three Sutter's Mill (SM) fragments (SM2 collected prerain, SM12, and SM41) and found to occur almost exclusively as linear species of 3- to 14-carbon long. Between these, concentrations were low, with measured quantities typically less than 10 nmole g-1 of meteorite and a maximum of 6.8 nmole g-1 of meteorite for suberic acid in SM12. The SM acids' molecular distribution is consistent with a nonbiological origin and differs from those of CMs, such as Murchison or Murray, and of some stones of the C2-ungrouped Tagish Lake meteorite, where they are abundant and varied. Powder X-ray diffraction of SM12 and SM41 show them to be dominated by clays/amorphous material, with lesser amounts of Fe-sulfides, magnetite, and calcite. Thermal gravimetric (TG) analysis shows mass losses up to 1000 °C of 11.4% (SM12) and 9.4% (SM41). These losses are low compared with other clay-rich carbonaceous chondrites, such as Murchison (14.5%) and Orgueil (21.1%). The TG data are indicative of partially dehydrated clays, in accordance with published work on SM2, for which mineralogical studies suggest asteroidal heating to around 500 °C. In view of these compositional traits and mineralogical features, it is suggested that the dicarboxylic acids observed in the SM fragments we analyzed likely represent a combination of molecular species original to the meteorite as well as secondary products formed during parent-body alteration processes, such as asteroidal heating.

Seasonal variations, molecular distributions, and stable carbon isotopic compositions of dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls in PM2.5 from Beijing, China

NASA Astrophysics Data System (ADS)

Zhao, W.; Kawamura, K.; Fu, P.

2016-12-01

Low molecular weight (LMW) dicarboxylic acids and related polar compounds comprise a significant fraction of atmospheric aerosols. Seasonal variations, molecular distributions, and stable carbon isotopic compositions of dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls, as well as organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC) and inorganic ionic species, were determined to better understand the sources and photochemical aging processes of carbonaceous aerosols in urban Beijing from Sept. 2013 to Jul. 2014 (n=65). Concentrations of total diacids ranged from 110-2580 ng m-3, while ketoacids (9.5-353 ng m-3) and dicarbonyls (1.5-85.9 ng m-3) were less abundant. Higher ambient concentrations of phthalic (Ph) (37.9±27.3 ng m-3), terephthalic (tPh) (48.7±51.1 ng m-3), and glyoxylic (ωC2) (44.3±69 ng m-3) acids were found in winter than other seasons. The temporal variations of malonic acid to succinic acid (C3/C4) ratios were relatively low throughout the whole year, most of which were less than or equal to unity, even in summer, implying more contributions of dicarboxylic acids from primary emissions, rather than aging processes during long-range atmospheric transport. The δ13C mean values of malonic acid (-18.7% to -17.3%) and succinic acid (-28.6% to -17.1%) were larger than those of oxalic acid (-22.9% to -20.1%) in both seasons, except for δ13C of succinic acid in summer. Lower δ13C values of these compounds in Beijing than those in marine areas may be mainly associated with primary emissions, such as biomass burning, vehicular exhaust, incomplete fossil fuel combustion and plastic wastes.

Thermoset coatings from epoxidized sucrose soyate and blocked, bio-based dicarboxylic acids.

PubMed

Kovash, Curtiss S; Pavlacky, Erin; Selvakumar, Sermadurai; Sibi, Mukund P; Webster, Dean C

2014-08-01

A new 100% bio-based thermosetting coating system was developed from epoxidized sucrose soyate crosslinked with blocked bio-based dicarboxylic acids. A solvent-free, green method was used to block the carboxylic acid groups and render the acids miscible with the epoxy resin. The thermal reversibility of this blocking allowed for the formulation of epoxy-acid thermoset coatings that are 100% bio-based. This was possible due to the volatility of the vinyl ethers under curing conditions. These systems have good adhesion to metal substrates and perform well under chemical and physical stress. Additionally, the hardness of the coating system is dependent on the chain length of the diacid used, making it tunable. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular distributions of water soluble dicarboxylic acids in marine aerosols over the Pacific Ocean including tropics

NASA Astrophysics Data System (ADS)

Kawamura, Kimitaka; Sakaguchi, Futoshi

1999-02-01

Remote marine aerosols collected over the western North to equatorial Pacific (34°N-14°S, 140°E-150°W) were studied for low molecular weight dicarboxylic acids using a capillary gas chromatography (GC) and GC/mass spectrometer, and for total carbon and nitrogen contents. Homologous series of dicarboxylic acids (C2-C10) including keto- and hydroxy-dicarboxylic acids were detected in the samples with a concentration range of 10-250 ng m-3 (average 63 ng m-3 and median 44 ng m-3). Their molecular distributions showed a predominance of oxalic acid (C2), followed by malonic acid (C3). The smallest diacid (C2, 6.5-161 ng m-3 with average 40 ng m-3 and median 17 ng m-3) composed 45-75% (average 65%) of the total diacids. The diacids showed higher concentrations in the western Pacific rim near Japanese islands and showed lower concentrations in the central and tropical Pacific. However, relative abundances of the diacid-carbon in the total aerosol carbon (1.1-15.8%) were found to be higher in the equatorial central Pacific. These diacids are probably in situ produced in the Pacific atmosphere by photochemical oxidation of gaseous and particulate precursors. Results of principal component analysis of individual diacid, coupled with an information on photochemical reactions, further support that C2 and C3 diacids are likely produced by the oxidation of C4 and longer-chain diacids, whereas longer-chain (C5-C10) diacids are produced through the oxidation of semivolatile fatty acids which are also oxidation products of unsaturated fatty acids. Concentrations of total C (0.069-5.27 μg m-3 with average 0.39 μg m-3 and median 0.15 μg m-3) and total N (0.026-1.44 μg m-3 with average 0.12 μg m-3 and median 0.077 μg m-3) were generally higher over the western Pacific.

Integrated production of lignin containing cellulose nanocrystals (LCNC) and nanofibrils (LCNF) using an easily recyclable di-carboxylic acid

Treesearch

Huiyang Bian; Liheng Chen; Hongqi Dai; J.Y. Zhu

2017-01-01

Here we demonstrate di-carboxylic acid hydrolysis for the integrated production of lignin containing cellulose nanocrystals (LCNC) and nanofibrils (LCNF) using two unbleached hardwood chemical pulps of lignin contents of 3.9 and 17.2%. Acid hydrolysis experiments used maleic acid solution of 60 wt% concentration at 120°C for 120 min under ambient pressure. Yields of...

Metastable equilibria among dicarboxylic acids and the oxidation state during aqueous alteration on the CM2 chondrite parent body

NASA Astrophysics Data System (ADS)

McAlister, Jason A.; Kettler, Richard M.

2008-01-01

Linear saturated dicarboxylic acids are present in carbonaceous chondrite samples at concentrations that suggest aqueous alteration under conditions of metastable equilibrium. In this study, previously published values of dicarboxylic acid concentrations measured in Murchison, Yamato-791198, and Tagish Lake carbonaceous chondrites are converted to aqueous activities during aqueous alteration assuming water:rock ratios that range from 1:10 to 10:1. Logarithmic plots of the aqueous activities of any two dicarboxylic acids are proximal to lines whose slope is fixed by the stoichiometry of reactions describing the oxidation-reduction equilibrium between the two species. The precise position of any line is controlled by the equilibrium constant of the reaction relating the species and the hydrogen fugacity for the reaction of interest. Reactions among succinic (C4), glutaric (C5), and adipic (C6) acids obtained from CM2 chondrites show evidence of metastable equilibrium and yield logf values that agree to within 0.3 log units at 298.15 K and 0.6 log units at 473.15 K. At a water:rock ratio of 1:1, metastable equilibrium among succinic, glutaric, and adipic acids results in calculated logf values during aqueous alteration that range from -6.2 at 298.15 K to -3.3 at 373.15 K. These values are consistent with those obtained in previous work on carbonaceous chondrites and with metastable equilibrium at temperatures ranging from 300 to 355 K in contact with cronstedtite + magnetite.

Coverage-Dependent Anchoring of 4,4'-Biphenyl Dicarboxylic Acid to CoO(111) Thin Films.

PubMed

Mohr, Susanne; Schmitt, Tobias; Döpper, Tibor; Xiang, Feifei; Schwarz, Matthias; Görling, Andreas; Schneider, M Alexander; Libuda, Jörg

2017-05-02

We investigated the adsorption behavior of 4,4'-biphenhyl dicarboxylic acid (BDA) on well-ordered CoO(111) films grown on Ir(100) as a function of coverage and temperature using time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) in combination with density functional theory (DFT) and scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV) conditions. To compare the binding behavior of BDA as a function of the oxide film thickness, three different CoO(111) film thicknesses were explored: films of about 20 bilayers (BLs) (approximately 5 nm), 2 BLs, and 1 BL. The two carboxylic acid groups of BDA offer two potential anchoring points to the oxide surface. At 150 K, intact BDA adsorbs on 20 BL thick oxide films in planar geometry with the phenyl rings aligned parallel to the surface. With decreasing oxide film thickness, we observe an increasing tendency for deprotonation and the formation of flat-lying BDA molecules anchored as dicarboxylates. After saturation of the first monolayer, intact BDA multilayers grow with molecules aligned parallel to the surface. The BDA multilayer desorbs at around 360 K. Completely different growth behavior is observed if BDA is deposited above the multilayer desorption temperature. Initially, doubly deprotonated dicarboxylates are formed by adopting a flat-lying orientation. With increasing exposure, however, the adsorbate layer transforms into upright standing monocarboxylates. A sharp OH stretching band (3584 cm -1 ) and a blue-shifted CO stretching band (1759 cm -1 ) indicate weakly interacting apical carboxylic acid groups at the vacuum interface. The anchored monocarboxylate phase slowly desorbs in a temperature range of up to 470 K. At higher temperature, a flat-lying doubly deprotonated BDA is formed, which desorbs and decomposes in a temperature range of up to 600 K.

Synthesis, structure and properties of zinc(II) coordination polymers with 9H-carbazole-2,7-dicarboxylic acid

NASA Astrophysics Data System (ADS)

Yi, Xiu-Chun; Xi, Fu-Gui; Wang, Kun; Su, Zhao; Gao, En-Qing

2013-10-01

From a new dicarboxylate ligand, 9H-carbazole-2,7-dicarboxylic acid (2,7-H2CDC), three Zn(II) metal-organic frameworks were synthesized in the absence or presence of ditopic N-donor ligands. They are formulated as [Zn5(μ3-OH)2(2,7-CDC)4(DEF)2] (1) (DEF=N,N-diethylformamide), [Zn2(2,7-CDC)2(DABCO)(H2O)]·5DMF·H2O (2) (DABCO=1-diaza-bicyclo[2.2.2]octane, DMF=N,N-dimethylformamide), and [Zn2(2,7-CDC)2(bpea)]·3DMA·2 H2O (3) (bpea=1,2-bis(4-pyridyl)ethylane, DMA=N,N-dimethylacetamide). Compounds 1 and 3 display the 3D pcu frameworks. In 1 the unusual pentanuclear [Zn5(μ3-OH)2(COO)8] secondary building units (SBUs) are linked by dicarboxylate ligands. Differently, in 3 the well-known paddle-wheel [Zn2(COO)4] SBUs are linked by dicarboxylate and dipyridyl ligands. Compound 2 shows the rare self-catenated 3D alb-3,6-C2/c net topology based on the dinuclear paddle-wheel SBU and a mononuclear unit. The stability and fluorescent properties of the compounds have been studied.

The development of benzo- and naphtho-fused quinoline-2,4-dicarboxylic acids as vesicular glutamate transporter (VGLUT) inhibitors reveals a possible role for neuroactive steroids

PubMed Central

Carrigan, Christina N.; Patel, Sarjubhai A.; Cox, Holly D.; Bolstad, Erin S.; Gerdes, John M.; Smith, Wesley E.; Bridges, Richard J.

2014-01-01

Substituted quinoline-2,4-dicarboxylates (QDCs) are conformationally-restricted mimics of glutamate that were previously reported to selectively block the glutamate vesicular transporters (VGLUTs). We find that expanding the QDC scaffold to benzoquinoline dicarboxylic acids (BQDC) and naphthoquinoline dicarboxylic acids (NQDCs) improves inhibitory activity with the NQDCs showing IC50 ~ 70 µM. Modeling overlay studies showed that the polycyclic QDCs resembled steroid structures and led to the identification and testing of estrone sulfate, pregnenolone sulfate and pregnanolone sulfate that blocked the uptake of l-Glu by 50%, 70% and 85% of control, respectively. Pregnanolone sulfate was further characterized by kinetic pharmacological determinations that demonstrated competitive inhibition and a Ki of ≈ 20 µM. PMID:24424130

Piezoelectric crystal microbalance measurements of enthalpy of sublimation of C2-C9 dicarboxylic acids

NASA Astrophysics Data System (ADS)

Dirri, F.; Palomba, E.; Longobardo, A.; Zampetti, E.

2015-07-01

We present here a novel experimental setup able to measure the enthalpy of sublimation of a given compound by means of Piezoelectric Crystal Microbalances (PCM). This experiment was performed in the TG-Lab facility in IAPS-INAF, dedicated to the development of TGA sensors for space measurements, such as detection of organic and non-organic volatile species and refractory materials in planetary environments. In order to study physical-chemical processes concerning the Volatile Organic Compounds (VOC) present in atmospheric environments, the setup has been tested on Dicarboxylic acids. Acids with low molecular weight are among the components of organic fraction of particulate matter in the atmosphere, coming from different sources (biogenic and anthropogenic). Considering their relative abundance, it is useful to consider Dicarboxylic acid as "markers" to define the biogenic or anthropogenic origin of the aerosol, thus obtaining some information of the emission sources. In this work, a temperature controlled effusion cell was used to sublimate VOC, creating a molecular flux that was collimated onto a cold PCM. The VOC re-condensed onto the PCM quartz crystal allowing the determination of the deposition rate. From the measurements of deposition rates, it was possible to infer the enthalpy of sublimation of Adipic acid, i.e. Δ Hsub: 141.6 ± 0.8 kJ mol-1, Succinic acid, i.e. 113.3 ± 1.3 kJ mol-1, Oxalic acid, i.e. 62.5 ± 3.1 kJ mol-1 and Azelaic acid, i.e. 124.2 ± 1.2 kJ mol-1 (weight average values). The results obtained are in very good agreement with literature within 10 % for the Adipic, Succinic and Oxalic acid.

Green and low-cost production of thermally stable and carboxylated cellulose Nanocrystals and nanofibrils using highly recyclable dicarboxylic acids

Treesearch

Huiyang Bian; Liheng Chen; Ruibin Wang; Junyong Zhu

2016-01-01

Here we demonstrate potentially low cost and green productions of high thermally stable and carboxylated cellulose nanocrystals (CNCs) and nanofibrils (CNF) from bleached eucalyptus pulp (BEP) and unbleached mixed hardwood kraft pulp (UMHP) fibers using highly recyclable dicarboxylic solid acids. Typical operating conditions were acid concentrations of 50 - 70 wt% at...

Chemical characteristics of dicarboxylic acids and related organic compounds in PM2.5 during biomass-burning and non-biomass-burning seasons at a rural site of Northeast China.

PubMed

Cao, Fang; Zhang, Shi-Chun; Kawamura, Kimitaka; Liu, Xiaoyan; Yang, Chi; Xu, Zufei; Fan, Meiyi; Zhang, Wenqi; Bao, Mengying; Chang, Yunhua; Song, Wenhuai; Liu, Shoudong; Lee, Xuhui; Li, Jun; Zhang, Gan; Zhang, Yan-Lin

2017-12-01

Fine particulate matter (PM2.5) samples were collected using a high-volume air sampler and pre-combusted quartz filters during May 2013 to January 2014 at a background rural site (47 ∘ 35 N, 133 ∘ 31 E) in Sanjiang Plain, Northeast China. A homologous series of dicarboxylic acids (C 2 -C 11 ) and related compounds (oxoacids, α-dicarbonyls and fatty acids) were analyzed by using a gas chromatography (GC) and GC-MS method employing a dibutyl ester derivatization technique. Intensively open biomass-burning (BB) episodes during the harvest season in fall were characterized by high mass concentrations of PM2.5, dicarboxylic acids and levoglucosan. During the BB period, mass concentrations of dicarboxylic acids and related compounds were increased by up to >20 times with different factors for different organic compounds (i.e., succinic (C 4 ) acid > oxalic (C 2 ) acid > malonic (C 3 ) acid). High concentrations were also found for their possible precursors such as glyoxylic acid (ωC 2 ), 4-oxobutanoic acid, pyruvic acid, glyoxal, and methylglyoxal as well as fatty acids. Levoglucosan showed strong correlations with carbonaceous aerosols (OC, EC, WSOC) and dicarboxylic acids although such good correlations were not observed during non-biomass-burning seasons. Our results clearly demonstrate biomass burning emissions are very important contributors to dicarboxylic acids and related compounds. The selected ratios (e.g., C 3 /C 4 , maleic acid/fumaric acid, C 2 /ωC 2 , and C 2 /levoglucosan) were used as tracers for secondary formation of organic aerosols and their aging process. Our results indicate that organic aerosols from biomass burning in this study are fresh without substantial aging or secondary production. The present chemical characteristics of organic compounds in biomass-burning emissions are very important for better understanding the impacts of biomass burning on the atmosphere aerosols. Copyright © 2017 Elsevier Ltd. All rights reserved.

Organic and inorganic aerosol compositions in Ulaanbaatar, Mongolia, during the cold winter of 2007 to 2008: Dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls

NASA Astrophysics Data System (ADS)

Jung, Jinsang; Tsatsral, Batmunkh; Kim, Young J.; Kawamura, Kimitaka

2010-11-01

To investigate the distributions and sources of water-soluble organic acids in the Mongolian atmosphere, aerosol samples (PM2.5, n = 34) were collected at an urban site (47.92°N, 106.90°E, ˜1300 m above sea level) in Ulaanbaatar, the capital of Mongolia, during the cold winter. The samples were analyzed for water-soluble dicarboxylic acids (C2-C12) and related compounds (ketocarboxylic acids and α-dicarbonyls), as well as organic carbon (OC), elemental carbon, water-soluble OC, and inorganic ions. Distributions of dicarboxylic acids and related compounds were characterized by a predominance of terephthalic acid (tPh; 130 ± 51 ng m-3, 19% of total detected organic acids) followed by oxalic (107 ± 28 ng m-3, 15%), succinic (63 ± 20 ng m-3, 9%), glyoxylic (55 ± 18 ng m-3, 8%), and phthalic (54 ± 27 ng m-3, 8%) acids. Predominance of terephthalic acid, which has not been reported previously in atmospheric aerosols, was mainly due to uncontrolled burning of plastic bottles and bags in home stoves for heating and waste incineration during the cold winter. This study demonstrated that most of the air pollutants were directly emitted from local sources such as heat and power plants, home stoves, and automobiles. Development of an inversion layer (<700 m above ground level) over the basin of Ulaanbaatar accelerated the accumulation of pollutants, causing severe haze episodes during the winter season.

Preferential deprotonation and conformational stability of dicarboxylic acids: A packing effect

NASA Astrophysics Data System (ADS)

Barooah, Nilotpal; Singh, W. Marjit; Baruah, Jubaraj B.

2008-03-01

Crystal structures of a series of salts of (6-carboxymethyl-1,3,5,7-tetraoxo-3,5,6,7-tetrahydro-1 H-pyrrolo[3,4- f]isoindol-2-yl)-acetic acid ( 1) and 2-carboxymethyl-1,3-dioxo-2,3-dihydro-1 H-isoinodole-5-carboxylic acid ( 2) with different polynuclear nitrogen containing heterocyclic compounds, namely, quinoline, 1,10-phenanthroline and 8-hydroxyquinoline are determined. In the case of salt of 1 with quinolinium and 1,10-phenanthrolinium cations syn disposition between the carboxylate anion and carboxylic acid groups is observed; whereas in the case of the 8-hydroxyquinolinium salt of 1, it is the anti disposition. It is also found that the solid state structure of 1,10-phenanthrolinium salt of 2 has deprotonation at the aromatic end, whereas in 8-hydroxy-quinolinium salt of 2 is formed by deprotonation of carboxylic acid group on the aliphatic side. The dicarboxylic acid 2 forms 1:2 co-crystals with quinoline. From crystallographic study it is shown that the weak interactions become prominent in stabilising the observed conformers and also in stabilising specific deprotonated species.

Two novel dicarboxylic Acid derivatives and a new dimeric hydrolyzable tannin from walnuts.

PubMed

Ito, Hideyuki; Okuda, Takahiro; Fukuda, Toshiyuki; Hatano, Tsutomu; Yoshida, Takashi

2007-02-07

In addition to the 16 previously reported polyphenols including 3 new ellagitannins, 2 novel dicarboxylic acid derivatives, glansreginins A (1) and B (2), and a new dimeric hydrolyzable tannin, glansrin D (3), were isolated, together with 15 known compounds from walnuts, the seeds of Juglans regia. The structures of the new compounds were elucidated on the basis of 1D- and 2D-NMR analyses and chemical data. The antioxidant effect of these isolates was also evaluated by SOD-like and DPPH radical scavenging activities.

Water soluble dicarboxylic acids and related compounds in Antarctic aerosols

NASA Astrophysics Data System (ADS)

Kawamura, Kimitaka; SeméRé, Richard; Imai, Yoshie; Fujii, Yoshiyuki; Hayashi, Masahiko

1996-08-01

Antarctic aerosols collected at Syowa Station were studied for water soluble organic compounds by employing a water extraction and dibutyl ester derivatization and using a capillary gas chromatography (GC) and GC/mass spectrometry (GC/MS). Total carbon and nitrogen were also determined. A homologous series of α,ω-dicarboxylic acids (C2-C11), ω-oxocarboxylic acids (C2-C9), and α-dicarbonyls (C2-C3) were detected, as well as pyruvic acid and aromatic (phthalic) diacid. Succinic (C4) or oxalic (C2) acid was found to be the dominant diacid species, followed by azelaic (C9), adipic (C6), or malonic (C3) acid. Concentration range of the total diacids was 5.9-88 ng m-3, with an average of 29 ng m-3. Highest concentrations were observed in the summer sample with a predominance of succinic acid (61.5 ng m-3), which comprised approximately 70% of the total diacids and accounted for 3.5% of total aerosol carbon (1020 ng m-3). The succinic acid (C4) is likely produced by photooxidation of 4-oxocarboxylic acids, which are present in the atmosphere as intermediates of the photooxidation of unsaturated fatty acids. These results indicate that the Antarctic organic aerosols originate from marine-derived lipids and are transformed largely by photochemical oxidations. ω-Oxocarboxylic acids (C2-C9, 0.36-3.0 ng m-3) also showed the highest concentration in the summer sample, again suggesting a secondary production in the atmosphere of the Antarctic and in the Southern Ocean.

Morphology and phase transformations of tin oxide nanostructures synthesized by the hydrothermal method in the presence of dicarboxylic acids

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

Zima, Tatyana, E-mail: zima@solid.nsc.ru; Novosibirsk State Technical University, 20 K. Marx Prospect, Novosibirsk 630092; Bataev, Ivan

A new approach to the synthesis of non-stoichiometric tin oxide structures with different morphologies and the phase compositions has been evaluated. The nanostructures were synthesized by hydrothermal treatment of the mixtures of dicarboxylic acids ― aminoterephthalic or oxalic ― with nanocrystalline SnO{sub 2} powder, which was obtained via the sol-gel technology. The products were characterized by Raman and IR spectroscopy, SEM, HRTEM, and XRD analysis. It was shown that the controlled addition of a dicarboxylic acid leads not only to a change in the morphology of the nanostructures, but also to SnO{sub 2}–SnO{sub 2}/Sn{sub 3}O{sub 4}–Sn{sub 3}O{sub 4}–SnO phase transformations.more » A single-phase Sn{sub 3}O{sub 4} in the form of the well-separated hexagonal nanoplates and mixed SnO{sub 2}/Sn{sub 3}O{sub 4} phases in the form of hierarchical flower-like structures were obtained in the presence of organic additives. The effects of concentration, redox activity of the acids and heat treatment on the basic characteristics of the synthesized tin oxide nanostructures and phase transformations in the synthesized materials are discussed. - Graphical abstract: The controlled addition of aminoterephthalic or oxalic acid leads not only to a change in the morphology of the nanostructures, but also to SnO{sub 2}–SnO{sub 2}/Sn{sub 3}O{sub 4}–Sn{sub 3}O{sub 4}–SnO phase transformations. - Highlights: • A new approach to the synthesis of non-stoichiometric tin oxide structures is studied. • Tin oxide structures are synthesized via hydrothermal method with dicarboxylic acids. • Morphology and phase composition are changed with redox activity and dosage of acid. • The redox activity of acid has an effect on ratio of SnO and SnO{sub 2} in crystal structure. • A pure phase Sn{sub 3}O{sub 4} nanoplates and SnO{sub 2}/Sn{sub 3}O{sub 4} hierarchical structures are formed.« less

Morphology and phase transformations of tin oxide nanostructures synthesized by the hydrothermal method in the presence of dicarboxylic acids

NASA Astrophysics Data System (ADS)

Zima, Tatyana.; Bataev, Ivan

2016-11-01

A new approach to the synthesis of non-stoichiometric tin oxide structures with different morphologies and the phase compositions has been evaluated. The nanostructures were synthesized by hydrothermal treatment of the mixtures of dicarboxylic acids ― aminoterephthalic or oxalic ― with nanocrystalline SnO2 powder, which was obtained via the sol-gel technology. The products were characterized by Raman and IR spectroscopy, SEM, HRTEM, and XRD analysis. It was shown that the controlled addition of a dicarboxylic acid leads not only to a change in the morphology of the nanostructures, but also to SnO2-SnO2/Sn3O4-Sn3O4-SnO phase transformations. A single-phase Sn3O4 in the form of the well-separated hexagonal nanoplates and mixed SnO2/Sn3O4 phases in the form of hierarchical flower-like structures were obtained in the presence of organic additives. The effects of concentration, redox activity of the acids and heat treatment on the basic characteristics of the synthesized tin oxide nanostructures and phase transformations in the synthesized materials are discussed.

Stable carbon isotope ratios of low molecular weight dicarboxylic acids, ketoacids and glyoxal in marine aerosols from the western North Pacific: Long-term trends in Chichijima Island

NASA Astrophysics Data System (ADS)

Kawamura, K.; Tachibana, E.

2012-12-01

Dicarboxylic acids such as oxalic, malonic and succinic acids are the most abundant water-soluble organic compound class in aerosols. To better understand the source and photochemical processes of water-soluble organic aerosols in the remote marine aerosols, we measured stable carbon isotopic composition (δ13C) of dicarboxylic acids and related compounds using a GC/IR/MS technique. The aerosol samples were collected in 2001-2011 at a remote island, Chichijima (27°04'E; 142°13'N) in the western North Pacific. Here we present decadal variations of the isotopic composition of dicarboxylic acids (C2-C9), ketoacids (C2-C8) and glyoxal in summertime aerosols (June, July and August). The molecular distributions of diacids were characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids. Oxalic acid showed higher δ13C values than other species ranging from -18‰ to -2‰ with no clear decadal trend. In contrast, C3 and C4 diacids showed δ13C values of -24 to -5‰ and -40 to -12‰ with a decadal decline. Glyoxal (-60 to -10‰) and ωC7 acid (-34 to -12‰) also showed lower values toward 2011. However, azelaic acid (C9) (-32 to -24‰) stayed relatively constant throughout the observation period. We will discuss the detailed isotopic compositions of these organic species in terms of the photochemical aging and processing in the western North Pacific and the changes in the sources and source regions.

Fragment-based discovery of novel and selective mPGES-1 inhibitors Part 1: identification of sulfonamido-1,2,3-triazole-4,5-dicarboxylic acid.

PubMed

Lee, Kijae; Pham, Van Chung; Choi, Min Ji; Kim, Kyung Ju; Lee, Kyung-Tae; Han, Seong-Gu; Yu, Yeon Gyu; Lee, Jae Yeol

2013-01-01

Microsomal prostaglandin E synthase-1 (mPGES-1) is an inducible prostaglandin E synthase that catalyzes the conversion of prostaglandin PGH(2) to PGE(2) and represents a novel target for therapeutic treatment of inflammatory disorders. It is essential to identify mPGES-1 inhibitor with novel scaffold as new hit or lead compound for the purpose of the next-generation anti-inflammatory drugs. Herein we report the discovery of sulfonamido-1,2,3-triazole-4,5-dicarboxylic derivatives as a novel class of mPGES-1 inhibitors identified through fragment-based virtual screening and in vitro assays on the inhibitory activity of the actual compounds. 1-[2-(N-Phenylbenzenesulfonamido)ethyl]-1H-1,2,3-triazole-4,5-dicarboxylic acid (6f) inhibits human mPGES-1 (IC(50) of 1.1 μM) with high selectivity (ca.1000-fold) over both COX-1 and COX-2 in a cell-free assay. In addition, the activity of compound 6f was again tested at 10 μM concentration in presence of 0.1% Triton X-100 and found to be reduced to 1/4 of its original activity without this detergent. Compared to the complete loss of activity of nuisance inhibitor with the detergent, therefore, compound 6f would be regarded as a partial nuisance inhibitor of mPGES-1 with a novel scaffold for the optimal design of more potent mPGES-1 inhibitors. Copyright © 2012 Elsevier Ltd. All rights reserved.

Crystal engineering of novel cocrystals of a triazole drug with 1,4-dicarboxylic acids.

PubMed

Remenar, Julius F; Morissette, Sherry L; Peterson, Matthew L; Moulton, Brian; MacPhee, J Michael; Guzmán, Héctor R; Almarsson, Orn

2003-07-16

Cocrystals of the poorly soluble antifungal drug cis-itraconazole (1) with 1,4-dicarboxylic acids have been prepared. The crystal structure of the succinic acid cocrystal with 1 was determined to be a trimer by single-crystal X-ray. The trimer is comprised of two molecules of 1 oriented in antiparallel fashion to form a pocket with a triazole at either end. The extended succinic acid molecule fills the pocket, bridging the triazole groups through hydrogen-bonding interactions rather than interacting with the more basic piperazine nitrogens. The solubility and dissolution rate of some of the cocrystals are approximately the same as those of the amorphous drug in the commercial formulation and are much higher than those for the crystalline free base. The results suggest that cocrystals of drug molecules have the possibility of achieving the higher oral bioavailability common for amorphous forms of water-insoluble drugs while maintaining the long-term chemical and physical stability that crystal forms provide.

Cyclohexane-1,2-dicarboxylic acid diisononyl ester and metabolite effects on rat epididymal stromal vascular fraction differentiation of adipose tissue

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

Campioli, Enrico; Department of Medicine, McGill University, Montréal, Québec; Duong, Tam B.

Plastics are generally mixed with additives like plasticizers to enhance their flexibility, pliability, and elasticity proprieties. Plasticizers are easily released into the environment and are absorbed mainly through ingestion, dermal contact, and inhalation. One of the main classes of plasticizers, phthalates, has been associated with endocrine and reproductive diseases. In 2002, 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH) was introduced in the market for use in plastic materials and articles intended to come into contact with food, and it received final approval from the European Food Safety Authority in 2006. At present, there is limited knowledge about the safety and potentialmore » metabolic and endocrine-disrupting properties of DINCH and its metabolites. The purpose of this study was to evaluate the biological effects of DINCH and its active metabolites, cyclohexane-1,2-dicarboxylic acid (CHDA) and cyclohexane-1,2-dicarboxylic acid mono isononyl ester (MINCH), on rat primary stromal vascular fraction (SVF) of adipose tissue. DINCH and its metabolite, CHDA, were not able to directly affect SVF differentiation. However, exposure of SVF to 50 μM and 100 μM concentrations of MINCH affected the expression of Cebpa and Fabp4, thus inducing SVF preadipocytes to accumulate lipids and fully differentiate into mature adipocytes. The effect of MINCH was blocked by the specific peroxisome proliferator-activated receptor (PPAR)-α antagonist, GW6471. Taken together, these results suggest that MINCH is a potent PPAR-α agonist and a metabolic disruptor, capable of inducing SVF preadipocyte differentiation, that may interfere with the endocrine system in mammals. - Highlights: • DINCH and CHDA did not affect the adipogenesis of the SVF. • MINCH affected the adipogenesis of the SVF. • MINCH effect was blocked by the specific PPAR-α antagonist GW6471. • MINCH exerted a similar effect as MEHP on SVF adipogenesis. • DINCH/MINCH are potential

A Na+-coupled C4-dicarboxylate transporter (Asuc_0304) and aerobic growth of Actinobacillus succinogenes on C4-dicarboxylates.

PubMed

Rhie, Mi Na; Yoon, Hyo Eun; Oh, Hye Yun; Zedler, Sandra; Unden, Gottfried; Kim, Ok Bin

2014-07-01

Actinobacillus succinogenes, which is known to produce large amounts of succinate during fermentation of hexoses, was able to grow on C4-dicarboxylates such as fumarate under aerobic and anaerobic conditions. Anaerobic growth on fumarate was stimulated by glycerol and the major product was succinate, indicating the involvement of fumarate respiration similar to succinate production from glucose. The aerobic growth on C4-dicarboxylates and the transport proteins involved were studied. Fumarate was oxidized to acetate. The genome of A. succinogenes encodes six proteins with similarity to secondary C4-dicarboxylate transporters, including transporters of the Dcu (C4-dicarboxylate uptake), DcuC (C4-dicarboxylate uptake C), DASS (divalent anion : sodium symporter) and TDT (tellurite resistance dicarboxylate transporter) family. From the cloned genes, Asuc_0304 of the DASS family protein was able to restore aerobic growth on C4-dicarboxylates in a C4-dicarboxylate-transport-negative Escherichia coli strain. The strain regained succinate or fumarate uptake, which was dependent on the electrochemical proton potential and the presence of Na(+). The transport had an optimum pH ~7, indicating transport of the dianionic C4-dicarboxylates. Transport competition experiments suggested substrate specificity for fumarate and succinate. The transport characteristics for C4-dicarboxylate uptake by cells of aerobically grown A. succinogenes were similar to those of Asuc_0304 expressed in E. coli, suggesting that Asuc_0304 has an important role in aerobic fumarate uptake in A. succinogenes. Asuc_0304 has sequence similarity to bacterial Na(+)-dicarboxylate cotransporters and contains the carboxylate-binding signature. Asuc_0304 was named SdcA (sodium-coupled C4-dicarboxylate transporter from A. succinogenes). © 2014 The Authors.

Designing and Creating a Synthetic Omega Oxidation Pathway in Saccharomyces cerevisiae Enables Production of Medium-Chain α, ω-Dicarboxylic Acids

PubMed Central

Han, Li; Peng, Yanfeng; Zhang, Yuangyuan; Chen, Wujiu; Lin, Yuping; Wang, Qinhong

2017-01-01

Medium-chain (C8–C14) α, ω-dicarboxylic acids (α, ω-DCAs), which have numerous applications as raw materials for producing various commodities and polymers in chemical industry, are mainly produced from chemical or microbial conversion of petroleum-derived alkanes or plant-derived fatty acids at present. Recently, significant attention has been gained to microbial production of medium-chain α, ω-DCAs from simple renewable sugars. Here, we designed and created a synthetic omega oxidation pathway in Saccharomyces cerevisiae to produce C10 and C12 α, ω-DCAs from renewable sugars and fatty acids by introducing a heterogeneous cytochrome P450 CYP94C1 and cytochrome reductase ATR1. Furthermore, the deletion of fatty acyl-CoA synthetase genes FAA1 and FAA4 increased the production of medium-chain α, ω-DCAs from 4.690 ± 0.088 mg/L to 12.177 ± 0.420 mg/L and enabled the production of C14 and C16 α, ω-DCAs at low percentage. But blocking β-oxidation pathway by deleting fatty-acyl coenzyme A oxidase gene POX1 and overexpressing different thioesterase genes had no significant impact on the production and the composition of α, ω-dicarboxylic acids. Overall, our study indicated the potential of microbial production of medium-chain α, ω-DCAs from renewable feedstocks using engineered yeast. PMID:29163455

Biotransformation of 5-hydroxy-methylfurfural into 2,5-furan-dicarboxylic acid by bacterial isolate using thermal acid algal hydrolysate.

PubMed

Yang, Chu-Fang; Huang, Ci-Ruei

2016-08-01

Thermal acid hydrolysis is often used to deal with lignocellulosic biomasses, but 5-hydroxy-methylfurfural (5-HMF) formed during hydrolysis deeply influences downstream fermentation. 2,5-Furan-dicarboxylic acid (FDCA), which is in the list of future important biomass platform molecules can be obtained using 5-HMF biotransformation. Based on the connection between 5-HMF removal in acid hydrolysate and FDCA production, the optimum thermal acid hydrolysis condition for macroalgae Chaetomorpha linum was established. Potential microbes capable of transforming 5-HMF into FDCA were isolated and characterized under various parameters and inoculated into algal hydrolysate to perform 5-HMF biotransformation. The optimum hydrolysis condition was to apply 0.5M HCl to treat 3% algal biomass under 121°C for 15min. Isolated Burkholderia cepacia H-2 could transform 2000mg/L 5-HMF at the initial pH of 7 at 28°C and 1276mg/L FDCA was received. Strain B. cepacia H-2 was suitable for treating the algal hydrolysate without dilution, receiving 989.5mg/L FDCA. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis, characterization, crystal structure and solution studies of a novel proton transfer (charge transfer) complex of 2,2‧-dipyridylamine with 2,6-pyridine dicarboxylic acid

NASA Astrophysics Data System (ADS)

Ghasemi, Khaled; Rezvani, Ali Reza; Shokrollahi, Ardeshir; Zarghampour, Fereshteh; Moghimi, Abolghasem; García-Granda, Santiago; Mendoza-Meroño, Rafael

2015-06-01

Reaction between 2,2‧-dipyridylamine (DPA) and 2,6-pyridine dicarboxylic acid (dipicolinic acid, dipicH2), in water results in the formation of a proton transfer or charge transfer (CT) complex, (DPAH)+(dipicH)-·H2O, 1. The characterization was performed using 1H NMR and FTIR spectroscopy, elemental analysis and X-ray crystallography. The crystal system is triclinic with space group P1. The structural investigations exhibit that the hydrogen bonds and π-π stacking interactions stabilize the crystal structure of proton transfer complex. The protonation constants of 2,6-pyridine dicarboxylic acid, 2,2‧-dipyridylamine and the equilibrium constants for dipic-DPA (1:1) proton transfer system were calculated by potentiometric pH titration method using Hyperquad2008 program. The stoichiometries of the proton transfer species in solution was in agreement with the solid state result.

Field Observation of Heterogeneous Formation of Dicarboxylic acids, Keto-carboxylic acids, α-Dicarbonyls and Nitrate in Xi'an, China during Asian dust storm periods

NASA Astrophysics Data System (ADS)

Wang, G.; Wang, J.; Ren, Y.; Li, J.

2015-12-01

To understand the formation mechanism of secondary organic aerosols (SOA) on dust surfaces, this study investigated the concentrations and compositions of dicarboxylic acids (C2-C11), keto-carboxylic acids (C3-C7), α-dicarbonyls and inorganic ions in size-segregated aerosols (9-stages) collected in Xi'an, China during the nondust storm and dust storm periods of 2009 and 2011. During the events the ambient particulate dicarboxylic acids were 932-2240 ng m-3, which are comparable and even higher than those in nondust periods. Molecular compositions of the above SOA are similar to those in nondust periods with oxalic acid being the leading species. In the presence of the dust storms, all the above mentioned SOA species in Xi'an were predominantly enriched on the coarse particles (>2.1μm), and oxalic acid well correlated with NO3- (R2=0.72, p<0.001) rather than SO42-.This phenomenon differs greatly from the SOA in any other nondust period that is characterized by an enrichment of oxalic acid in fine particles and a strong correlation of oxalic acid with SO42-. Our results further demonstrate that NO3- in the dust periods in Xi'an was mostly derived from secondary oxidation, whereas SO42- during the events was largely derived from surface soil of Gobi deserts. We propose a formation pathway to explain these observations, in which nitric acid and/or nitrogen oxides react with dust to produce Ca(NO3)2 and form a liquid phase on the surface of dust aerosols via water vapor-absorption of Ca(NO3)2, followed by a partitioning of the gas-phase water-soluble organic precursors (e.g.,glyoxal and methylglyoxal) into the aqueous-phase and a subsequent oxidation into oxalic acid. To the best of our knowledge, we found for the first time the enrichment of glyoxal and methylglyoxal on dust surface. Our data suggest an important role of nitrate in the heterogeneous formation process of SOA on the surface of Asian dust.

A Family of Uranyl Coordination Polymers Containing O-Donor Dicarboxylates and Trispyridyltriazine Guests

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

Thangavelu, Sonia G.; Cahill, Christopher L.

Four uranyl coordination polymers [UO2(C6H8O4)(H2O)2](C18H12N6)2 (1), [UO2(C8H4O4)(H2O)2](C18H12N6)2 (2), Na[(UO2)(C12H6O4)2](C18H13N6)·H2O (3), and Na[(UO2)(C16H8O4)(C6H3NO2)](C18H12N6)·H2O (4) containing aliphatic (adipic acid) or aromatic linkers (1,4-benzene dicarboxylic acid (BDC), 1,4-napthalene dicarboxylic acid (NDC), anthracene 9,10-dicarboxylic acid (ADC)) were synthesized and characterized using single crystal X-ray diffraction, powder X-ray diffraction, and luminescence spectroscopy. The π-stacking distances or the number of π–π interactions present between trispyridyltriazine (TPTZ) guests or the host framework in 1–4 may be affected by the size of the O-donor linker (adipic acid < BDC < NDC < ADC). Luminescence studies show that substitution between adipic acid and BDC influences the emission of 1more » and 2, in which the emission of 1 shows a red shift relative to that of 2. Uranyl emission was not observed in 3 and 4, and may be attributed to the position of the NDC and ADC triplet state relative to the emissive uranyl species.« less

A Family of Uranyl Coordination Polymers Containing O-Donor Dicarboxylates and Trispyridyltriazine Guests

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

Thangavelu, Sonia G.; Cahill, Christopher L.

2016-01-06

Four uranyl coordination polymers [UO2(C6H8O4)(H2O)2](C18H12N6)2 (1), [UO2(C8H4O4)(H2O)2](C18H12N6)2 (2), Na[(UO2)(C12H6O4)2](C18H13N6)·H2O (3), and Na[(UO2)(C16H8O4)(C6H3NO2)](C18H12N6)·H2O (4) containing aliphatic (adipic acid) or aromatic linkers (1,4-benzene dicarboxylic acid (BDC), 1,4-napthalene dicarboxylic acid (NDC), anthracene 9,10-dicarboxylic acid (ADC)) were synthesized and characterized using single crystal X-ray diffraction, powder X-ray diffraction, and luminescence spectroscopy. The π-stacking distances or the number of π–π interactions present between trispyridyltriazine (TPTZ) guests or the host framework in 1–4 may be affected by the size of the O-donor linker (adipic acid < BDC < NDC < ADC). Luminescence studies show that substitution between adipic acid and BDC influences the emission of 1more » and 2, in which the emission of 1 shows a red shift relative to that of 2. Uranyl emission was not observed in 3 and 4, and may be attributed to the position of the NDC and ADC triplet state relative to the emissive uranyl species.« less

Molecular distributions and isotopic compositions of marine aerosols over the western North Atlantic: Dicarboxylic acids, ketoacids, α-dicarbonyls (glyoxal and methylglyoxal), fatty acids, sugars, and SOA tracers

NASA Astrophysics Data System (ADS)

Kawamura, K.; Ono, K.; Tachibana, E.; Quinn, P.; Bates, T. S.

2013-12-01

Marine aerosols were collected over the western North Atlantic from off the coast of Boston to Bermuda during the WACS (Western Atlantic Climate Study) cruise of R/V Ronald H. Brown in August 2012 using a high volume air sampler and pre-combusted quartz fiber filters. Aerosol filter samples (n=5) were analyzed for OC/EC, major inorganic ions, low molecular weight dicarboxylic acids and various secondary organic aerosol (SOA) tracers using carbon analyzer, ion chromatograph, GC/FID and GC/MS, respectively. Homologous series (C2-C12) of dicarboxylic acids (31-335 ng m-3) were detected with a predominance of oxalic acid. Total carbon and nitrogen and their stable isotope ratios were determined as well as stable carbon isotopic compositions of individual diacids using IRMS. Diacids were found to be the most abundant compound class followed by monoterpene-SOA tracers > isoprene-SOA tracers > sugar compounds > ketoacids > fatty alcohols > fatty acids > α-dicarbonyls > aromatic acids > n-alkanes. The concentrations of these compounds were higher in the coastal site and decreased in the open ocean. However, diacids stayed relatively high even in the remote ocean. Interestingly, contributions of oxalic acid to total aerosol carbon increased from the coast (2.3%) to the remote ocean (5.6%) during long-range atmospheric transport. Stable carbon isotopic composition of oxalic acid increased from the coast (-17.5‰) to open ocean (-12.4‰), suggesting that photochemical aging of organic aerosols occurred during the atmospheric transport over the ocean. Stable carbon isotope ratios of bulk aerosol carbon also increased from the coast near Boston to the open ocean near Bermuda.

Novel one-pot synthesis of dicarboxylic acids mediated alginate-zirconium biopolymeric complex for defluoridation of water.

PubMed

Prabhu, Subbaiah Muthu; Meenakshi, Sankaran

2015-04-20

The present investigation explains the fluoride removal from aqueous solution using alginate-zirconium complex prepared with respective dicarboxylic acids like oxalic acid (Ox), malonic acid (MA) and succinic acid (SA) as a medium. The complexes viz., alginate-oxalic acid-zirconium (Alg-Ox-Zr), alginate-malonic acid-zirconium (Alg-MA-Zr) and alginate-succinic acid-zirconium (Alg-SA-Zr) were synthesized and studied for fluoride removal. The synthesized complexes were characterized by FTIR, XRD, SEM with EDAX and mapping images. The effects of various operating parameters were optimized. The result showed that the maximum removal of fluoride 9653mgF(-)/kg was achieved by Alg-Ox-Zr complex at acidic pH in an ambient atmospheric condition. Equilibrium data of Alg-Ox-Zr complex was fitted well with Freundlich isotherm. The calculated values of thermodynamic parameters indicated that the fluoride adsorption is spontaneous and endothermic in nature. The mechanism of fluoride removal behind Alg-Ox-Zr complex has been proposed in detail. The suitability of the Alg-Ox-Zr complex has been tested with the field sample collected in a nearby fluoride endemic area. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sources and formation processes of water-soluble dicarboxylic acids, ω-oxocarboxylic acids, α-dicarbonyls, and major ions in summer aerosols from eastern central India

NASA Astrophysics Data System (ADS)

Deshmukh, Dhananjay K.; Kawamura, Kimitaka; Deb, Manas K.; Boreddy, Suresh K. R.

2017-03-01

The sources and formation processes of dicarboxylic acids are still under investigation. Size-segregated aerosol (nine-size) samples collected in the urban site (Raipur: 21.2°N and 82.3°E) in eastern central India during summer of 2013 were measured for water-soluble diacids (C2-C12), ω-oxoacids (ωC2-ωC9), α-dicarbonyls (C2-C3), and inorganic ions to better understand their sources and formation processes. Diacids showed the predominance of oxalic acid (C2), whereas ω-oxoacids showed the predominance of glyoxylic acid (ωC2), and glyoxal (Gly) was a major α-dicarbonyl in all the sizes. Diacids, ω-oxoacids, and α-dicarbonyls as well as SO42

Ruthenium water oxidation catalysts containing the non-planar tetradentate ligand, biisoquinoline dicarboxylic acid (biqaH2).

PubMed

Scherrer, Dominik; Schilling, Mauro; Luber, Sandra; Fox, Thomas; Spingler, Bernhard; Alberto, Roger; Richmond, Craig J

2016-12-06

Two ruthenium complexes containing the tetradentate ligand [1,1'-biisoquinoline]-3,3'-dicarboxylic acid, and 4-picoline or 6-bromoisoquinoline as axial ligands have been prepared. The complexes have been fully characterised and initial studies on their potential to function as molecular water oxidation catalysts have been performed. Both complexes catalyse the oxidation of water in acidic media with Ce IV as a stoichiometric chemical oxidant, although turnover numbers and turnover frequencies are modest when compared with the closely related Ru-bda and Ru-pda analogues. Barriers for the water nucleophilic attack and intermolecular coupling pathways were obtained from density functional theory calculations and the crucial influence of the ligand framework in determining the most favourable reaction pathway was elucidated from a combined analysis of the theoretical and experimental results.

Temperature dependences of saturated vapor pressure and the enthalpy of vaporization of n-pentyl esters of dicarboxylic acids

NASA Astrophysics Data System (ADS)

Portnova, S. V.; Krasnykh, E. L.; Levanova, S. V.

2016-05-01

The saturated vapor pressures and enthalpies of vaporization of n-pentyl esters of linear C2-C6 dicarboxylic acids are determined by the transpiration method in the temperature range of 309.2-361.2 K. The dependences of enthalpies of vaporization on the number of carbon atoms in the molecule and on the retention indices have been determined. The predictive capabilities of the existing calculation schemes for estimation of enthalpy of vaporization of the studied compounds have been analyzed.

Luminescence recognition of different organophosphorus pesticides by the luminescent Eu(III)-pyridine-2,6-dicarboxylic acid probe.

PubMed

Azab, Hassan A; Duerkop, Axel; Anwar, Z M; Hussein, Belal H M; Rizk, Moustafa A; Amin, Tarek

2013-01-08

Luminescence quenching of a novel long lived Eu(III)-pyridine-2,6-dicarboxylic acid probe of 1:2 stoichiometric ratio has been studied in 0.10 volume fraction ethanol-water mixture at pH 7.5 (HEPES buffer) in the presence of the organophosphorus pesticides chlorfenvinphos (P1), malathion (P2), azinphos (P3), and paraxon ethyl (P4). The luminescence intensity of Eu(III)-(PDCA)(2) probe decreases as the concentration of the pesticide increases. It was observed that the quenching due to P3 and P4 proceeds via both diffusional and static quenching processes. Direct methods for the determination of the pesticides under investigation have been developed using the luminescence quenching of Eu(III)-pyridine-2,6-dicarboxylic acid probe in solution. The linear range for determination of the selected pesticides is 1.0-35.0 μM. The detection limits were 0.24-0.55 μM for P3, P4, and P1 and 2.5 μM for P2, respectively. The binding constants (K), and thermodynamic parameters of the OPs with Eu(III)-(PDCA)(2) were evaluated. Positive and negative values of entropy (ΔS) and enthalpy (ΔH) changes for Eu(III)-(PDCA)(2)-P1 ternary complex were calculated. As the waters in this study do not contain the above mentioned OPs over the limit detectable by the method, a recovery study was carried out after the addition of the adequate amounts of the organophosphorus pesticides under investigation. Copyright © 2012 Elsevier B.V. All rights reserved.

Engineering Escherichia coli for Conversion of Glucose to Medium-Chain ω-Hydroxy Fatty Acids and α,ω-Dicarboxylic Acids.

PubMed

Bowen, Christopher H; Bonin, Jeff; Kogler, Anna; Barba-Ostria, Carlos; Zhang, Fuzhong

2016-03-18

In search of sustainable approaches to plastics production, many efforts have been made to engineer microbial conversions of renewable feedstock to short-chain (C2-C8) bifunctional polymer precursors (e.g., succinic acid, cadaverine, 1,4-butanediol). Less attention has been given to medium-chain (C12-C14) monomers such as ω-hydroxy fatty acids (ω-OHFAs) and α,ω-dicarboxylic acids (α,ω-DCAs), which are precursors to high performance polyesters and polyamides. Here we engineer a complete microbial conversion of glucose to C12 and C14 ω-OHFAs and α,ω-DCAs, with precise control of product chain length. Using an expanded bioinformatics approach, we screen a wide range of enzymes across phyla to identify combinations that yield complete conversion of intermediates to product α,ω-DCAs. Finally, through optimization of culture conditions, we enhance production titer of C12 α,ω-DCA to nearly 600 mg/L. Our results indicate potential for this microbial factory to enable commercially relevant, renewable production of C12 α,ω-DCA-a valuable precursor to the high-performance plastic, nylon-6,12.

Crystal structures of 4-meth-oxy-benzoic acid-1,3-bis-(pyridin-4-yl)propane (2/1) and biphenyl-4,4'-di-carb-oxy-lic acid-4-meth-oxy-pyridine (1/2).

PubMed

Gotoh, Kazuma; Ishida, Hiroyuki

2017-07-01

The crystal structures of two hydrogen-bonded compounds, namely 4-meth-oxy-benzoic acid-1,3-bis-(pyridin-4-yl)propane (2/1), C 13 H 14.59 N 2 ·C 8 H 7.67 O 3 ·C 8 H 7.74 O 3 , (I), and biphenyl-4,4'-di-carb-oxy-lic acid-4-meth-oxy-pyridine (1/2), C 14 H 9.43 O 4 ·C 6 H 7.32 NO·C 6 H 7.25 NO, (II), have been determined at 93 K. In (I), the asymmetric unit consists of two crystallographically independent 4-meth-oxy-benzoic acid mol-ecules and one 1,3-bis-(pyridin-4-yl)propane mol-ecule. The asymmetric unit of (II) comprises one biphenyl-4,4'-di-carb-oxy-lic acid mol-ecule and two independent 4-meth-oxy-pyridine mol-ecules. In each crystal, the acid and base mol-ecules are linked by short O-H⋯N/N-H⋯O hydrogen bonds, in which H atoms are disordered over the acid O-atom and base N-atom sites, forming a linear hydrogen-bonded 2:1 or 1:2 unit of the acid and the base. The 2:1 units of (I) are linked via C-H⋯π, π-π and C-H⋯O inter-actions into a tape structure along [101], while the 1:2 units of (II) form a double-chain structure along [-101] through π-π and C-H⋯O inter-actions.

Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

1999-10-01

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid

Carboxylic and Dicarboxylic Acids Extracted from Crushed Magnesium Oxide Single Crystals

NASA Technical Reports Server (NTRS)

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

1998-01-01

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.

Carboxylic and dicarboxylic acids extracted from crushed magnesium oxide single crystals

NASA Technical Reports Server (NTRS)

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

1999-01-01

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.

High abundances of water-soluble dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the mountaintop aerosols over the North China Plain during wheat burning season

NASA Astrophysics Data System (ADS)

Kawamura, K.; Tachibana, E.; Okuzawa, K.; Aggarwal, S. G.; Kanaya, Y.; Wang, Z. F.

2013-08-01

Aerosol (TSP) samples were collected at the summit of Mount Tai (elevation: 1534 m a.s.l., 36.25° N, 117.10° E) located in the North China Plain using a high-volume air sampler and pre-combusted quartz filters. Sampling was conducted on day/night or 3 h basis in the period from 29 May to 28 June 2006 during the field burning of wheat straw residue and the post-burning season. The filter samples were analyzed for low-molecular-weight dicarboxylic acids, ketoacids and α-dicarbonyls using capillary gas chromatography (GC) and GC-MS employing water extraction and butyl ester derivatization. Molecular distributions of dicarboxylic acids (C2-C11, 220-6070 ng m-3) were characterized by a predominance of oxalic (C2) acid (105-3920 ng m-3) followed by succinic (C4) or malonic (C3) acid. Unsaturated aliphatic diacids, including maleic (M), isomaleic (iM) and fumaric (F) acids, were also detected together with aromatic diacids (phthalic, isophthalic and terephthalic acids). ω-oxocarboxylic acids (C2-C9, 24-610 ng m-3) were detected as the second most abundant compound class with the predominance of glyoxylic acid (11-360 ng m-3), followed by α-ketoacid (pyruvic acid, 3-140 ng m-3) and α-dicarbonyls (glyoxal, 1-230 ng m-3 and methylglyoxal, 2-120 ng m-3). We found that these levels (>6000 ng m-3 for diacids) are several times higher than those reported in Chinese megacities at ground levels. The concentrations of diacids increased from late May to early June, showing a maximum on 7 June, and then significantly decreased during the period 8-11 June, when the wind direction shifted from southerly to northerly. Similar temporal trends were found for ketocarboxylic acids and α-dicarbonyls as well as total carbon (TC) and water-soluble organic carbon (WSOC). The temporal variations of water-soluble organics were interpreted by the direct emission from the field burning of agricultural wastes (wheat straw) in the North China Plain and the subsequent photochemical oxidation of

Photo and Thermal Behavior of New Reinforced Polyamide-nanocomposite Montmorillonite on 2,3-Pyrazin Dicarboxylic Acid

NASA Astrophysics Data System (ADS)

Faghihi, Khalil; Samiei, Mojtaba; Hajibeygi, Mohsen

2012-06-01

Two new samples of reinforce polyamidemontmorillonite nanocomposites were synthesized by a convenient solution intercalation technique. Polyamide (PA) 3 as a source of polymer matrix was synthesized by the direct polycondensation reaction of pyrazine 2,3-dicarboxylic acid 1 with 4,4'-diamino diphenyl ether 2 in the presence of triphenyl phosphite (TPP), CaCl2, pyridine and N-methyl-2-pyrrolidone (NMP). The resulting nanocomposite films were characterized by Fourier transform infrared spectra (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The results showed that organo-modified clay was dispersed homogeneously in PA matrix. TGA indicated an enhancement of thermal stability of new nanocomposites compared with the pure polymer.

Impaired pH homeostasis in Arabidopsis lacking the vacuolar dicarboxylate transporter and analysis of carboxylic acid transport across the tonoplast.

PubMed

Hurth, Marco Alois; Suh, Su Jeoung; Kretzschmar, Tobias; Geis, Tina; Bregante, Monica; Gambale, Franco; Martinoia, Enrico; Neuhaus, H Ekkehard

2005-03-01

Arabidopsis (Arabidopsis thaliana) mutants lacking the tonoplastic malate transporter AttDT (A. thaliana tonoplast dicarboxylate transporter) and wild-type plants showed no phenotypic differences when grown under standard conditions. To identify putative metabolic changes in AttDT knock-out plants, we provoked a metabolic scenario connected to an increased consumption of dicarboxylates. Acidification of leaf discs stimulated dicarboxylate consumption and led to extremely low levels of dicarboxylates in mutants. To investigate whether reduced dicarboxylate concentrations in mutant leaf cells and, hence, reduced capacity to produce OH(-) to overcome acidification might affect metabolism, we measured photosynthetic oxygen evolution under conditions where the cytosol is acidified. AttDT::tDNA protoplasts showed a much stronger inhibition of oxygen evolution at low pH values when compared to wild-type protoplasts. Apparently citrate, which is present in higher amounts in knock-out plants, is not able to replace dicarboxylates to overcome acidification. To raise more information on the cellular level, we performed localization studies of carboxylates. Although the total pool of carboxylates in mutant vacuoles was nearly unaltered, these organelles contained a lower proportion of malate and fumarate and a higher proportion of citrate when compared to wild-type vacuoles. These alterations concur with the observation that radioactively labeled malate and citrate are transported into Arabidopsis vacuoles by different carriers. In addition, wild-type vacuoles and corresponding organelles from AttDT::tDNA mutants exhibited similar malate channel activities. In conclusion, these results show that Arabidopsis vacuoles contain at least two transporters and a channel for dicarboxylates and citrate and that the activity of AttDT is critical for regulation of pH homeostasis.

Longitudinal distributions of dicarboxylic acids, ω-oxoacids, pyruvic acid, α-dicarbonyls, and fatty acids in the marine aerosols from the central Pacific including equatorial upwelling

NASA Astrophysics Data System (ADS)

Hoque, Mir Md. Mozammal; Kawamura, Kimitaka

2016-03-01

Remote marine aerosol samples (total suspended particles) were collected during a cruise in the central Pacific from Japan to Mexico (1°59'N-35°N and 171°54'E-90°58'W). The aerosol samples were analyzed for dicarboxylic acids (C2-C11), ω-oxoacids, pyruvic acid, α-dicarbonyls, and fatty acids as well as organic and elemental carbon, water-soluble organic carbon, and total nitrogen (WSTN). During the study, diacids were the most abundant compound class followed by fatty acids, ω-oxoacids, and α-dicarbonyls. Molecular compositions of diacids showed a predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids. Oxalic acid comprises 74% of total diacids. This result suggests that photochemical production of oxalic acid is significant over the central Pacific. Spatial distributions of diacids, ω-oxoacids, pyruvic acid, α-dicarbonyls, and fatty acids together with total carbon and WSTN showed higher abundances in the eastern equatorial Pacific where the upwelling of high-nutrient waters followed by high biological productivity is common, indicating that their in situ production is important in the warmer central Pacific through photochemical oxidation from their gaseous and particulate precursors. This study demonstrates that there is a strong linkage in biogeochemical cycles of carbon in the sea-air interface via ocean upwelling, phytoplankton productivity, sea-to-air emissions of organic matter, and formation of secondary organic aerosols in the eastern equatorial Pacific.

Piezoelectric crystal microbalance measurements of enthalpy of sublimation of C2-C9 dicarboxylic acids

NASA Astrophysics Data System (ADS)

Dirri, F.; Palomba, E.; Longobardo, A.; Zampetti, E.

2016-02-01

We present here a novel experimental set-up that is able to measure the enthalpy of sublimation of a given compound by means of piezoelectric crystal microbalances (PCMs). The PCM sensors have already been used for space measurements, such as for the detection of organic and non-organic volatile species and refractory materials in planetary environments. In Earth atmospherics applications, PCMs can be also used to obtain some physical-chemical processes concerning the volatile organic compounds (VOCs) present in atmospheric environments. The experimental set-up has been developed and tested on dicarboxylic acids. In this work, a temperature-controlled effusion cell was used to sublimate VOC, creating a molecular flux that was collimated onto a cold PCM. The VOC recondensed onto the PCM quartz crystal, allowing the determination of the deposition rate. From the measurements of deposition rates, it has been possible to infer the enthalpy of sublimation of adipic acid, i.e. ΔHsub : 141.6 ± 0.8 kJ mol-1, succinic acid, i.e. 113.3 ± 1.3 kJ mol-1, oxalic acid, i.e. 62.5 ± 3.1 kJ mol-1, and azelaic acid, i.e. 124.2 ± 1.2 kJ mol-1. The results obtained show an accuracy of 1 % for succinic, adipic, and azelaic acid and within 5 % for oxalic acid and are in very good agreement with previous works (within 6 % for adipic, succinic, and oxalic acid and within 11 % or larger for azelaic acid).

Cocrystallization of adamantane-1,3-dicarboxylic acid and 4,4'-bipyridine.

PubMed

Pan, Yue; Li, Kunhao; Bi, Wenhua; Li, Jing

2008-02-01

The cocrystallization of adamantane-1,3-dicarboxylic acid (adc) and 4,4'-bipyridine (4,4'-bpy) yields a unique 1:1 cocrystal, C(12)H(16)O(4).C(10)H(8)N(2), in the C2/c space group, with half of each molecule in the asymmetric unit. The mid-point of the central C-C bond of the 4,4'-bpy molecule rests on a center of inversion, while the adc molecule straddles a twofold rotation axis that passes through two of the adamantyl C atoms. The constituents of this cocrystal are joined by hydrogen bonds, the stronger of which are O-H...N hydrogen bonds [O...N = 2.6801 (17) A] and the weaker of which are C-H...O hydrogen bonds [C...O = 3.367 (2) A]. Alternate adc and 4,4'-bpy molecules engage in these hydrogen bonds to form zigzag chains. In turn, these chains are linked through pi-pi interactions along the c axis to generate two-dimensional layers. These layers are neatly packed into a stable crystalline three-dimensional form via weak C-H...O hydrogen bonds [C...O = 3.2744 (19) A] and van der Waals attractions.

High abundances of water-soluble dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the mountain aerosols over the North China Plain during wheat burning season

NASA Astrophysics Data System (ADS)

Kawamura, K.; Tachibana, E.; Okuzawa, K.; Aggarwal, S. G.; Kanaya, Y.; Wang, Z. F.

2013-02-01

Aerosol (TSP) samples were collected at the summit of Mount Tai (elevation: 1534 m a.s.l., 36.25° N; 117.10° E) located in the North China Plain using a high-volume air sampler and pre-combusted quartz filters. Sampling was conducted on day/night or 3 h basis in the period from 29 May to 28 June 2006 during the field burning of wheat straw residue and the post-burning season. The filter samples were analyzed for low molecular weight dicarboxylic acids, ketoacids and α-dicarbonyls using capillary gas chromatography (GC) and GC-MS employing water extraction and butyl ester derivatization. Dicarboxylic acids (C2-C11, 220-6070 ng m-3) were characterized by a predominance of oxalic (C2) acid (105-3920 ng m-3) followed by succinic (C4) or malonic (C3) acid. Unsaturated aliphatic diacids, including maleic (M), isomaleic (iM) and fumaric (F) acid, were also detected together with aromatic diacids (phthalic, iso-phthalic and tere-phthalic acids). ω-Oxocarboxylic acids (C2-C9, 24-610 ng m-3) were detected as the second most abundant compound class with the predominance of glyoxylic acid (11-360 ng m-3), followed by α-ketoacid (pyruvic acid, 3-140 ng m-3) and α-dicarbonyls (glyoxal, 1-230 ng m-3 and methylglyoxal, 2-120 ng m-3). We found that these levels (> 6000 ng m-3 for diacids) are several times higher than those reported in Chinese megacities at ground levels. The concentrations of diacids increased from late May to early June showing a maximum on 7 June and then significantly decreased during 8-11 June when the wind direction shifted from northeasterly to northerly. Similar temporal trends were found for ketocarboxylic acids and α-dicarbonyls as well as total carbon (TC) and water-soluble organic carbon (WSOC). The temporal variations of water-soluble organics were interpreted by the direct emission from the field burning products of agricultural wastes (wheat straw) in the North China Plain and the subsequent photochemical oxidation of volatile and semi

Urinary concentrations of cyclohexane-1,2-dicarboxylic acid monohydroxy isononyl ester, a metabolite of the non-phthalate plasticizer di(isononyl)cyclohexane-1,2-dicarboxylate (DINCH), and markers of ovarian response among women attending a fertility center

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

Mínguez-Alarcón, Lidia, E-mail: lminguez@hsph.harv

Di(isononyl)cyclohexane-1,2-dicarboxylate (DINCH), a non-phthalate plasticizer, was introduced commercially in 2002 as an alternative to ortho-phthalate esters because of its favorable toxicological profile. However, the potential health effects from DINCH exposure remain largely unknown. We explored the associations between urinary concentrations of metabolites of DINCH on markers of ovarian response among women undergoing in vitro fertilization (IVF) treatments. Between 2011 and 2015, 113 women enrolled a prospective cohort study at the Massachusetts General Hospital Fertility Center and provided up to two urine samples prior to oocyte retrieval. The urinary concentrations of two DINCH metabolites, cyclohexane-1,2-dicarboxylic acid monohydroxy isononyl ester (MHiNCH) andmore » cyclohexane-1,2-dicarboxylic acid monocarboxyisooctyl ester (MCOCH), were quantified by isotope dilution tandem mass spectrometry. We used generalized linear mixed models to evaluate the association between urinary metabolite concentrations and markers of ovarian response, accounting for multiple IVF cycles per woman via random intercepts. On average, women with detectable urinary MHiNCH concentrations, as compared to those below LOD, had a lower estradiol levels (−325 pmol/l, p=0.09) and number of retrieved oocytes (−1.8, p=0.08), with a stronger association among older women. However, urinary MHiNCH concentrations were unrelated to mature oocyte yield and endometrial wall thickness. In conclusion, we found suggestive negative associations between urinary MHiNCH concentrations and peak estradiol levels and number of total oocyte yields. This is the first study evaluating the effect of DINCH exposure on human reproductive health and raises the need for further experimental and epidemiological studies to better understand the potential effects of this chemical on health. - Highlights: • Women with detectable urinary MHiNCH concentrations had a lower estradiol levels and number of

Methanogenic Paraffin Biodegradation: Alkylsuccinate Synthase Gene Quantification and Dicarboxylic Acid Production.

PubMed

Oberding, Lisa K; Gieg, Lisa M

2018-01-01

Paraffinic n -alkanes (>C 17 ) that are solid at ambient temperature comprise a large fraction of many crude oils. The comparatively low water solubility and reactivity of these long-chain alkanes can lead to their persistence in the environment following fuel spills and pose serious problems for crude oil recovery operations by clogging oil production wells. However, the degradation of waxy paraffins under the anoxic conditions characterizing contaminated groundwater environments and deep subsurface energy reservoirs is poorly understood. Here, we assessed the ability of a methanogenic culture enriched from freshwater fuel-contaminated aquifer sediments to biodegrade the model paraffin n -octacosane (C 28 H 58 ). Compared with that in controls, the consumption of n -octacosane was coupled to methane production, demonstrating its biodegradation under these conditions. Smithella was postulated to be an important C 28 H 58 degrader in the culture on the basis of its high relative abundance as determined by 16S rRNA gene sequencing. An identified assA gene (known to encode the α subunit of alkylsuccinate synthase) aligned most closely with those from other Smithella organisms. Quantitative PCR (qPCR) and reverse transcription qPCR assays for assA demonstrated significant increases in the abundance and expression of this gene in C 28 H 58 -degrading cultures compared with that in controls, suggesting n -octacosane activation by fumarate addition. A metabolite analysis revealed the presence of several long-chain α,ω-dicarboxylic acids only in the C 28 H 58 -degrading cultures, a novel observation providing clues as to how methanogenic consortia access waxy hydrocarbons. The results of this study broaden our understanding of how waxy paraffins can be biodegraded in anoxic environments with an application toward bioremediation and improved oil recovery. IMPORTANCE Understanding the methanogenic biodegradation of different classes of hydrocarbons has important

Methanogenic Paraffin Biodegradation: Alkylsuccinate Synthase Gene Quantification and Dicarboxylic Acid Production

PubMed Central

Oberding, Lisa K.

2017-01-01

ABSTRACT Paraffinic n-alkanes (>C17) that are solid at ambient temperature comprise a large fraction of many crude oils. The comparatively low water solubility and reactivity of these long-chain alkanes can lead to their persistence in the environment following fuel spills and pose serious problems for crude oil recovery operations by clogging oil production wells. However, the degradation of waxy paraffins under the anoxic conditions characterizing contaminated groundwater environments and deep subsurface energy reservoirs is poorly understood. Here, we assessed the ability of a methanogenic culture enriched from freshwater fuel-contaminated aquifer sediments to biodegrade the model paraffin n-octacosane (C28H58). Compared with that in controls, the consumption of n-octacosane was coupled to methane production, demonstrating its biodegradation under these conditions. Smithella was postulated to be an important C28H58 degrader in the culture on the basis of its high relative abundance as determined by 16S rRNA gene sequencing. An identified assA gene (known to encode the α subunit of alkylsuccinate synthase) aligned most closely with those from other Smithella organisms. Quantitative PCR (qPCR) and reverse transcription qPCR assays for assA demonstrated significant increases in the abundance and expression of this gene in C28H58-degrading cultures compared with that in controls, suggesting n-octacosane activation by fumarate addition. A metabolite analysis revealed the presence of several long-chain α,ω-dicarboxylic acids only in the C28H58-degrading cultures, a novel observation providing clues as to how methanogenic consortia access waxy hydrocarbons. The results of this study broaden our understanding of how waxy paraffins can be biodegraded in anoxic environments with an application toward bioremediation and improved oil recovery. IMPORTANCE Understanding the methanogenic biodegradation of different classes of hydrocarbons has important applications for

Alternative plasticizer, 4-cyclohexene-1,2-dicarboxylic acid dinonyl ester, for blood containers with protective effects on red blood cells and improved cold resistance.

PubMed

Morishita, Yuki; Nomura, Yusuke; Fukui, Chie; Fujisawa, Ayano; Watanabe, Kayo; Fujimaki, Hideo; Kumada, Hidefumi; Inoue, Kaoru; Morikawa, Tomomi; Takahashi, Miwa; Kawakami, Tsuyoshi; Sakoda, Hideyuki; Mukai, Tomokazu; Yuba, Toshiyasu; Inamura, Ken-Ichi; Tanoue, Akito; Miyazaki, Ken-Ichi; Chung, Ung-Il; Ogawa, Kumiko; Yoshida, Midori; Haishima, Yuji

2018-04-01

Di (2-ethylhexyl) phthalate (DEHP), a typical plasticizer used for polyvinyl chloride (PVC), is eluted from PVC-made blood containers and protects against red blood cell (RBC) hemolysis. However, concerns have arisen regarding the reproductive and developmental risks of DEHP in humans, and the use of alternative plasticizers for medical devices has been recommended worldwide. In this study, we propose that the use of a novel plasticizer, 4-cyclohexene-1,2-dicarboxylic acid dinonyl ester (DL9TH), could help produce more useful and safe blood containers. PVC sheet containing DL9TH and di (2-ethylhexyl) 4-cyclohexene-1,2-dicarboxylate (DOTH) provides comparable or superior protective effects to RBCs relative to PVC sheet containing DEHP or di-isononyl-cyclohexane-1,2-dicarboxylate (DINCH ® , an alternative plasticizer that has been used in PVC sheets for blood containers). The total amount of plasticizer eluted from DOTH/DL9TH-PVC sheets is nearly the same as that eluted from DEHP-PVC sheets. In addition, DOTH/DL9TH-PVC has better cold resistance than DEHP- and DINCH ® -PVC sheets. In vitro and in vivo tests for biological safety based on International Organization for Standardization guidelines (10993 series) suggest that the DOTH/DL9TH-PVC sheet can be used safely. Subchronic toxicity testing of DL9TH in male rats in accordance with the principles of Organisation for Economic Co-operation and Development Test Guideline 408 showed that DL9TH did not induce adverse effects up to the highest dose level tested (717 mg/kg body weight/day). There were no effects on testicular histopathology and sperm counts, and no indications of endocrine effects: testosterone, thyroid-stimulating hormone, follicle-stimulating hormone, and 17β-estradiol were unchanged by the treatment, compared with the control group. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1052-1063, 2018. © 2017 Wiley Periodicals, Inc.

Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

NASA Astrophysics Data System (ADS)

Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

2015-01-01

To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic aerosols (BA), for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2) and malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment, except for ω-oxooctanoic acid (ωC8) that showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids dominates their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

NASA Astrophysics Data System (ADS)

Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

2015-07-01

To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

Preparation, characterisation and study of in vitro biologically active azamacrocyclic Cu(II) dicarboxylate complexes

NASA Astrophysics Data System (ADS)

Antonijević-Nikolić, Mirjana; Antić-Stanković, Jelena; Tanasković, Sladjana B.; Korabik, Maria J.; Gojgić-Cvijović, Gordana; Vučković, Gordana

2013-12-01

New cationic Cu(II) complexes with N, N‧, N″, N″‧-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane (tpmc) and aliphatic dicarboxylic acids: pentanedioic (glutaric acid = glutH2), hexanedioic acid (adipic acid = adipH2) and decanedioic acid (sebacic acid = sebH2) of general formula [Cu4(L)(tpmc)2](ClO4)6·xH2O, L = glut, x = 2; L = adip, x = 7; L = seb, x = 6 were isolated. Their composition and charges are proposed based on elemental analyses and molar conductivity measurements. By the comparison of their UV-Vis, reflectance, FTIR and EPR spectral data, CV and SQUID magnetic measurements, with those for the complex with butanedioic acid (succinic acid = succH2) of known molecular structure and analysis of LC/MS spectra, geometry with two [Cu2tpmc]4+ units bridged by dicarboxylate dianion engaging all oxygens is proposed. Within units, Cu(II) ions are also bridged with N portion of cyclam ring. All four complexes were screened to in vitro antimicrobial and cytotoxic activity along with free primary and secondary ligands, Cu(II) salt and solvent controls. Detected antibacterial and cytotoxic activity for the complexes was enhanced in most cases than the corresponding controls.

Impaired pH Homeostasis in Arabidopsis Lacking the Vacuolar Dicarboxylate Transporter and Analysis of Carboxylic Acid Transport across the Tonoplast1

PubMed Central

Hurth, Marco Alois; Suh, Su Jeoung; Kretzschmar, Tobias; Geis, Tina; Bregante, Monica; Gambale, Franco; Martinoia, Enrico; Neuhaus, H. Ekkehard

2005-01-01

Arabidopsis (Arabidopsis thaliana) mutants lacking the tonoplastic malate transporter AttDT (A. thaliana tonoplast dicarboxylate transporter) and wild-type plants showed no phenotypic differences when grown under standard conditions. To identify putative metabolic changes in AttDT knock-out plants, we provoked a metabolic scenario connected to an increased consumption of dicarboxylates. Acidification of leaf discs stimulated dicarboxylate consumption and led to extremely low levels of dicarboxylates in mutants. To investigate whether reduced dicarboxylate concentrations in mutant leaf cells and, hence, reduced capacity to produce OH− to overcome acidification might affect metabolism, we measured photosynthetic oxygen evolution under conditions where the cytosol is acidified. AttDT::tDNA protoplasts showed a much stronger inhibition of oxygen evolution at low pH values when compared to wild-type protoplasts. Apparently citrate, which is present in higher amounts in knock-out plants, is not able to replace dicarboxylates to overcome acidification. To raise more information on the cellular level, we performed localization studies of carboxylates. Although the total pool of carboxylates in mutant vacuoles was nearly unaltered, these organelles contained a lower proportion of malate and fumarate and a higher proportion of citrate when compared to wild-type vacuoles. These alterations concur with the observation that radioactively labeled malate and citrate are transported into Arabidopsis vacuoles by different carriers. In addition, wild-type vacuoles and corresponding organelles from AttDT::tDNA mutants exhibited similar malate channel activities. In conclusion, these results show that Arabidopsis vacuoles contain at least two transporters and a channel for dicarboxylates and citrate and that the activity of AttDT is critical for regulation of pH homeostasis. PMID:15728336

Effect of aliphatic, monocarboxylic, dicarboxylic, heterocyclic and sulphur-containing amino acids on Leishmania spp. chemotaxis.

PubMed

Diaz, E; Zacarias, A K; Pérez, S; Vanegas, O; Köhidai, L; Padrón-Nieves, M; Ponte-Sucre, A

2015-11-01

In the sand-fly mid gut, Leishmania promastigotes are exposed to acute changes in nutrients, e.g. amino acids (AAs). These metabolites are the main energy sources for the parasite, crucial for its differentiation and motility. We analysed the migratory behaviour and morphological changes produced by aliphatic, monocarboxylic, dicarboxylic, heterocyclic and sulphur-containing AAs in Leishmania amazonensis and Leishmania braziliensis and demonstrated that L-methionine (10-12 m), L-tryptophan (10-11 m), L-glutamine and L-glutamic acid (10-6 m), induced positive chemotactic responses, while L-alanine (10-7 m), L-methionine (10-11 and 10-7 m), L-tryptophan (10-11 m), L-glutamine (10-12 m) and L-glutamic acid (10-9 m) induced negative chemotactic responses. L-proline and L-cysteine did not change the migratory potential of Leishmania. The flagellum length of L. braziliensis, but not of L. amazonensis, decreased when incubated in hyperosmotic conditions. However, chemo-repellent concentrations of L-alanine (Hypo-/hyper-osmotic conditions) and L-glutamic acid (hypo-osmotic conditions) decreased L. braziliensis flagellum length and L-methionine (10-11 m, hypo-/hyper-osmotic conditions) decreased L. amazonensis flagellum length. This chemotactic responsiveness suggests that Leishmania discriminate between slight concentration differences of small and structurally closely related molecules and indicates that besides their metabolic effects, AAs play key roles linked to sensory mechanisms that might determine the parasite's behaviour.

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

PubMed Central

Bassanini, Ivan; Hult, Karl

2015-01-01

Summary Dicarboxylic acids and their derivatives (esters and anhydrides) have been used as acylating agents in lipase-catalyzed reactions in organic solvents. The synthetic outcomes have been dimeric or hybrid derivatives of bioactive natural compounds as well as functionalized polyesters. PMID:26664578

Genome-scale model-driven strain design for dicarboxylic acid production in Yarrowia lipolytica.

PubMed

Mishra, Pranjul; Lee, Na-Rae; Lakshmanan, Meiyappan; Kim, Minsuk; Kim, Byung-Gee; Lee, Dong-Yup

2018-03-19

Recently, there have been several attempts to produce long-chain dicarboxylic acids (DCAs) in various microbial hosts. Of these, Yarrowia lipolytica has great potential due to its oleaginous characteristics and unique ability to utilize hydrophobic substrates. However, Y. lipolytica should be further engineered to make it more competitive: the current approaches are mostly intuitive and cumbersome, thus limiting its industrial application. In this study, we proposed model-guided metabolic engineering strategies for enhanced production of DCAs in Y. lipolytica. At the outset, we reconstructed genome-scale metabolic model (GSMM) of Y. lipolytica (iYLI647) by substantially expanding the previous models. Subsequently, the model was validated using three sets of published culture experiment data. It was finally exploited to identify genetic engineering targets for overexpression, knockout, and cofactor modification by applying several in silico strain design methods, which potentially give rise to high yield production of the industrially relevant long-chain DCAs, e.g., dodecanedioic acid (DDDA). The resultant targets include (1) malate dehydrogenase and malic enzyme genes and (2) glutamate dehydrogenase gene, in silico overexpression of which generated additional NADPH required for fatty acid synthesis, leading to the increased DDDA fluxes by 48% and 22% higher, respectively, compared to wild-type. We further investigated the effect of supplying branched-chain amino acids on the acetyl-CoA turn-over rate which is key metabolite for fatty acid synthesis, suggesting their significance for production of DDDA in Y. lipolytica. In silico model-based strain design strategies allowed us to identify several metabolic engineering targets for overproducing DCAs in lipid accumulating yeast, Y. lipolytica. Thus, the current study can provide a methodological framework that is applicable to other oleaginous yeasts for value-added biochemical production.

Solid-state acid-base interactions in complexes of heterocyclic bases with dicarboxylic acids: crystallography, hydrogen bond analysis, and 15N NMR spectroscopy.

PubMed

Li, Z Jane; Abramov, Yuriy; Bordner, Jon; Leonard, Jason; Medek, Ales; Trask, Andrew V

2006-06-28

A cancer candidate, compound 1, is a weak base with two heterocyclic basic nitrogens and five hydrogen-bonding functional groups, and is sparingly soluble in water rendering it unsuitable for pharmaceutical development. The crystalline acid-base pairs of 1, collectively termed solid acid-base complexes, provide significant increases in the solubility and bioavailability compared to the free base, 1. Three dicarboxylic acid-base complexes, sesquisuccinate 2, dimalonate 3, and dimaleate 4, show the most favorable physicochemical profiles and are studied in greater detail. The structural analyses of the three complexes using crystal structure and solid-state NMR reveal that the proton-transfer behavior in these organic acid-base complexes vary successively correlating with Delta pKa. As a result, 2 is a neutral complex, 3 is a mixed ionic and zwitterionic complex and 4 is an ionic salt. The addition of the acidic components leads to maximized hydrogen bond interactions forming extended three-dimensional networks. Although structurally similar, the packing arrangements of the three complexes are considerably different due to the presence of multiple functional groups and the flexible backbone of 1. The findings in this study provide insight into the structural characteristics of complexes involving heterocyclic bases and carboxylic acids, and demonstrate that X-ray crystallography and 15N solid-state NMR are truly complementary in elucidating hydrogen bonding interactions and the degree of proton transfer of these complexes.

Latitudinal distributions of atmospheric dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls over the western North Pacific: Sources and formation pathways

NASA Astrophysics Data System (ADS)

Bikkina, Srinivas; Kawamura, Kimitaka; Miyazaki, Yuzo

2015-05-01

The present study aims to assess the molecular distributions of water-soluble dicarboxylic acids (diacids: C2-C12), oxocarboxylic acids (C2-C9), and α-dicarbonyls (glyoxal and methylglyoxal) in aerosols collected over the western North Pacific (WNP) during a summer cruise (August to September 2008). The measured water-soluble organics show pronounced latitudinal distributions with higher concentrations in the region of 30°N-45°N (average 63 ng m-3) than 10°N-30°N (18 ng m-3). Mass fraction of oxalic acid (C2) in total aliphatic diacids (ΣC2-C12) showed higher values (72 ± 10%) in lower latitude (10°N-30°N) than that (56 ± 16%) in higher latitude (30°N-45°N), suggesting a photochemical production of C2 due to an increased insolation over the tropical WNP. A similar trend was found in other diagnostic ratios such as oxalic to succinic (C2/C4) and oxalic to glyoxylic acid (C2/ωC2), which further corroborate an enhanced photochemical aging over the WNP. In addition, relative abundances of oxalic acid in total diacids showed a marked increase as a function of ambient temperature, supporting their photochemical production. Constantly low concentration ratios of adipic and phthalic acids relative to azelaic acid suggest a small contribution of anthropogenic sources and an importance of oceanic sources during the study period. Significant production of C2 through oxidation of biogenic volatile organic compounds emitted from the sea surface is also noteworthy, as inferred from the strong linear correlations among water-soluble organic carbon, methanesulphonic acid, and oxalic acid. Sea-to-air emission of unsaturated fatty acids also contributes to formation of diacids over the WNP.

Structure-activity relationships among derivatives of dicarboxylic acid esters of tropine.

PubMed

Gyermek, Laszlo

2002-10-01

Several categories of neuromuscular blocking bisquaternary tropine and tropane derivatives were synthesized and studied in the past five decades, mainly with the purpose of arriving at meaningful information about structure-activity relationships. Such a structure-activity relationship database is important in the development of new muscle relaxants with improved pharmacological characteristics. Although quaternary tropine diesters were explored since 1952, most of them were developed in the last decade. Over 250 such agents are being reviewed here. The skeleton of the majority of them consists of two tropines, connected through their 3-OH group with various dicarboxylic acid ester linkages and quaternized by several mostly di- and trisubstituted benzyl groups. The significance of changing the quaternizing group; the diester linker; and, to a smaller extent, the substituents and their steric orientation on the tropane ring and some alterations of the tropane ring itself have been explored in in vivo experiments on anesthetized rats. Di- or trisubstituted alkoxy and/or acyloxybenzyl quaternaries of certain tropinyl diesters, e.g., glutaryl, fumaryl, and cyclobutane-1,2-dicarboxylyl, showed an optimal profile with respect to desirable neuromuscular blocking actions and side effects, which was confirmed on other experimental animal species. The details of the structural changes toward obtaining new ultrashort-acting nondepolarizing muscle relaxants are discussed.

Selective Mono-reduction of Pyrrole-2,5 and 2,4-Dicarboxylates.

PubMed

Yasui, Eiko; Tsuda, Jyunpei; Ohnuki, Satoshi; Nagumo, Shinji

2016-01-01

Pyrrole-2,5-dicarboxylates were rapidly and selectively reduced to the corresponding mono-alcohol using 3 eq of diisobutylaluminum hydride at 0°C. Pyrrole-2,4-dicarboxylate showed the same reactivity; however, the selectivity decreased with pyrrole-3,4-dicarboxylate. When the nitrogen atom of the pyrrole-2,5-dicarboxylate is protected with a benzyl group, selective mono-reduction does not occur. Considering that furan-2,5-dicarboxylates did not give the corresponding mono-alcohol under the same conditions, the unprotected nitrogen atom of pyrrole apparently plays an important role in this selective mono-reduction.

Identification of three new phase II metabolites of a designer drug methylone formed in rats by N-demethylation followed by conjugation with dicarboxylic acids.

PubMed

Židková, Monika; Linhart, Igor; Balíková, Marie; Himl, Michal; Dvořáčková, Veronika; Lhotková, Eva; Páleníček, Tomáš

2018-06-01

1. Methylone (3,4-methylenedioxy-N-methylcathinone, MDMC), which appeared on the illicit drug market in 2004, is a frequently abused synthetic cathinone derivative. Known metabolic pathways of MDMC include N-demethylation to normethylone (3,4-methylenedioxycathinone, MDC), aliphatic chain hydroxylation and oxidative demethylenation followed by monomethylation and conjugation with glucuronic acid and/or sulphate. 2. Three new phase II metabolites, amidic conjugates of MDC with succinic, glutaric and adipic acid, were identified in the urine of rats dosed subcutaneously with MDMC.HCl (20 mg/kg body weight) by LC-ESI-HRMS using synthetic reference standards to support identification. 3. The main portion of administered MDMC was excreted unchanged. Normethylone, was a major urinary metabolite, of which a minor part was conjugated with dicarboxylic acids. 4. Previously identified ring-opened metabolites 4-hydroxy-3-methoxymethcathinone (4-OH-3-MeO-MC), 3-hydroxy-4-methoxymeth-cathinone (3-OH-4-MeO-MC) and 3,4-dihydroxymethcathinone (3,4-di-OH-MC) mostly in conjugated form with glucuronic and/or sulphuric acids were also detected. 5. Also, ring-opened metabolites derived from MDC, namely, 4-hydroxy-3-methoxycathinone (4-OH-3-MeO-C), 3-hydroxy-4-methoxycathinone (3-OH-4-MeO-C) and 3,4-dihydroxycathinone (3,4-di-OH-C) were identified for the first time in vivo.

Pyridine 2,4-dicarboxylic acid suppresses tomato seedling growth

NASA Astrophysics Data System (ADS)

Fragkostefanakis, Sotirios; Kaloudas, Dimitrios; Kalaitzis, Panagiotis

2018-01-01

Pyridine 2,4-dicarboxylic acid is a structural analogue of 2-oxoglutarate and is known to inhibit 2-oxoglutare-dependent dioxygenases. The effect of this inhibitor in tomato seedlings grown in MS media supplied with various concentrations of PDCA was investigated, resulting in shorter roots and hypocotyls in a dose-dependent manner. The partial inhibition of growth in roots was more drastic compared to hypocotyls and was attributed to a decrease in the elongation of root and hypocotyl cells. Concentrations of 100 and 250 μΜ of PDCA decreased hydroxyproline content in roots while only the 250 μΜ treatment reduced the hydroxyproline content in shoots. Seedlings treated with 100 μΜ PDCA exhibited enhanced growth of hypocotyl and cotyledon cells and higher hydroxyproline content resulting in cotyledons with greater surface area. However, no alterations in hypocotyl length were observed. Prolyl 4 hydroxylases (P4Hs) are involved in the O-glycosylation of AGPs and were also highly expressed during seedling growth. Moreover PDCA induced a decrease in the accumulation of HRGPs and particularly in AGPs-bound epitopes in a dose dependent-manner while more drastic reduction were observed in roots compared to shoots. In addition, bulged root epidermal cells were observed at the high concentration of 250 μΜ which is characteristic of root tissues with glycosylation defects. These results indicate that PDCA induced pleiotropic effects during seedling growth while further studies are required to better investigate the physiological significance of this 2-oxoglutarate analogue. This pharmacological approach might be used as a tool to better understand the physiological significance of HRGPs and probably P4Hs in various growth and developmental programs in plants.

A review of dicarboxylic acids and related compounds in atmospheric aerosols: Molecular distributions, sources and transformation

NASA Astrophysics Data System (ADS)

Kawamura, Kimitaka; Bikkina, Srinivas

2016-03-01

This review aims to update our understanding on molecular distributions of water-soluble dicarboxylic acids and related compounds in atmospheric aerosols with a focus on their geographical variability, size distribution, sources and formation pathways. In general, molecular distributions of diacids in aerosols from the continental sites and over the open ocean waters are often characterized by the predominance of oxalic acid (C2) followed by malonic acid (C3) and/or succinic acid (C4), while those sampled over the polar regions often follow the order of C4 ≥ C2 and C3. The most abundant and ubiquitous diacid is oxalic acid, which is principally formed via atmospheric oxidation of its higher homologues of long chain diacids and other pollution-derived organic precursors (e.g., olefins and aromatic hydrocarbons). However, its occurrence in marine aerosols is mainly due to the transport from continental outflows (e.g., East Asian outflow during winter/spring to the North Pacific) and/or governed by photochemical/aqueous phase oxidation of biogenic unsaturated fatty acids (e.g., oleic acid) and isoprene emitted from the productive open ocean waters. The long-range atmospheric transport of pollutants from mid latitudes to the Arctic in dark winter facilitates to accumulate the reactants prior to their intense photochemical oxidation during springtime polar sunrise. Furthermore, the relative abundances of C2 in total diacid mass showed similar temporal trends with downward solar irradiation and ambient temperatures, suggesting the significance of atmospheric photochemical oxidation processing. Compound-specific isotopic analyses of oxalic acid showed the highest δ13C among diacids whereas azelaic acid showed the lowest value, corroborating the significance of atmospheric aging of oxalic acid. On the other hand, other diacids gave intermediate values between these two diacids, suggesting that aging of oxalic acid is associated with 13C enrichment.

Synthesis and physicochemical properties of the furan dicarboxylic acid, 3-carboxy-4-methyl-5-propyl-2-furanpropanoic acid, an inhibitor of plasma protein binding in uraemia.

PubMed

Costigan, M G; Gilchrist, T L; Lindup, W E

1996-06-01

The furan dicarboxylic acid, 3-carboxy-4-methyl-5-propyl-2-furanpropanoic acid (5-propyl FPA) accumulates in the plasma of patients with chronic renal failure and is a major contributor to the drug binding defect of uraemic plasma. This acid has also been implicated in several other aspects of the uraemic syndrome: anaemia, irregularities of thyroid function, neurological symptoms and inhibition of active tubular secretion. The acid is not commercially available and its synthesis, starting with Meldrum's acid and methyl succinyl chloride, is described. The pKa values were measured by titration and values of 3.2 and 3.6 respectively were assigned to the carboxylic acid groups attached directly to the ring at position 3 and at position 2 (on the side-chain). The partition coefficient (log P) between hydrochloric acid and octanol was 1.2 and the distribution coefficient (log D; octanol-phosphate buffer pH 7.4) was -0.59. The pKa values and the degree of hydrophobic character of 5-propyl FPA are consistent with those of other protein-bound acids which undergo active tubular secretion by the kidney and this substance may serve as an endogenous marker for the effects of drugs and disease on this process.

Water-soluble dicarboxylic acids and ketocarboxylic acids in the aerosols collected during ACE-Asia/C-130 aircraft campaign 2001

NASA Astrophysics Data System (ADS)

Kawamura, K.; Mochida, M.; Uemoto, N.; Bertram, T.; Huebert, B.

2001-12-01

During the ACE-Asia campaign with C-130 aircraft, aerosol samples were collected over the western North Pacific, East China Sea, and Japan Sea, as well as over Japanese Islands and Korean Peninsula in 8 April to 3 May 2001. The filter samples (N=15) were extracted with organic-free pure water to separate water-soluble dicarboxylic acids and related compounds. The extracts were reacted with 14% BF3 in n-butanol and the dibutyl esters and other derivatives were determined using a capillary GC and GC/MS. The results showed that 14 species of diacids (C2-C11) and 4 species of ketoacids (C2-C4) were detected in the aerosols over the East Asia. Total concentrations of the diacids were 113-500 (av. 330) ng/m3 whereas those of ketoacids were 43-260 (av. 103) ng/m3. The concentrations are equivalent to or more abundant than those reported for the urban Tokyo atmosphere in this season on the ground level. All the samples showed that oxalic acid (C2) is the most abundant diacid, which accounted for 58-83% of total diacids. These values are greater than that (ca. 50%) reported in the urban air near the ground, suggesting that oxalic acid is preferentially produced and/or longer diacids are selectively decomposed in the upper troposphere. Malonic (C3) acid is the second most abundant species followed by succinic (C4) acid. Longer diacids are less abundant, but azelaic (C9) acid is generally more abundant than C6-C8 diacids. Glyoxylic acid (C2) is the most abundant ketoacid followed by pyruvic acid. However, C3 and C4 omega-oxoacids were found as minor species. Although oxalic acid is the dominant component in the aerosols, few samples showed the predominance of glyoxylic acid over oxalic acid. This feature has not been reported for the urban aerosols collected near the ground level. We will discuss a potential photochemical production of water-soluble organic acids in the upper troposphere over the eastern ridge of the Asian continent.

Synthesis, characterization and biological activities of metal(II) dipicolinate complexes derived from pyridine-2,6-dicarboxylic acid and 2-(piperazin-1-yl)ethanol

NASA Astrophysics Data System (ADS)

Büyükkıdan, Nurgün; Yenikaya, Cengiz; İlkimen, Halil; Karahan, Ceyda; Darcan, Cihan; Korkmaz, Tülin; Süzen, Yasemin

2015-12-01

The new water-soluble and air stable compounds (H2ppz)[Co(dipic)2]·6H2O (1), (H2ppz)[Ni(dipic)2]·6H2O (2) and (H2ppz)[Zn(dipic)2]·6H2O (3) were prepared by the reaction of corresponding metal(II) acetates and a proton transfer salt, (H2ppz) (Hdipic)2, (4) of pyridine-2,6-dicarboxylic acid (H2dipic) and 2-(piperazin-1-yl)ethanol (ppz). The compounds 1-3 were characterized by elemental, IR, UV-vis. thermal analyses, magnetic measurement and single crystal X-ray diffraction studies. The molecular structures of the title compounds consist of one 1-(2-hydroxyethyl)piperazine-1,4-diium (H2ppz+2) cation, one bis(pyridine-2,6-dicarboxylate)metal(II) [M(dipic)2]2- anion, and six uncoordinated water molecules. In compounds 1-3 the metal ions coordinate to two oxygen and one nitrogen atoms of two pyridine-2,6-dicarboxylate molecules forming an octahedral environment. Antimicrobial activities against Gram (-) wild type (Escherichia coli and Pseudomonas aeruginosa), Gram (+) wild type (Staphylococcus aureus, Staphylococcus epidermidis, Bacillus cereus and Bacillus subtilis) and clinical isolate (Morganella morganii, Proteus vulgaris and Enterobacter aeruginosa) were also studied. The results were reported, discussed and compared with the corresponding starting materials ((H2ppz) (Hdipic)2 (4), H2dipic and ppz). MIC (Minimal Inhibition Concentration) values of the newly synthesized compounds were determined as 4000 μg/ml (except B. subtilis and clinical isolate E. aeruginosa, >4000 μg/ml).

Benzene-1,3-dicarboxylic acid 2,5-dimethylpyrrole derivatives as multiple inhibitors of bacterial Mur ligases (MurC-MurF).

PubMed

Perdih, Andrej; Hrast, Martina; Barreteau, Hélène; Gobec, Stanislav; Wolber, Gerhard; Solmajer, Tom

2014-08-01

Enzymes catalyzing the biosynthesis of bacterial peptidoglycan represent traditionally a collection of highly selective targets for novel antibacterial drug design. Four members of the bacterial Mur ligase family-MurC, MurD, MurE and MurF-are involved in the intracellular steps of peptidoglycan biosynthesis, catalyzing the synthesis of the peptide moiety of the Park's nucleotide. In our previous virtual screening campaign, a chemical class of benzene-1,3-dicarboxylic acid 2,5-dimethylpyrrole derivatives exhibiting dual MurD/MurE inhibition properties was discovered. In the present study we further investigated this class of compounds by performing inhibition assays on all four Mur ligases (MurC-MurF). Furthermore, molecular dynamics (MD) simulation studies of one of the initially discovered compound 1 were performed to explore its geometry as well as its energetic behavior based on the Linear Interaction Energy (LIE) method. Further in silico virtual screening (VS) experiments based on the parent active compound 1 were conducted to optimize the discovered series. Selected hits were assayed against all Escherichia coli MurC-MurF enzymes in biochemical inhibition assays and molecules 10-14 containing benzene-1,3-dicarboxylic acid 2,5-dimethylpyrrole coupled with five member-ring rhodanine moiety were found to be multiple inhibitors of the whole MurC-MurF cascade of bacterial enzymes in the micromolar range. Steady-state kinetics studies suggested this class to act as competitive inhibitors of the MurD enzyme towards d-Glu. These compounds represent novel valuable starting point in the development of novel antibacterial agents. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls in fine aerosols over central Alaska: Implications for sources and atmospheric processes

NASA Astrophysics Data System (ADS)

Deshmukh, Dhananjay K.; Mozammel Haque, Md.; Kawamura, Kimitaka; Kim, Yongwon

2018-04-01

The presence of water-soluble dicarboxylic acids in atmospheric aerosols has a significant influence on the regional radiative forcing through direct aerosol effect and cloud formation process. Fine aerosol (PM2.5) samples collected in central Alaska (Fairbanks: 64.51°N and 147.51°W) during summer of 2009 were measured for water-soluble diacids (C2-C12), oxoacids (C2-C9) and α-dicarbonyls (C2-C3) as well as elemental carbon (EC), organic carbon (OC) and water-soluble OC (WSOC) to assess their sources and formation processes. We found the predominance of oxalic acid (C2) followed by malonic (C3) and succinic acid (C4) in Alaskan aerosols. Higher C3/C4 diacid ratios (ave. 1.2) in Alaskan aerosols than those reported for fresh aerosols emitted from fossil fuel combustion (ave. 0.35) and biomass burning (0.51-0.66) suggest that organic aerosols in central Alaska were photochemically processed. The relatively high correlations of major diacids and related compounds with levoglucosan (r = 0.80-0.99) than those with 2-methylglyceric acid (r = 0.59-0.98) suggest that they were significantly produced from biomass burning emission. Strong correlations of C2 with normal-chain saturated diacids (C3-C9: r = 0.80-0.98), glyoxylic acid (ωC2: r = 0.95) and methylglyoxal (MeGly: r = 0.88), together with strong correlations of solar radiation with ratio of C2 to C2-C12 diacids (r = 0.83), ωC2 (r = 0.80) and MeGly (r = 0.82) suggest that oxalic acid in PM2.5 aerosol was produced by the photooxidation of higher homologous diacids, glyoxylic acid and methylglyoxal in the atmosphere of central Alaska. These results reveal that photochemical processing of organic precursors mainly produced from biomass burning control the water-soluble organic chemical composition of fine aerosols in central Alaska.

Distributions of low molecular weight dicarboxylic acids, ketoacids and α-dicarbonyls in the marine aerosols collected over the Arctic Ocean during late summer

NASA Astrophysics Data System (ADS)

Kawamura, K.; Ono, K.; Tachibana, E.; Charriére, B.; Sempéré, R.

2012-11-01

Oxalic and other small dicarboxylic acids have been reported as important water-soluble organic constituents of atmospheric aerosols from different environments. Their molecular distributions are generally characterized by the predominance of oxalic acid (C2) followed by malonic (C3) and/or succinic (C4) acids. In this study, we collected marine aerosols from the Arctic Ocean during late summer in 2009 when sea ice was retreating. The marine aerosols were analyzed for the molecular distributions of dicarboxylic acids as well as ketocarboxylic acids and α-dicarbonyls to better understand the source of water-soluble organics and their photochemical processes in the high Arctic marine atmosphere. We found that diacids are more abundant than ketoacids and α-dicarbonyls, but their concentrations are generally low (< 30 ng m-3), except for one sample (up to 70 ng m-3) that was collected near the mouth of Mackenzie River during clear sky condition. Although the molecular compositions of diacids are in general characterized by the predominance of oxalic acid, a depletion of C2 was found in two samples in which C4 became the most abundant. Similar depletion of oxalic acid has previously been reported in the Arctic aerosols collected at Alert after polar sunrise and in the summer aerosols from the coast of Antarctica. Because the marine aerosols that showed a depletion of C2 were collected under the overcast and/or foggy conditions, we suggest that a photochemical decomposition of oxalic acid may have occurred in aqueous phase of aerosols over the Arctic Ocean via the photo dissociation of oxalate-Fe (III) complex. We also determined stable carbon isotopic compositions (δ13C) of bulk aerosol carbon and individual diacids. The δ13C of bulk aerosols showed -26.5‰ (range: -29.7 to -24.7‰, suggesting that marine aerosol carbon is derived from both terrestrial and marine organic materials. In contrast, oxalic acid showed much larger δ13C values (average: -20.9‰, range

Distributions of low molecular weight dicarboxylic acids, ketoacids and α-dicarbonyls in the marine aerosols collected over the Arctic Ocean during late summer

NASA Astrophysics Data System (ADS)

Kawamura, K.; Ono, K.; Tachibana, E.; Charriére, B.; Sempéré, R.

2012-08-01

Oxalic and other small dicarboxylic acids have been reported as important water-soluble organic constituents of atmospheric aerosols from different environments. Their molecular distributions are generally characterized by the predominance of oxalic acid (C2) followed by malonic (C3) and/or succinic (C4) acids. In this study, we collected marine aerosols from the Arctic Ocean during late summer in 2009 when sea ice is retreated. The marine aerosols were analyzed for the molecular distributions of dicarboxylic acids as well as ketocarboxylic acids and α-dicarbonyls to better understand the source of water-soluble organics and their photochemical processes in the high Arctic marine atmosphere. We found that diacids are more abundant than ketoacids and α-dicarbonyls, but their concentrations are generally low (< 30 ng m-3), except for one sample (up to 70 ng m-3) that was collected near the mouth of Mackenzie River during clear sky condition. Although the molecular compositions of diacids are in general characterized by the predominance of oxalic acid, a depletion of C2 was found in two samples in which C4 became the most abundant. Similar depletion of oxalic acid has previously been reported in the Arctic aerosols collected at Alert after polar sunrise and in the summer aerosols from the coastal Antarctica. Because the marine aerosols that showed a depletion of C2 were observed under the overcast and/or foggy conditions, we suggest that a photochemical decomposition of oxalic acid may have occurred in aqueous phase of aerosols over the Arctic Ocean via the photo dissociation of oxalate-Fe (III) complex. We also determined stable carbon isotopic compositions (δ13C) of bulk aerosol carbon and individual diacids. The δ13C of bulk aerosols showed -26.5‰ (range: -29.7‰ to -24.7‰), suggesting that marine aerosol carbon is derived from both terrestrial and marine organic materials. In contrast, oxalic acid showed much larger δ13C values (average: -20.9‰, range

Supramolecular assembly of biphenyl dicarboxylic acid on Au(1 1 1)

NASA Astrophysics Data System (ADS)

Zhu, N.; Osada, T.; Komeda, T.

2007-04-01

We investigate the structure of submonolayer film of 4,4'-biphenyl dicarboxylic acid (BDA) molecules on Au(1 1 1)-22 × √3 reconstructed surface with the use of scanning tunneling microscopy (STM). The BDA molecules form ordered structures on Au(1 1 1) surface which are commensurate with the substrate. We have concluded that the molecule-molecule interaction is mainly through hydrogen bonding formed by a straight dimer of BDA molecules. The straight dimer can be expressed as 4 s + 2 t or its six crystallographic equivalents using the unit vectors of the gold substrate of s and t. The length of hydrogen bonding (O-H-O) is estimated to be 0.31 nm assuming nearest neighbor distance of gold atoms of 0.275 nm. The ordering shows a clear contrast with the case of BDA on Cu(1 0 0) surface [S. Stepanow, N. Lin, F. Vidal, A. Landa, M. Ruben, J.V. Barth, K. Kern, Nanoletters 5 (2005) 901] in which a square type of ordering of molecules is observed by the formation of hydrogen bonding between a carboxylate (COO) and a benzene ring. The clear difference of the ordered structure on Cu(1 0 0) and Au(1 1 1) surface demonstrates that the absence (presence) of deprotonation of carboxyl group of BDA molecule on Au(1 1 1) (Cu(1 0 0)) switches the straight and square type ordering of BDA molecules.

A new redox-active coordination polymer with cobalticinium dicarboxylate.

PubMed

Kondo, Mitsuru; Hayakawa, Yuri; Miyazawa, Makoto; Oyama, Aiko; Unoura, Kei; Kawaguchi, Hiroyuki; Naito, Tetsuyoshi; Maeda, Kenji; Uchida, Fumio

2004-09-20

A new two-dimensional coordination polymer with cobalticinium 1,1'-dicarboxylate (ccdc) incorporated in the framework has been prepared, the ccdc functioning as unique monoanionic dicarboxylate ligands. The compound shows a high redox activity based on the ccdc units. Copyright 2004 American Chemical Society

Water-soluble organic carbon, dicarboxylic acids, ketoacids, and α-dicarbonyls in the tropical Indian aerosols

NASA Astrophysics Data System (ADS)

Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.

2010-06-01

Tropical aerosol (PM10) samples (n = 49) collected from southeast coast of India were studied for water-soluble dicarboxylic acids (C2-C12), ketocarboxylic acids (C2-C9), and α-dicarbonyls (glyoxal and methylglyoxal), together with analyses of total carbon (TC) and water-soluble organic carbon (WSOC). Their distributions were characterized by a predominance of oxalic acid followed by terephthalic (t-Ph), malonic, and succinic acids. Total concentrations of diacids (227-1030 ng m-3), ketoacids (16-105 ng m-3), and dicarbonyls (4-23 ng m-3) are comparative to those from other Asian megacities such as Tokyo and Hong Kong. t-Ph acid was found as the second most abundant diacid in the Chennai aerosols. This feature has not been reported previously in atmospheric aerosols. t-Ph acid is most likely derived from the field burning of plastics. Water-soluble diacids were found to contribute 0.4%-3% of TC and 4%-11% of WSOC. Based on molecular distributions and backward air mass trajectories, we found that diacids and related compounds in coastal South Indian aerosols are influenced by South Asian and Indian Ocean monsoons. Organic aerosols are also suggested to be significantly transported long distances from North India and the Middle East in early winter and from Southeast Asia in late winter, but some originate from photochemical reactions over the Bay of Bengal. In contrast, the Arabian Sea, Indian Ocean, and South Indian continent are suggested as major source regions in summer. We also found daytime maxima of most diacids, except for C9 and t-Ph acids, which showed nighttime maxima in summer. Emissions from marine and terrestrial plants, combined with land/sea breezes and in situ photochemical oxidation, are suggested especially in summer as an important factor that controls the composition of water-soluble organic aerosols over the southeast coast of India. Regional emissions from anthropogenic sources are also important in megacity Chennai, but their influence is

Syntheses, structures, photoluminescence of four dicarboxylate-controlled Zn(II) coordination complexes incorporating flexible 1-(4-pyridylmethyl)-benzimidazole ligand

NASA Astrophysics Data System (ADS)

Hao, Hong-Jun; Du, Ming-Yue; Wang, Dan-Feng; Sun, Cheng-Jie; Wang, Zhan-Hui; Huang, Rong-Bin; Zheng, Lan-Sun

2013-09-01

Four Zn(II) coordination complexes, namely {[Zn(pmbm)2(tpa)]·H2O}n (1), {[Zn(pmbm)(phda)]·2(H2O)}n (2), [Zn(pmbm)(aze)]n (3), {[Zn(pmbm)(1,4-ndc)]·2(CH3OH)}n (4) [pmbm = 1-(4-pyridylmethyl)-benzimidazole, H2tpa = terephthalic acid, H2phda = phenylenediacetic acid, H2aze = azelaic acid, 1,4-ndcH2 = 1,4-naphthalenedicarboxylic acid] have been synthesized by solution phase ultrasonic reactions of Zn(AC)2·2H2O with pmbm and various dicarboxylates ligands under the ammoniacal condition. All the complexes have been characterized by elemental analyses, IR spectra and X-ray diffraction. Complexes 1 and 2 exhibit one-dimensional chains structure and complex 3 and 4 are two-dimensional sheets structure with (4,4) topology. Complexes 1-4 spanning from one-dimensional chains to two-dimensional sheets suggest that dicarboxylates play significant roles in the formation of such coordination architectures. The photoluminescences of the complexes were also investigated in the solid state at room temperature.

Biotypes analysis of Corynebacterium glutamicum growing in dicarboxylic acids demonstrates the existence of industrially-relevant intra-species variations.

PubMed

Pérez-García, Fernando; Vasco-Cárdenas, María F; Barreiro, Carlos

2016-09-02

Production enhancement of industrial microbial products or strains has been traditionally tackled by mutagenesis with chemical methods, irradiation or genetic manipulation. However, the final yield increase must go hand in hand with the resistance increasing against the usual inherent toxicity of the final products. Few studies have been carried out on resistance improvement and even fewer on the initial selection of naturally-generated biotypes, which could decrease the artificial mutagenesis. This fact is vital in the case of GRAS microorganisms as Corynebacterium glutamicum involved in food, feed and cosmetics production. The characteristic wide diversity and plasticity in terms of their genetic material of Actinobacteria eases the biotypes generation. Thus, differences in morphology, glutamate and lysine production and growth in media supplemented with dicarboxylic acids were analysed in four biotypes of C. glutamicum ATCC 13032. A 2D-DIGE analysis of these biotypes growing with itaconic acid allowed us to define their differences. Thus, an optimized central metabolism and better protection against the generated stress conditions present the CgL biotype as a suitable platform for production of itaconic acid, which is used as a building block (e.g.: acrylic plastic). This analysis highlights the preliminary biotypes screening as a way to reach optimal industrial productions.

Spatio-temporal distributions of dicarboxylic acids, ω-oxocarboxylic acids, pyruvic acid, α-dicarbonyls and fatty acids in the marine aerosols from the North and South Pacific

NASA Astrophysics Data System (ADS)

Hoque, Mir Md. Mozammal; Kawamura, Kimitaka; Uematsu, Mitsuo

2017-03-01

Aerosol samples (TSP) were collected during a cruise in the North (3°05‧N-34°02‧N) and South (6°59‧S-25°46‧S) Pacific to investigate the spatio-temporal distributions of water-soluble dicarboxylic acids and related compounds. The molecular distributions of diacids were characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and then succinic (C4) acid. However, we found a predominance of C4 over C3 in the aerosol sample that was collected in the western North Pacific Rim with a heavy influence from continental air masses. Atmospheric abundances of short chain diacids (C2-C4) are 2-3 times higher in the North Pacific than in the South Pacific. During the cruise, abundances of C2 in the western North Pacific are 5 times higher than those in the rest of the samples collected. Moreover, the aerosol samples collected in the western North Pacific demonstrated that glyoxylic (ωC2) acid and methylglyoxal (MeGly) were dominant together with C2. We found a strong correlation between C2 and ωC2 (r = 0.87) and C2 and MeGly (r = 0.97) in the western North Pacific aerosols but the correlations are significantly weak in the samples from the central North Pacific and Southern Ocean. Diacids were found to account for 1.6 to 14% of organic carbon with higher values in the western North Pacific. These results, together with 7-day backward air mass trajectories, indicate that ωC2 and MeGly are both originated from the photochemical oxidation of continent-derived organic precursors including isoprene, which can serve as precursors for the production of C2 during long-range atmospheric transport.

Studies of the acidic components of the Colorado Green River formation oil shale-Mass spectrometric identification of the methyl esters of extractable acids.

NASA Technical Reports Server (NTRS)

Haug, P.; Schnoes, H. K.; Burlingame, A. L.

1971-01-01

Study of solvent extractable acidic constituents of oil shale from the Colorado Green River Formation. Identification of individual components is based on gas chromatographic and mass spectrometric data obtained for their respective methyl esters. Normal acids, isoprenoidal acids, alpha, omega-dicarboxylic acids, mono-alpha-methyl dicarboxylic acids and methyl ketoacids were identified. In addition, the presence of monocyclic, benzoic, phenylalkanoic and naphthyl-carboxylic acids, as well as cycloaromatic acids, is demonstrated by partial identification.

Plasma acylcarnitine profiling indicates increased fatty acid oxidation relative to tricarboxylic acid cycle capacity in young, healthy low birth weight men.

PubMed

Ribel-Madsen, Amalie; Ribel-Madsen, Rasmus; Brøns, Charlotte; Newgard, Christopher B; Vaag, Allan A; Hellgren, Lars I

2016-10-01

We hypothesized that an increased, incomplete fatty acid beta-oxidation in mitochondria could be part of the metabolic events leading to insulin resistance and thereby an increased type 2 diabetes risk in low birth weight (LBW) compared with normal birth weight (NBW) individuals. Therefore, we measured fasting plasma levels of 45 acylcarnitine species in 18 LBW and 25 NBW men after an isocaloric control diet and a 5-day high-fat, high-calorie diet. We demonstrated that LBW men had higher C2 and C4-OH levels after the control diet compared with NBW men, indicating an increased fatty acid beta-oxidation relative to the tricarboxylic acid cycle flux. Also, they had higher C6-DC, C10-OH/C8-DC, and total hydroxyl-/dicarboxyl-acylcarnitine levels, which may suggest an increased fatty acid omega-oxidation in the liver. Furthermore, LBW and NBW men decreased several acylcarnitine levels in response to overfeeding, which is likely a result of an upregulation of fatty acid oxidation due to the dietary challenge. Moreover, C10-OH/C8-DC and total hydroxyl-/dicarboxyl-acylcarnitine levels tended to be negatively associated with the serum insulin level, and the total hydroxyl-/dicarboxyl-acylcarnitine level additionally tended to be negatively associated with the hepatic insulin resistance index. This indicates that an increased fatty acid omega-oxidation could be a compensatory mechanism to prevent an accumulation of lipid species that impair insulin signaling. © 2016 The Authors. Physiological Reports published by Wiley Periodicals, Inc. on behalf of the American Physiological Society and The Physiological Society.

Characterization of the newly isolated ω-oxidizing yeast Candida sorbophila DS02 and its potential applications in long-chain dicarboxylic acid production.

PubMed

Lee, Heeseok; Sugiharto, Yohanes Eko Chandra; Lee, Seunghoon; Park, Gyuyeon; Han, Changpyo; Jang, Hyeran; Jeon, Wooyoung; Park, Heejoon; Ahn, Jungoh; Kang, Kyungbo; Lee, Hongwoen

2017-08-01

α, ω-Dicarboxylic acids (DCAs) are multipurpose chemicals widely used in polymers, perfumes, plasticizers, lubricants, and adhesives. The biotransformation of DCAs from alkanes and fatty acids by microorganisms has attracted recent interest, since synthesis via chemical oxidation causes problems in terms of the environment and safety. We isolated an ω-oxidizing yeast from a wastewater disposal facility of a petrochemical factory by chemostat enrichment culture. The haploid strain identified as Candida sorbophila DS02 grew on glucose and dodecane, exhibiting greater cell shrinkage on the latter. In flask cultures with mixed alkanes (C10-16) and fatty acid methyl esters (C10-16), DS02 used mixed alkanes simultaneously unlike Candida tropicalis and Yarrowia lipolytica and showed high substrate resistance. In flask cultures with acrylic acid-a known inhibitor of β-oxidation-DS02 produced 0.28 g/l dodecanedioic acid (DDDA) from dodecane, similar to wild-type C. tropicalis ATCC 20336. In fed-batch fermentation, DS02 produced 9.87 g/l DDDA, which was 5.7-fold higher than wild-type C. tropicalis. These results suggest that C. sorbophila strain DS02 has potential applications for the large-scale production of DCA.

Aircraft measurement of dicarboxylic acids in the free tropospheric aerosols over the western to central North Pacific

NASA Astrophysics Data System (ADS)

Narukawa, M.; Kawamura, K.; Okada, K.; Zaizen, Y.; Makino, Y.

2003-07-01

Aircraft observation of aerosols was conducted in February 2000, for spatial and vertical distributions of dicarboxylic acids in the free troposphere over the western to central North Pacific. Oxalic, malonic, adipic and azelaic acids were detected in the aerosol samples as the major species. Concentrations of these diacids decreased exponentially with an increase in altitude. They were higher in the western North Pacific (130°E) and decrease eastward. Local flights conducted over Naha (Okinawa), Iwo-jima and Saipan showed that diacid concentrations decreased from the lower to upper troposphere. In the atmosphere over Saipan, where the air is not strongly affected from polluted East Asia, diacid concentrations were almost below the detection limit. Vertical profiles of diacids over Naha and Iwo-jima would be typical over the western North Pacific during winter, suggesting that diacids were significantly injected to the free troposphere from East Asia. Backward air mass trajectories also suggested that the diacids in the free troposphere over the North Pacific are strongly affected by the outflow from East Asia. Diacids, which were produced by both primary emission and secondary photochemical processes in polluted air of East Asia, could alter the physico-chemical properties of aerosols in the free troposphere over the western North Pacific.

One- and two-dimensional divalent copper coordination polymers based on kinked organodiimine and long flexible aliphatic dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Mallika Krishnan, Subhashree; Supkowski, Ronald M.; LaDuca, Robert L.

2008-11-01

Hydrothermal synthesis under acidic conditions has afforded a pair of divalent copper coordination polymers containing the kinked dipodal tethering organodiimine 4,4'-dipyridylamine (dpa) and flexible long-chain aliphatic dicarboxylate ligands. The new materials were characterized by single crystal X-ray structure determination, infrared spectroscopy, and thermogravimetric analysis. [CuCl(suberate) 0.5(dpa)] ( 1) manifests 1-D ladder-like motifs aggregated into 3-D through hydrogen bonding and copper-mediated supramolecular interactions. Extension of the aliphatic chain within the dicarboxylate ligand by one methylene unit resulted in {[Cu(azelate)(dpa)(H 2O)] · 3H 2O} ( 2), a (4,4) rhomboid grid 2-D coordination polymer encapsulating acyclic water molecule trimers.

Aerosol volatility and enthalpy of sublimation of carboxylic acids.

PubMed

Salo, Kent; Jonsson, Asa M; Andersson, Patrik U; Hallquist, Mattias

2010-04-08

The enthalpy of sublimation has been determined for nine carboxylic acids, two cyclic (pinonic and pinic acid) and seven straight-chain dicarboxylic acids (C(4) to C(10)). The enthalpy of sublimation was determined from volatility measurements of nano aerosol particles using a volatility tandem differential mobility analyzer (VTDMA) set-up. Compared to the previous use of a VTDMA, this novel method gives enthalpy of sublimation determined over an extended temperature range (DeltaT approximately 40 K). The determined enthalpy of sublimation for the straight-chain dicarboxylic acids ranged from 96 to 161 kJ mol(-1), and the calculated vapor pressures at 298 K are in the range of 10(-6)-10(-3) Pa. These values indicate that dicarboxylic acids can take part in gas-to-particle partitioning at ambient conditions and may contribute to atmospheric nucleation, even though homogeneous nucleation is unlikely. To obtain consistent results, some experimental complications in producing nanosized crystalline aerosol particles were addressed. It was demonstrated that pinonic acid "used as received" needed a further purification step before being suspended as a nanoparticle aerosol. Furthermore, it was noted from distinct differences in thermal properties that aerosols generated from pimelic acid solutions gave two types of particles. These two types were attributed to crystalline and amorphous configurations, and based on measured thermal properties, the enthalpy of vaporization was 127 kJ mol(-1) and that of sublimation was 161 kJ mol(-1). This paper describes a new method that is complementary to other similar methods and provides an extension of existing experimental data on physical properties of atmospherically relevant compounds.

Seasonal cycle and temperature dependence of pinene oxidation products, dicarboxylic acids and nitrophenols in fine and coarse air particulate matter

NASA Astrophysics Data System (ADS)

Zhang, Y. Y.; Müller, L.; Winterhalter, R.; Moortgat, G. K.; Hoffmann, T.; Pöschl, U.

2010-08-01

Filter samples of fine and coarse air particulate matter (PM) collected over a period of one year in central Europe (Mainz, Germany) were analyzed for water-soluble organic compounds (WSOCs), including the α- and β-pinene oxidation products pinic acid, pinonic acid and 3-methyl-1,2,3-butanetricarboxylic acid (3-MBTCA), as well as a variety of dicarboxylic acids and nitrophenols. Seasonal variations and other characteristic features in fine, coarse, and total PM (TSP) are discussed with regard to aerosol sources and sinks in comparison to data from other studies and regions. The ratios of adipic acid and phthalic acid to azelaic acid indicate that the investigated aerosol samples were mainly influenced by biogenic sources. A strong Arrhenius-type correlation was found between the 3-MBTCA concentration and inverse temperature (R2 = 0.79, n = 52, Ea = 126 ± 10 kJ mol-1, temperature range 275-300 K). Model calculations suggest that the temperature dependence observed for 3-MBTCA can be explained by enhanced photochemical production due to an increase of hydroxyl radical (OH) concentration with increasing temperature, whereas the influence of gas-particle partitioning appears to play a minor role. The results indicate that the OH-initiated oxidation of pinonic acid is the rate-limiting step in the formation of 3-MBTCA, and that 3-MBTCA may be a suitable tracer for the chemical aging of biogenic secondary organic aerosol (SOA) by OH radicals. An Arrhenius-type temperature dependence was also observed for the concentration of pinic acid (R2 = 0.60, n = 56, Ea = 84 ± 9 kJ mol-1); it can be tentatively explained by the temperature dependence of biogenic pinene emission as the rate-limiting step of pinic acid formation.

Seasonal cycle and temperature dependence of pinene oxidation products, dicarboxylic acids and nitrophenols in fine and coarse air particulate matter

NASA Astrophysics Data System (ADS)

Zhang, Y.; Müller, L.; Winterhalter, R.; Moortgat, G. K.; Hoffmann, T.; Pöschl, U.

2010-05-01

Filter samples of fine and coarse air particulate matter (PM) collected over a period of one year in central Europe (Mainz, Germany) were analyzed for water-soluble organic compounds (WSOCs), including the α- and β-pinene oxidation products pinic acid, pinonic acid and 3-methyl-1,2,3-butanetricarboxylic acid (3-MBTCA), as well as a variety of dicarboxylic acids and nitrophenols. Seasonal variations and other characteristic features in fine, coarse, and total PM (TSP) are discussed with regard to aerosol sources and sinks in comparison to data from other studies and regions. The ratios of adipic acid and phthalic acid to azelaic acid indicate that the investigated samples were mainly influenced by biogenic sources. A strong Arrhenius-type correlation was found between the 3-MBTCA concentration and inverse temperature (R2=0.79, n=52, Ea=126±10 kJ mol-1, temperature range 275-300 K). Model calculations suggest that the temperature dependence observed for 3-MBTCA can be explained by enhanced photochemical production due to an increase of hydroxyl radical (OH) concentration with increasing temperature, whereas the influence of gas-particle partitioning appears to play a minor role. The results indicate that the OH-initiated oxidation of pinonic acid is the rate-limiting step in the formation of 3-MBTCA, and that 3-MBTCA may be a suitable tracer for the chemical aging of biogenic secondary organic aerosol (SOA) by OH radicals. An Arrhenius-type temperature dependence was also observed for the concentration of pinic acid (R2=0.60, n=56, Ea=84±9 kJ mol-1); it can be tentatively explained by the temperature dependence of biogenic pinene emission as the rate-limiting step of pinic acid formation.

Seasonal variations of low molecular weight hydroxy-dicarboxylic acids and oxaloacetic acid in remote marine aerosols from Chichijima Island in the western North Pacific (December 2010-November 2011)

NASA Astrophysics Data System (ADS)

Gowda, Divyavani; Kawamura, Kimitaka

2018-05-01

Concentrations of homologous hydroxy-dicarboxylic acids (diacids) (hC3-hC6) and keto-diacid (oxaloacetic acid) were measured in the atmospheric aerosols collected at Chichijima Island (27.04° N, 142.13° E) in the western North Pacific from December 2010 to November 2011. The monthly averaged concentrations of hydroxy-diacids and oxaloacetic acid were significantly higher in spring followed by winter and autumn. Molecular distributions of hydroxy-diacids demonstrated that malic acid was the most abundant species in all four seasons, followed by tartronic acid in winter and spring and 3- and 2-hydroxyglutaric acids in summer and autumn. Hydroxy-diacids and keto-diacid maximized in spring and winter when air masses originated from the Asian continent with westerly winds. The concentrations of total hydroxy-diacids and oxaloacetic acid ranged from 0.1 to 27.3 ng m-3 and <0.005 to 2 ng m-3, respectively. The enhanced concentrations of diacids and their intermediates in winter and spring are associated with a long-range atmospheric transport of pollutants from East Asia to remote Chichijima Island followed by photochemical processing of organic aerosols. Seasonal molecular distribution of hydroxy-diacids and oxaloacetic acid was found to be dependent on the source strengths and plausible photochemical processing to form smaller diacids. Moderate to strong correlations among hydroxy-diacids, oxaloacetic acid and low molecular weight (LMW) diacids suggest that hydroxy-diacids and oxaloacetic acid are the intermediates in the photochemical oxidation of LMW diacid. Hence, photochemical formation of the most abundant LMW diacids, i.e., oxalic acid, could be produced from hydroxy- and keto-diacid as intermediates.

Molecular distribution and compound-specific stable carbon isotopic composition of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls in PM2.5 from Beijing, China

NASA Astrophysics Data System (ADS)

Zhao, Wanyu; Kawamura, Kimitaka; Yue, Siyao; Wei, Lianfang; Ren, Hong; Yan, Yu; Kang, Mingjie; Li, Linjie; Ren, Lujie; Lai, Senchao; Li, Jie; Sun, Yele; Wang, Zifa; Fu, Pingqing

2018-02-01

This study investigates the seasonal variation, molecular distribution and stable carbon isotopic composition of diacids, oxocarboxylic acids and α-dicarbonyls to better understand the sources and formation processes of fine aerosols (PM2.5) in Beijing. The concentrations of total dicarboxylic acids varied from 110 to 2580 ng m-3, whereas oxoacids (9.50-353 ng m-3) and dicarbonyls (1.50-85.9 ng m-3) were less abundant. Oxalic acid was found to be the most abundant individual species, followed by succinic acid or occasionally by terephthalic acid (tPh), a plastic waste burning tracer. Ambient concentrations of phthalic acid (37.9 ± 27.3 ng m-3) and tPh (48.7 ± 51.1 ng m-3) were larger in winter than in other seasons, illustrating that fossil fuel combustion and plastic waste incineration contribute more to wintertime aerosols. The year-round mass concentration ratios of malonic acid to succinic acid (C3 / C4) were relatively low by comparison with those in other urban aerosols and remote marine aerosols. The values were less than or equal to unity in Beijing, implying that the degree of photochemical formation of diacids in Beijing is insignificant. Moreover, strong correlation coefficients of major oxocarboxylic acids and α-dicarbonyls with nss-K+ suggest that biomass burning contributes significantly to these organic acids and related precursors. The mean δ13C value of succinic acid is the highest among all species, with values of -17.1 ± 3.9 ‰ (winter) and -17.1 ± 2.0 ‰ (spring), while malonic acid is more enriched in 13C than others in autumn (-17.6 ± 4.6 ‰) and summer (-18.7 ± 4.0 ‰). The δ13C values of major species in Beijing aerosols are generally lower than those in the western North Pacific atmosphere, the downwind region, which indicates that stable carbon isotopic compositions of diacids depend on their precursor sources in Beijing. Therefore, our study demonstrates that in addition to photochemical oxidation, high abundances of diacids

Atmospheric oxalic acid and related secondary organic aerosols in Qinghai Lake, a continental background site in Tibet Plateau

NASA Astrophysics Data System (ADS)

Meng, Jingjing; Wang, Gehui; Li, Jianjun; Cheng, Chunlei; Cao, Junji

2013-11-01

Summertime PM2.5 aerosols collected from Qinghai Lake (3200 m a.s.l.), a remote continental site in the northeastern part of Tibetan Plateau, were analyzed for dicarboxylic acids (C2-C11), ketocarboxylic acids and α-dicarbonyals. Oxalic acid (C2) is the dominant dicarboxylic acid in the samples, followed by malonic, succinic and azelaic acids. Total dicarboxylic acids (231 ± 119 ng m-3), ketocarboxylic acids (8.4 ± 4.3 ng m-3), and α-dicarbonyls (2.7 ± 2.1 ng m-3) at the Tibetan background site are 2-5 times less than those detected in lowland areas such as 14 Chinese megacities. Compared to those in other urban and marine areas enhancements in relative abundances of C2/total diacids and diacids-C/WSOC of the PM2.5 samples suggest that organic aerosols in the region are more oxidized due to strong solar radiation. Molecular compositions and air mass trajectories demonstrate that the above secondary organic aerosols in the Qinghai Lake atmosphere are largely derived from long-range transport. Ratios of oxalic acid, glyoxal and methylglyoxal to levoglucosan in PM2.5 aerosols emitted from household burning of yak dung, a major energy source for Tibetan in the region, are 30-400 times lower than those in the ambient air, which further indicates that primary emission from biomass burning is a negligible source of atmospheric oxalic acid and α-dicarbonyls at this background site.

Two novel copper(II) complexes constructed from dicarboxylate ligands with different spacer lengths and 2-phenylimidazo[4,5- f]1,10-phenanthroline (PIP): Synthesis, structures and properties

NASA Astrophysics Data System (ADS)

Wang, X.-L.; Chen, Yongqiang; Liu, Guocheng; Lin, Hongyan; Zhang, Jinxia

2009-09-01

Two novel metal-organic coordination polymers [Cu(PIP)(bpea)(H 2O)]·H 2O ( 1) and [Cu(PIP)(1,4-bdc)] ( 2) have been obtained from hydrothermal reaction of copper(II) with the mixed ligands [biphenylethene-4,4'-dicarboxylic acid (bpea) for 1, benzene-1,4-dicarboxylic acid (1,4-H 2bdc) for 2, and 2-phenylimidazo[4,5- f]1,10-phenanthroline (PIP)]. Both complexes have been structurally characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. Structural analyses reveal that complex 1 possesses infinite one-dimensional zigzag chain, 2 exhibits a two-dimensional (4,4) network, both of which are extended into three-dimensional supramolecular network by weak interactions. The different structures of the title complexes illustrate the influence of the flexibility (the spacer length of carboxyl groups and the structural rigidity of the spacer) of organic dicarboxylate ligands on the formation of such coordination architectures. Moreover, the thermal properties and the voltammetric behavior of complexes 1 and 2 have been reported.

Ligand-controlled assembly of Cd(II) coordination polymers based on mixed ligands of naphthalene-dicarboxylate and dipyrido[3,2-d:2',3'-f]quinoxaline: From 0D+1D cocrystal, 2D rectangular network (4,4), to 3D PtS-type architecture

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

Liu Guocheng; Chen Yongqiang; Wang Xiuli

Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H{sub 2}O){sub 2}][Cd(Dpq)(1,8-NDC)].2H{sub 2}O (1), [Cd(Dpq)(1,4-NDC)(H{sub 2}O)] (2), and [Cd(Dpq)(2,6-NDC)] (3) have been obtained from hydrothermal reactions of cadmium(II) nitrate with the mixed ligands dipyrido [3,2-d:2',3'-f]quinoxaline (Dpq) and three structurally related naphthalene-dicarboxylate ligands [1,8-naphthalene-dicarboxylic acid (1,8-H{sub 2}NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H{sub 2}NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H{sub 2}NDC)]. Single-crystal X-ray diffraction analysis reveals that the three polymers exhibit novel structures due to different naphthalene-dicarboxylic acid. Compound 1 is a novel cocrystal of left- and right-handed helical chains and binuclear complexes and ultimately packed into a 3D supramolecular structure through hydrogen bonds and {pi}-{pi} stacking interactions. Compoundmore » 2 shows a 2D rectangular network (4,4) bridged by 1,4-NDC with two kinds of coordination modes and ultimately packed into a 3D supramolecular structure through inter-layer {pi}-{pi} stacking interactions. Compound 3 is a new 3D coordination polymer with distorted PtS-type network. In addition, the title compounds exhibit blue/green emission in solid state at room temperature. - Graphical abstract: Three novel Cd(II) compounds have been synthesized under hydrothermal conditions exhibiting a systematic variation of architecture by the employment of three structurally related naphthalene-dicarboxylate ligands.« less

Ligand-controlled assembly of Cd(II) coordination polymers based on mixed ligands of naphthalene-dicarboxylate and dipyrido[3,2-d:2‧,3‧-f]quinoxaline: From 0D+1D cocrystal, 2D rectangular network (4,4), to 3D PtS-type architecture

NASA Astrophysics Data System (ADS)

Liu, Guocheng; Chen, Yongqiang; Wang, Xiuli; Chen, Baokuan; Lin, Hongyan

2009-03-01

Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H 2O) 2][Cd(Dpq)(1,8-NDC)]·2H 2O ( 1), [Cd(Dpq)(1,4-NDC)(H 2O)] ( 2), and [Cd(Dpq)(2,6-NDC)] ( 3) have been obtained from hydrothermal reactions of cadmium(II) nitrate with the mixed ligands dipyrido [3,2-d:2',3'-f]quinoxaline (Dpq) and three structurally related naphthalene-dicarboxylate ligands [1,8-naphthalene-dicarboxylic acid (1,8-H 2NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H 2NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H 2NDC)]. Single-crystal X-ray diffraction analysis reveals that the three polymers exhibit novel structures due to different naphthalene-dicarboxylic acid. Compound 1 is a novel cocrystal of left- and right-handed helical chains and binuclear complexes and ultimately packed into a 3D supramolecular structure through hydrogen bonds and π- π stacking interactions. Compound 2 shows a 2D rectangular network (4,4) bridged by 1,4-NDC with two kinds of coordination modes and ultimately packed into a 3D supramolecular structure through inter-layer π- π stacking interactions. Compound 3 is a new 3D coordination polymer with distorted PtS-type network. In addition, the title compounds exhibit blue/green emission in solid state at room temperature.

Quantitative analysis of glycerol in dicarboxylic acid-rich cutins provides insights into Arabidopsis cutin structure.

PubMed

Yang, Weili; Pollard, Mike; Li-Beisson, Yonghua; Ohlrogge, John

2016-10-01

Cutin is an extracellular lipid polymer that contributes to protective cuticle barrier functions against biotic and abiotic stresses in land plants. Glycerol has been reported as a component of cutin, contributing up to 14% by weight of total released monomers. Previous studies using partial hydrolysis of cuticle-enriched preparations established the presence of oligomers with glycerol-aliphatic ester links. Furthermore, glycerol-3-phosphate 2-O-acyltransferases (sn-2-GPATs) are essential for cutin biosynthesis. However, precise roles of glycerol in cutin assembly and structure remain uncertain. Here, a stable isotope-dilution assay was developed for the quantitative analysis of glycerol by GC/MS of triacetin with simultaneous determination of aliphatic monomers. To provide clues about the role of glycerol in dicarboxylic acid (DCA)-rich cutins, this methodology was applied to compare wild-type (WT) Arabidopsis cutin with a series of mutants that are defective in cutin synthesis. The molar ratio of glycerol to total DCAs in WT cutins was 2:1. Even when allowing for a small additional contribution from hydroxy fatty acids, this is a substantially higher glycerol to aliphatic monomer ratio than previously reported for any cutin. Glycerol content was strongly reduced in both stem and leaf cutin from all Arabidopsis mutants analyzed (gpat4/gpat8, att1-2 and lacs2-3). In addition, the molar reduction of glycerol was proportional to the molar reduction of total DCAs. These results suggest "glycerol-DCA-glycerol" may be the dominant motif in DCA-rich cutins. The ramifications and caveats for this hypothesis are presented. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Construction of Eu(III)- and Tb(III)-MOFs with photoluminescence for sensing small molecules based on furan-2,5-dicarboxylic acid

NASA Astrophysics Data System (ADS)

Zhao, Shuai; Hao, Xue-Min; Liu, Jia-Lin; Wu, Lin-Wei; Wang, Hao; Wu, Yi-Bo; Yang, Dan; Guo, Wen-Li

2017-11-01

Two isostructural lanthanide MOFs, [Ln3K2(FDA)4(NO3)3(MeCN)2]n (Ln = Eu 1, Tb 2) (H2FDA= furan-2,5-dicarboxylic acid), have been constructed under solvothermal conditions. Structures analyses demonstrate two complexes possess three-dimensional network with monoclinic space group C2/c. The topology analysis shows that the whole framework can be simplified to a 3,8T24 topology constructed from trinuclear {Ln3} as secondary building units (SBUs) without considering K+ ions. Solid state luminescent studies indicate that 1 and 2 show the characteristic red and green emissions of the corresponding Ln3+ ions, respectively. The luminescence lifetimes of 1 and 2 are approximately 1.04 ms and 0.41 ms. In addition, activated 1 exhibits excellent fluorescence sensing for small molecules, especially for nitrobenzene.

Identification of Conformationally Sensitive Amino Acids in the Na+/Dicarboxylate Symporter (SdcS)†

PubMed Central

Joshi, Aditya D.; Pajor, Ana M.

2009-01-01

The Na+/dicarboxylate symporter (SdcS) from Staphylococcus aureus is a homolog of the mammalian Na+/dicarboxylate cotransporters (NaDC1) from solute carrier family 13 (SLC 13). The present study examined succinate transport by SdcS heterologously expressed in Escherichia coli, using right-side-out (RSO) and inside-out (ISO) membrane vesicles. The Km values for succinate in RSO and ISO vesicles were similar, about 30 μM. The single cysteine of SdcS was replaced to produce the cysteineless transporter, C457S, which demonstrated similar functional characteristics as the wild-type. Single cysteine mutants were made in SdcS-C457S at positions that are functionally important in the mammalian NaDC1. Mutant N108C of SdcS was sensitive to chemical labeling by MTSET ([2-(trimethylammonium)ethyl]-methanethiosulfonate) from both the cytoplasmic and extracellular side, depending on the conformational state of the transporter, suggesting that Asn-108 may be found in the translocation pore of the protein. Mutant D329C was sensitive to MTSET in the presence of Na+ but only from the extracellular side. Finally, mutant L436C was insensitive to MTSET although changes in its kinetic properties indicate that this residue may be important in substrate binding. In conclusion, this work identifies Asn-108 as a key residue in the translocation pathway of the protein, accessible in different states from both sides of the membrane. Functional characterization of SdcS should provide useful structural as well as functional details about mammalian transporters from the SLC 13 family. PMID:19260674

Synthesis and characterization of Mg-Al-layered double hydroxides intercalated with cubane-1,4-dicarboxylate anions.

PubMed

Rezvani, Zolfaghar; Arjomandi Rad, Farzad; Khodam, Fatemeh

2015-01-21

In the present work, Mg2Al-layered double hydroxide (LDH) intercalated with cubane-1,4-dicarboxylate anions was prepared from the reaction of solutions of Mg(ii) and Al(iii) nitrate salts with an alkaline solution of cubane-1,4-dicarboxylic acid by using the coprecipitation method. The successful preparation of a nanohybrid of cubane-1,4-dicarboxylate(cubane-dc) anions with LDH was confirmed by powder X-ray diffraction, FTIR spectroscopy and thermal gravimetric analysis (TGA). The increase in the basal spacing of LDHs from 8.67 Å to 13.40 Å shows that cubane-dc anions were successfully incorporated into the interlayer space. Thermogravimetric analyses confirm that the thermal stability of the intercalated cubane-dc anions is greater than that of the pure form before intercalation because of host-guest interactions involving hydrogen bonds. The interlayer structure, hydrogen bonding, and subsequent distension of LDH compounds containing cubane-dc anions were shown by molecular simulation. The RDF (radial distribution function), mean square displacement (MSD), and self-diffusion coefficient were calculated using the trajectory files on the basis of molecular dynamics (MD) simulations, and the results indicated that the cubane-dc anions were more stable when intercalated into the LDH layers. A good agreement was obtained between calculated and measured X-ray diffraction patterns and between experimental and calculated basal spacings.

Thermodynamic aspects of dicarboxylate recognition by simple artificial receptors.

PubMed

Linton, B R; Goodman, M S; Fan, E; van Arman, S A; Hamilton, A D

2001-11-02

Recognition of dicarboxylates by bis-functional hydrogen-bonding receptors displays divergent thermodynamics in different solvent systems. NMR titration and isothermal titration calorimetry indicated that neutral bis-urea and bis-thiourea receptors form exothermic complexes with dicarboxylates in DMSO, with a near zero entropic contribution to binding. The increased binding strength of bis-guanidinium receptors precluded quantitative measurement of binding constants in DMSO, but titration calorimetry offered a qualitative picture of the association. Formation of these 1:1 complexes was also exothermic, but additional endothermic events occurred at both lower and higher host-guest ratios. These events indicated multiple binding equilibria but did not always occur at a discrete 2:1 or 1:2 host-guest molar ratio, suggesting higher aggregates. With increasing amounts of methanol as solvent, bis-guanidinium receptors form more endothermic complexes with dicarboxylates, with a favorable entropy of association. This switch from association driven by enthalpy to one driven by entropy may reflect a change from complexation involving the formation of hydrogen bonds to that promoted by solvent liberation from binding sites.

Benzoate Mediates Repression of C4-Dicarboxylate Utilization in “Aromatoleum aromaticum” EbN1

PubMed Central

Trautwein, Kathleen; Grundmann, Olav; Wöhlbrand, Lars; Eberlein, Christian; Boll, Matthias

2012-01-01

Diauxic growth was observed in anaerobic C4-dicarboxylate-adapted cells of “Aromatoleum aromaticum” EbN1 due to preferred benzoate utilization from a substrate mixture of a C4-dicarboxylate (succinate, fumarate, or malate) and benzoate. Differential protein profiles (two-dimensional difference gel electrophoresis [2D DIGE]) revealed dynamic changes in abundance for proteins involved in anaerobic benzoate catabolism and C4-dicarboxylate uptake. In the first active growth phase, benzoate utilization was paralleled by maximal abundance of proteins involved in anaerobic benzoate degradation (e.g., benzoyl-coenzyme A [CoA] reductase) and minimal abundance of DctP (EbA4158), the periplasmic binding protein of a predicted C4-dicarboxylate tripartite ATP-independent periplasmic (TRAP) transporter (DctPQM). The opposite was observed during subsequent succinate utilization in the second active growth phase. The increased dctP (respectively, dctPQM) transcript and DctP protein abundance following benzoate depletion suggests that repression of C4-dicarboxylate uptake seems to be a main determinant for the observed diauxie. PMID:22081395

A Dicarboxylate Transporter, LjALMT4, Mainly Expressed in Nodules of Lotus japonicus.

PubMed

Takanashi, Kojiro; Sasaki, Takayuki; Kan, Tomohiro; Saida, Yuka; Sugiyama, Akifumi; Yamamoto, Yoko; Yazaki, Kazufumi

2016-07-01

Legume plants can establish symbiosis with soil bacteria called rhizobia to obtain nitrogen as a nutrient directly from atmospheric N2 via symbiotic nitrogen fixation. Legumes and rhizobia form nodules, symbiotic organs in which fixed-nitrogen and photosynthetic products are exchanged between rhizobia and plant cells. The photosynthetic products supplied to rhizobia are thought to be dicarboxylates but little is known about the movement of dicarboxylates in the nodules. In terms of dicarboxylate transporters, an aluminum-activated malate transporter (ALMT) family is a strong candidate responsible for the membrane transport of carboxylates in nodules. Among the seven ALMT genes in the Lotus japonicus genome, only one, LjALMT4, shows a high expression in the nodules. LjALMT4 showed transport activity in a Xenopus oocyte system, with LjALMT4 mediating the efflux of dicarboxylates including malate, succinate, and fumarate, but not tricarboxylates such as citrate. LjALMT4 also mediated the influx of several inorganic anions. Organ-specific gene expression analysis showed LjALMT4 mRNA mainly in the parenchyma cells of nodule vascular bundles. These results suggest that LjALMT4 may not be involved in the direct supply of dicarboxylates to rhizobia in infected cells but is responsible for supplying malate as well as several anions necessary for symbiotic nitrogen fixation, via nodule vasculatures.

Dicarboxylic acids and levoglucosan in aerosols from Indo-Gangetic Plain: Inferences from day night variability during wintertime.

PubMed

Sorathia, Fena; Rajput, Prashant; Gupta, Tarun

2018-05-15

This study assesses daytime and nighttime atmospheric abundance and molecular distribution of dicarboxylic acids (DCA: C 2 -C 10 ) and biomass burning tracers (levoglucosan and biomass burning derived potassium: K + BB ) in PM 10 (particulate matter with aerodynamic diameter≤10μm) from an urban location, Kanpur (in central Indo-Gangetic Plain: IGP) during wintertime (December 2015-February 2016). In this study, PM 10 varied from 130 to 242 and 175-388μgm -3 during daytime and nighttime, respectively. The average ratios of OC/EC (day: 12.3; night: 9.3) and WSOC/OC (day: 0.74; night: 0.48) were relatively high during daytime (OC: organic carbon; EC: elemental carbon; WSOC: water-soluble organic carbon). Strong linear correlations (R 2 ≥0.6; p<0.05) of OC with levoglucosan and K + BB suggest biomass burning emission as predominant source of organic aerosols over the IGP. The measured concentrations of total DCA (ΣC 2 -C 10 ) showed pronounced diurnal variability with a higher concentration during nighttime (2510±1025ngm -3 ) as compared to that in daytime (1499±562ngm -3 ). Concentrations of oxalic acid (C 2 ), succinic acid (C 4 ) and malonic acid (C 3 ) were predominantly high as compared to other congeners of DCA (C 2 -C 10 ) over central IGP. Relatively higher mass fraction (73.4%) of C 2 in total DCA during nighttime than that in daytime (61.5%) indicates role of secondary organic aerosols (SOAs) formation involving aqueous-phase chemistry. Strong linear correlations of C 2 with C 3 and C 4 plausibly suggest that C 2 can have predominant formation pathways via decomposition of higher congeners of DCA. Overall, strong linear correlations of C 2 with levoglucosan and sulphate suggest that biomass burning emission and secondary transformations are predominant sources of DCA over IGP during wintertime. Copyright © 2017 Elsevier B.V. All rights reserved.

Stable carbon isotopic compositions of total carbon, dicarboxylic acids and glyoxylic acid in the tropical Indian aerosols: Implications for sources and photochemical processing of organic aerosols

NASA Astrophysics Data System (ADS)

Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.; Tachibana, Eri

2011-09-01

The tropical Indian aerosols (PM10) collected on day- and nighttime bases in winter and summer, 2007 from Chennai (13.04°N; 80.17°E) were studied for stable carbon isotopic compositions (δ13C) of total carbon (TC), individual dicarboxylic acids (C2-C9) and glyoxylic acid (ωC2). δ13C values of TC ranged from -23.9‰ to -25.9‰ (-25.0 ± 0.6‰; n = 49). Oxalic (C2) (-17.1 ± 2.5‰), malonic (C3) (-20.8 ± 1.8‰), succinic (C4) (-22.5 ± 1.5‰) and adipic (C6) (-20.6 ± 4.1‰) acids and ωC2 acid (-22.4 ± 5.5‰) were found to be more enriched with 13C compared to TC. In contrast, suberic (C8) (-29.4 ± 1.8‰), phthalic (Ph) (-30.1 ± 3.5‰) and azelaic (C9) (-28.4 ± 5.8‰) acids showed smaller δ13C values than TC. Based on comparisons of δ13C values of TC in Chennai aerosols to those (-24.7 ± 2.2‰) found in unburned cow-dung samples collected from Chennai and isotopic signatures of the particles emitted from point sources, we found that biofuel/biomass burning are the major sources of carbonaceous aerosols in South and Southeast Asia. The decrease in δ13C values of C9 diacid by about 5‰ from winter to summer suggests that tropical plant emissions also significantly contribute to organic aerosol in this region. Significant increase in δ13C values from C4 to C2 diacids in Chennai aerosols could be attributed for their photochemical processing in the tropical atmosphere during long-range transport from source regions.

Application of microalgae hydrolysate as a fermentation medium for microbial production of 2-pyrone 4,6-dicarboxylic acid.

PubMed

Htet, April N; Noguchi, Mana; Ninomiya, Kazuaki; Tsuge, Yota; Kuroda, Kosuke; Kajita, Shinya; Masai, Eiji; Katayama, Yoshihiro; Shikinaka, Kazuhiro; Otsuka, Yuichiro; Nakamura, Masaya; Honda, Ryo; Takahashi, Kenji

2018-06-01

Actual biomass of microalgae was tested as a fermentation substrate for microbial production of 2-pyrone 4,6-dicarboxylic acid (PDC). Acid-hydrolyzed green microalgae Chlorella emersonii (algae hydrolysate) was diluted to adjust the glucose concentration to 2 g/L and supplemented with the nutrients of Luria-Bertani (LB) medium (tryptone 10 g/L and yeast extract 5 g/L). When the algae hydrolysate was used as a fermentation source for recombinant Escherichia coli producing PDC, 0.43 g/L PDC was produced with a yield of 20.1% (mol PDC/mol glucose), whereas 0.19 g/L PDC was produced with a yield of 8.6% when LB medium supplemented with glucose was used. To evaluate the potential of algae hydrolysate alone as a fermentation medium for E. coli growth and PDC production, the nutrients of LB medium were reduced from the algae hydrolysate medium. Interestingly, 0.17 g/L PDC was produced even without additional nutrient, which was comparable to the case using pure glucose medium with nutrients of LB medium. When using a high concentration of hydrolysate without additional nutrients, 1.22 g/L PDC was produced after a 24-h cultivation with the yield of 16.1%. Overall, C. emersonii has high potential as cost-effective fermentation substrate for the microbial production of PDC. Copyright © 2018 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Coligand-regulated assembly, fluorescence, and magnetic properties of Co(II) and Cd(II) complexes with a non-coplanar dicarboxylate

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

Xin, Ling-Yun; Liu, Guang-Zhen, E-mail: gzliuly@126.com; Ma, Lu-Fang

A non-coplanar dicarboxylate ndca (H{sub 2}ndca=5-norbornene-2,3-dicarboxylic acid), combining with various dipyridyl-typed tectons, constructs six Cd(II)/Co(II) coordination polymers under hydrothermal conditions, namely [Co(ndca)(H{sub 2}O)]{sub n} (1), ([Co(ndca)(bpe)(H{sub 2}O)]·H{sub 2}O){sub n} (2), [Co(ndca)(bpa){sub 0.5}(H{sub 2}O)]{sub n} (3), [Cd(ndca)(bpe)(H{sub 2}O)]{sub n} (4), ([Cd(ndca)(bpa)(H{sub 2}O)]·0.5H{sub 2}O){sub n} (5), and ([Cd(ndca)(bpp) (H{sub 2}O)]·H{sub 2}O){sub n} (6) (bpe=1,2-di(4-pyridyl)ethylene, bpa=1,2-bi(4-pyridyl)ethane, and bpp=1,3-bis(4-pyridyl)propane). All these compounds contain various metal(II)–carboxylate motifs, including carboxylate binuclear (2, 4, 5), carboxylate chain (1, 6) and carboxylate layer (3), which are further extended by dipyridyl-typed coligands to afford a vast diversity of the structures with 2D pyknotic layers (1, 6), 2D open layermore » (5), 2D→3D interpenetrated networks (2,4), and 3D pillared-layer framework (3), respectively. In addition, fluorescent spectra of Cd(II) complexes and magnetic properties of Co(II) complexes are also given. - Graphical abstract: Six various cadmium(II)/cobalt(II)–organic frameworks were constructed by 5-norbornene-2,3-dicarboxylic acid and different bis(pyridine) rod-like tectons, and Cd (II) complexes exhibit blue–violet emissions, whereas Co (II) complexes show antiferromagnetic behaviours. Display Omitted.« less

Characterization of mitochondrial dicarboxylate/tricarboxylate transporters from grape berries.

PubMed

Regalado, Ana; Pierri, Ciro Leonardo; Bitetto, Maria; Laera, Valentina Liliana; Pimentel, Catarina; Francisco, Rita; Passarinho, José; Chaves, Maria M; Agrimi, Gennaro

2013-03-01

Grape berries (Vitis vinifera L fruit) exhibit a double-sigmoid pattern of development that results from two successive periods of vacuolar swelling during which the nature of accumulated solutes changes significantly. Throughout the first period, called green or herbaceous stage, berries accumulate high levels of organic acids, mainly malate and tartrate. At the cellular level fruit acidity comprises both metabolism and vacuolar storage. Malic acid compartmentation is critical for optimal functioning of cytosolic enzymes. Therefore, the identification and characterization of the carriers involved in malate transport across sub-cellular compartments is of great importance. The decrease in acid content during grape berry ripening has been mainly associated to mitochondrial malate oxidation. However, no Vitis vinifera mitochondrial carrier involved in malate transport has been reported to date. Here we describe the identification of three V. vinifera mitochondrial dicarboxylate/tricarboxylate carriers (VvDTC1-3) putatively involved in mitochondrial malate, citrate and other di/tricarboxylates transport. The three VvDTCs are very similar, sharing a percentage of identical residues of at least 83 %. Expression analysis of the encoding VvDTC genes in grape berries shows that they are differentially regulated exhibiting a developmental pattern of expression. The simultaneous high expression of both VvDTC2 and VvDTC3 in grape berry mesocarp close to the onset of ripening suggests that these carriers might be involved in the transport of malate into mitochondria.

Self-assembly in solvates of 2,4-diamino-6-(4-methyl- phenyl)-1,3,5-triazine and in its molecular adducts with some aliphatic dicarboxylic acids

NASA Astrophysics Data System (ADS)

Nandy, Purnendu; Nayak, Amrita; Biswas, Sharmita Nandy; Pedireddi, V. R.

2016-03-01

Solid state structures of 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 1, in the form of methanol and dimethylsulfoxide (DMSO) solvates, as well as supramolecular assemblies of 1 with various aliphatic dicarboxylic acids, oxalic (a), malonic (b), succinic (c), glutaric (d) and adipic (e) have been reported. Analysis of the assemblies has been carried out by single crystal X-ray diffraction and thermal methods. Triazine 1 yields anhydrous molecular adducts with acids a-d, upon co-crystallization either from CH3OH and DMSO solvents. However acid e gives anhydrous adduct from DMSO solvent, while it gives a methanol adduct from CH3OH. Structure determination reveals that molecular adducts 1a, 1d and 1e are in a 2:1 ratio of 1 and the corresponding acid. However the ratio is 1:1, in 1b, perhaps due to the involvement of one of the acid groups in the intramolecular hydrogen bonding and in adduct 1c the ratio observed is 3:2. Structural features in all these assemblies have been rationalised in terms of various recognition patterns formed between the acceptor and donor groups. A noteworthy feature is that -COOH groups in acid a establish interaction with 1 through amino groups, while such interactions are observed to be through hetero -N atoms in case of the acids b-e.

2,3-Pyridine dicarboxylic acid functionalized gold nanoparticles: Insight into experimental conditions for Cr3 + sensing

NASA Astrophysics Data System (ADS)

Shaikh, Ruqaya; Memon, Najma; Solangi, Amber R.; Shaikh, Huma I.; Agheem, Muhammad Hassan; Ali, Syed Abid; Shah, Muhammad Raza; Kandhro, Aftab

2017-02-01

Selectivity of gold nanoparticles (AuNPs) depends upon surface functionality; small changes in structure or concentration bring significant changes in the behavior of AuNPs. In this study, citrate-capped AuNPs were functionalized with ortho-dicarboxylate substituted pyridine (2,3-PDCA) and detailed studies on experimental conditions were carried out to check the stability of AuNPs and response for Cr3 +. Stability of PDCA-AuNPs was found sensitive to the pH, ionic strength of buffer and its type. Capping behavior of PDCA on C-AuNPs was examined by FTIR spectroscopy. Surface morphology and size of synthesized AuNPs were confirmed by AFM, XRD, and DLS techniques where particles were found 11 nm in size, monodisperse and spherical in shape. Interaction of stabilized AuNPs was tested with various metal ions; where Cr3 + induced the changes in localized surface plasmon band (LSPR) of PDCA-AuNPs which leads to a color change from wine red to violet blue. The phenomenon is explained as cooperative effect of citrate and pyridine nitrogen on surface of AuNPs in contrary to meta-dicarboxylate substituted pyridine derivatives. Further, under optimized and controlled conditions Cr3 + shows linear response with decrease in absorbance at LSPR intensity of AuNPs (518 nm). Moreover, to demonstrate the applicability of method, Cr3 + was determined in the presence of Cr (VI) which shows 96% recovery.

Dipeptides as effective prodrugs of the unnatural amino acid (+)-2-aminobicyclo[3.1.0]hexane-2,6-dicarboxylic acid (LY354740), a selective group II metabotropic glutamate receptor agonist.

PubMed

Bueno, Ana Belén; Collado, Iván; de Dios, Alfonso; Domínguez, Carmen; Martín, José Alfredo; Martín, Luisa M; Martínez-Grau, María Angeles; Montero, Carlos; Pedregal, Concepción; Catlow, John; Coffey, D Scott; Clay, Michael P; Dantzig, Anne H; Lindstrom, Terry; Monn, James A; Jiang, Haiyan; Schoepp, Darryle D; Stratford, Robert E; Tabas, Linda B; Tizzano, Joseph P; Wright, Rebecca A; Herin, Marc F

2005-08-11

(+)-2-Aminobicyclo[3.1.0]hexane-2,6-dicarboxylic acid (1), also known as LY354740, is a highly potent and selective agonist for group II metabotropic glutamate receptors (mGlu receptors 2 and 3) tested in clinical trials. It has been shown to block anxiety in the fear-potentiated startle model. Its relatively low bioavailability in different animal species drove the need for an effective prodrug form that would produce a therapeutic response at lower doses for the treatment of anxiety disorders. We have investigated the increase of intestinal absorption of this compound by targeting the human peptide transporter hPepT1 for active transport of di- and tripeptides derived from 1. We have found that oral administration of an N dipeptide derivative of 1 (12a) in rats shows up to an 8-fold increase in drug absorption and a 300-fold increase in potency in the fear-potentiated startle model in rats when compared with the parent drug 1.

Synthesis of 3,5-Isoxazolidinediones and 1H-2,3-Benzoxazine-1,4(3H)-diones from Aliphatic Oximes and Dicarboxylic Acid Chlorides

PubMed Central

2015-01-01

The synthesis of the title compounds was carried out by reacting dicarboxylic acid chlorides with oximes in the presence of excess triethylamine. Disubstituted malonyl chlorides gave 2-alkenyl-4,4-dialkyl-3,5-isoxazolidinediones (8a–f) and 2,2′-ethylidene-bis[4,4-dialkyl-3,5-isoxazolidinedione]s (9a–f). Compounds 9 were formed from 8 and its N-unsubstituted 3,5-isoxazolidinedione decomposition product. Phthaloyl chlorides reacted with acetone oxime to yield 3-(1-methylethenyl)-1H-2,3-benzoxazine-1,4(3H)-diones (16a–e). Products 16 spontaneously decomposed to give N-unsubstituted 1H-2,3-benzoxazine-1,4(3H)-diones (17a–e) at rates that were dependent on temperature and solvent. Kinetic studies showed that two of the compounds decomposed by zero-order kinetics under neutral conditions. Butanedioyl chloride did not produce a cyclic product. PMID:24620711

Synthesis of 3,5-isoxazolidinediones and 1H-2,3-benzoxazine-1,4(3H)-diones from aliphatic oximes and dicarboxylic acid chlorides.

PubMed

Izydore, Robert A; Jones, Joseph T; Mogesa, Benjamin; Swain, Ira N; Davis-Ward, Ronda G; Daniels, Dwayne L; Kpakima, Felicia Frazier; Spaulding-Phifer, Sharnelle T

2014-04-04

The synthesis of the title compounds was carried out by reacting dicarboxylic acid chlorides with oximes in the presence of excess triethylamine. Disubstituted malonyl chlorides gave 2-alkenyl-4,4-dialkyl-3,5-isoxazolidinediones (8a-f) and 2,2'-ethylidene-bis[4,4-dialkyl-3,5-isoxazolidinedione]s (9a-f). Compounds 9 were formed from 8 and its N-unsubstituted 3,5-isoxazolidinedione decomposition product. Phthaloyl chlorides reacted with acetone oxime to yield 3-(1-methylethenyl)-1H-2,3-benzoxazine-1,4(3H)-diones (16a-e). Products 16 spontaneously decomposed to give N-unsubstituted 1H-2,3-benzoxazine-1,4(3H)-diones (17a-e) at rates that were dependent on temperature and solvent. Kinetic studies showed that two of the compounds decomposed by zero-order kinetics under neutral conditions. Butanedioyl chloride did not produce a cyclic product.

The plant homolog to the human sodium/dicarboxylic cotransporter is the vacuolar malate carrier

PubMed Central

Emmerlich, Vera; Linka, Nicole; Reinhold, Thomas; Hurth, Marco A.; Traub, Michaela; Martinoia, Enrico; Neuhaus, H. Ekkehard

2003-01-01

Malate plays a central role in plant metabolism. It is an intermediate in the Krebs and glyoxylate cycles, it is the store for CO2 in C4 and crassulacean acid metabolism plants, it protects plants from aluminum toxicity, it is essential for maintaining the osmotic pressure and charge balance, and it is therefore involved in regulation of stomatal aperture. To fulfil many of these roles, malate has to be accumulated within the large central vacuole. Many unsuccessful efforts have been made in the past to identify the vacuolar malate transporter; here, we describe the identification of the vacuolar malate transporter [A. thaliana tonoplast dicarboxylate transporter (AttDT)]. This transporter exhibits highest sequence similarity to the human sodium/dicarboxylate cotransporter. Independent T-DNA [portion of the Ti (tumor-inducing) plasmid that is transferred to plant cells] Arabidopsis mutants exhibit substantially reduced levels of leaf malate, but respire exogenously applied [14C]malate faster than the WT. An AttDT-GFP fusion protein was localized to vacuole. Vacuoles isolated from Arabidopsis WT leaves exhibited carbonylcyanide m-chlorophenylhydrazone and citrate inhibitable malate transport, which was not stimulated by sodium. Vacuoles isolated from mutant plants import [14C]-malate at strongly reduced rates, confirming that this protein is the vacuolar malate transporter. PMID:12947042

The plant homolog to the human sodium/dicarboxylic cotransporter is the vacuolar malate carrier.

PubMed

Emmerlich, Vera; Linka, Nicole; Reinhold, Thomas; Hurth, Marco A; Traub, Michaela; Martinoia, Enrico; Neuhaus, H Ekkehard

2003-09-16

Malate plays a central role in plant metabolism. It is an intermediate in the Krebs and glyoxylate cycles, it is the store for CO2 in C4 and crassulacean acid metabolism plants, it protects plants from aluminum toxicity, it is essential for maintaining the osmotic pressure and charge balance, and it is therefore involved in regulation of stomatal aperture. To fulfil many of these roles, malate has to be accumulated within the large central vacuole. Many unsuccessful efforts have been made in the past to identify the vacuolar malate transporter; here, we describe the identification of the vacuolar malate transporter [A. thaliana tonoplast dicarboxylate transporter (AttDT)]. This transporter exhibits highest sequence similarity to the human sodium/dicarboxylate cotransporter. Independent T-DNA [portion of the Ti (tumor-inducing) plasmid that is transferred to plant cells] Arabidopsis mutants exhibit substantially reduced levels of leaf malate, but respire exogenously applied [14C]malate faster than the WT. An AttDT-GFP fusion protein was localized to vacuole. Vacuoles isolated from Arabidopsis WT leaves exhibited carbonylcyanide m-chlorophenylhydrazone and citrate inhibitable malate transport, which was not stimulated by sodium. Vacuoles isolated from mutant plants import [14C]-malate at strongly reduced rates, confirming that this protein is the vacuolar malate transporter.

The mitochondrial dicarboxylate and 2-oxoglutarate carriers do not transport glutathione

PubMed Central

Booty, Lee M.; King, Martin S.; Thangaratnarajah, Chancievan; Majd, Homa; James, Andrew M.; Kunji, Edmund R.S.; Murphy, Michael P.

2015-01-01

Glutathione carries out vital protective roles within mitochondria, but is synthesised in the cytosol. Previous studies have suggested that the mitochondrial dicarboxylate and 2-oxoglutarate carriers were responsible for glutathione uptake. We set out to characterise the putative glutathione transport by using fused membrane vesicles of Lactococcus lactis overexpressing the dicarboxylate and 2-oxoglutarate carriers. Although transport of the canonical substrates could be measured readily, an excess of glutathione did not compete for substrate uptake nor could transport of glutathione be measured directly. Thus these mitochondrial carriers do not transport glutathione and the identity of the mitochondrial glutathione transporter remains unknown. PMID:25637873

Aerobic Oxidation of 5-(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan-2,5-dicarboxylic Acid Formation with CeO2 -Supported Gold Catalyst.

PubMed

Kim, Minjune; Su, Yaqiong; Fukuoka, Atsushi; Hensen, Emiel J M; Nakajima, Kiyotaka

2018-05-14

The utilization of 5-(hydroxymethyl)furfural (HMF) for the large-scale production of essential chemicals has been largely limited by the formation of solid humin as a byproduct, which prevents the operation of stepwise batch-type and continuous flow-type processes. The reaction of HMF with 1,3-propanediol produces an HMF acetal derivative that exhibits excellent thermal stability. Aerobic oxidation of the HMF acetal with a CeO 2 -supported Au catalyst and Na 2 CO 3 in water gives a 90-95 % yield of furan 2,5-dicarboxylic acid, an increasingly important commodity chemical for the biorenewables industry, from concentrated solutions (10-20 wt %) without humin formation. The six-membered acetal ring suppresses thermal decomposition and self-polymerization of HMF in concentrated solutions. Kinetic studies supported by DFT calculations identify two crucial steps in the reaction mechanism, that is, the partial hydrolysis of the acetal into 5-formyl-2-furan carboxylic acid involving OH - and Lewis acid sites on CeO 2 , and subsequent oxidative dehydrogenation of the in situ generated hemiacetal involving Au nanoparticles. These results represent a significant advance over the current state of the art, overcoming an inherent limitation of the oxidation of HMF to an important monomer for biopolymer production. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diurnal variations of total carbon, dicarboxylic acids, ketoacids and α-dicarbonyls in aerosols in the northern vicinity of Beijing

NASA Astrophysics Data System (ADS)

He, N.; Kawamura, K.; Okuzawa, K.; Kanaya, Y.; Wang, Z. F.

2013-06-01

Aerosol samples (TSP, n=58) were collected on day- and night-time basis at Mangshan in the north of Beijing, China in autumn 2007 to better understand the status of air quality and the influence of urban pollutants in the northern vicinity of Beijing. The samples were analyzed for aerosol mass, total carbon (TC), low molecular weight α, ω-dicarboxylic acids (C2-C12), ketoacids (ωC2-ωC9, pyruvic acid), α-dicarbonyls (glyoxal and methylglyoxal), as well as aromatic (phthalic, iso- and tere-phthalic) diacids. Aerosol mass and TC concentrations are higher in daytime than in nighttime. TC/aerosol mass ratios in this study are lower than those reported in megacities in East Asia, but higher than those reported in marine aerosols. Molecular distributions of diacids demonstrated that oxalic (C2) acid was the most abundant species, comprising 38-77% of total diacids, followed by succinic (C4) and malonic (C3) acids. For most compounds, the concentrations were higher in daytime than nighttime, indicating that diacids are produced in daytime by photochemical oxidation of organic precursors emitted from anthropogenic sources in Beijing during the transport to Mangshan area by the northward wind. However, we found that C2 concentrations are higher in nighttime than in daytime. A positive correlation of C2 to glyoxylic acid (ωC2) was obtained at night when relative humidity increased up to 100%, suggesting that aqueous phase production of C2 occurs in nighttime via the oxidation of ωC2. Depletion of C2 by photolysis of Fe-oxalato complexes might be another reason for the lower concentrations of C2 in daytime samples. High phthalic acid/C4 ratios in the aerosol samples suggest that automobile combustion and coal burning products are important sources, which are subjected to photochemical oxidation during the atmospheric transport of urban aerosols from Beijing. In contrast, higher concentrations of methylglyoxal in nighttime than daytime may suggest that isoprene emitted

Unique (3,8)-connected lanthanide arenedisulfonate metal-organic frameworks containing benzimidazole-5,6-dicarboxylic acid co-ligand: Syntheses, structures and luminescence

NASA Astrophysics Data System (ADS)

Sun, Yan-Qiong; Liu, Qi; Zhong, Jie-Cen; Pan, Qun-Feng; Chen, Yi-Ping

2013-10-01

Two isostructural 3D lanthanide arenedisulfonate metal-organic frameworks (MOFs) [Ln(Hbidc)(nds)0.5(H2O)]n(Ln=Eu(1), La(2)) have been successfully synthesized by the hydrothermal reaction of lanthanide oxide with 2,6-naphthalenedisulfonate sodium (Na2nds) and an auxiliary ligand, 1H-benzimidazole-5,6-dicarboxylic acid (H3bidc). The two complexes are both constructed from 2D [Ln(Hbidc)]+ double layers pillared by nds2- ligands to generate 3D (3, 8)-connected open-framework structures with 1D long narrow channels running along the a axis. From topological point of view, the 3D framework is a (3, 8)-connected tfz-d net. The weak interactions including N-H⋯O, O-H⋯O hydrogen bonds and π-π stacking are observed in 1. The 2D IR correlation spectroscopy was applied to study the molecular interactions induced by thermal perturbation. The emission spectra of 1 exhibit the characteristic transition of 5D0→7FJ(J=0-4) of Eu(III).

ω-Oxidation of α-Chlorinated Fatty Acids

PubMed Central

Brahmbhatt, Viral V.; Albert, Carolyn J.; Anbukumar, Dhanalakshmi S.; Cunningham, Bryce A.; Neumann, William L.; Ford, David A.

2010-01-01

Myeloperoxidase-derived HOCl targets tissue- and lipoprotein-associated plasmalogens to generate α-chlorinated fatty aldehydes, including 2-chlorohexadecanal. Under physiological conditions, 2-chlorohexadecanal is oxidized to 2-chlorohexadecanoic acid (2-ClHA). This study demonstrates the catabolism of 2-ClHA by ω-oxidation and subsequent β-oxidation from the ω-end. Mass spectrometric analyses revealed that 2-ClHA is ω-oxidized in the presence of liver microsomes with initial ω-hydroxylation of 2-ClHA. Subsequent oxidation steps were examined in a human hepatocellular cell line (HepG2). Three different α-chlorinated dicarboxylic acids, 2-chlorohexadecane-(1,16)-dioic acid, 2-chlorotetradecane-(1,14)-dioic acid, and 2-chloroadipic acid (2-ClAdA), were identified. Levels of 2-chlorohexadecane-(1,16)-dioic acid, 2-chlorotetradecane-(1,14)-dioic acid, and 2-ClAdA produced by HepG2 cells were dependent on the concentration of 2-ClHA and the incubation time. Synthetic stable isotope-labeled 2-ClHA was used to demonstrate a precursor-product relationship between 2-ClHA and the α-chlorinated dicarboxylic acids. We also report the identification of endogenous 2-ClAdA in human and rat urine and elevations in stable isotope-labeled urinary 2-ClAdA in rats subjected to intraperitoneal administration of stable isotope-labeled 2-ClHA. Furthermore, urinary 2-ClAdA and plasma 2-ClHA levels are increased in LPS-treated rats. Taken together, these data show that 2-ClHA is ω-oxidized to generate α-chlorinated dicarboxylic acids, which include α-chloroadipic acid that is excreted in the urine. PMID:20956542

Ozonization of polyfunctional and humic acids of sapropelites

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

Verkhodanova, N.N.; Myakina, I.A.; Egor'kov, A.N.

Data are presented which show that in the ozonization of polyfunctional acids (PFAs) and humic acids (HAs) in glacial acetic acid, all the organic carbon can be converted into the soluble form. Mono- and dicarboxylic acids of normal structure have been detected in the ozonization products. 5 refs.

Long-term trend of dicarboxylic acids, ketoacids and dicarbonyls in the marine aerosols over the western North Pacific in 2001-2006

NASA Astrophysics Data System (ADS)

Kawamura, K.; Tachibana, E.; Mochida, M.

2006-12-01

To understand a long-range atmospheric transport of water-soluble organics in the western North Pacific, remote marine aerosols were collected on weekly basis at a subtropical island (Chichijima, 142E; 27N) from 2001 to 2006 using a high volume air sampler and pre-combusted quartz filter. The island is located in the boundary of westerly and trade wind regimes. The aerosols were analyzed for dicarboxylic acids, ketoacids and dicarbonyls employing butyl ester derivatization followed by GC determination. Homologous saturated diacids (C2-C11) were detected with a predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids as well as unsaturated diacids, including maleic (M), fumaric (F), phthalic acids. Ketoacids and dicarbonyls were also detected. Concentrations of total diacids fluctuated significantly in a range of 10-600 ngm-3 with winter/spring maximum and summer minimum. The winter/spring maximum can be explained by a combinattion of enhanced emissions of polluted aerosols and their precursors in Asia and the intensified westerlies over the North Pacific in the season. Seasonal trends of the molecular compositions were also found. For example, concentration ratios of C3 to C4 acid showed a maximum in summer, indicating more oxidation of longer-chain diacids to shorter ones. M/F ratios increased from summer to winter as a result of photochemically-induced isomerization of cis and trans configuration of unsaturated diacids. On the other hand, azelaic acid (C9) relative to other diacids showed a sharp increase in summer. Because C9 is a specific photo-oxidation product of unsaturated fatty acid such as oleic acid, this demonstrates an enhanced sea-to- air emission of unsaturated fatty acids in summer followed by photochemical oxidation. Long-term trends of diacids and related compounds in the aerosols will be discussed for 2001 to 2006. The results will also be compared with those obtained at the same site for 1990 to 1993 to detect long

Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species

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

Lashley, Mark A.; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.

Studies of the complexation of new promising ligands with uranyl (UO 2 2+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO 2 2+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO 2 2+, VO 2+, and VO 2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques,more » along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO 2 2+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO 2 2+, VO 2+, and VO 2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, and structural preor-ganization for UO 2 2+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.« less

Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species

DOE PAGES

Lashley, Mark A.; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.; ...

2016-09-30

Studies of the complexation of new promising ligands with uranyl (UO 2 2+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO 2 2+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO 2 2+, VO 2+, and VO 2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques,more » along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO 2 2+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO 2 2+, VO 2+, and VO 2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, and structural preor-ganization for UO 2 2+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.« less

Identification of keto- and hydroxy-dicarboxylic acids in remote marine aerosols from the western North Pacific: GC and GC/TOF-MS measurements

NASA Astrophysics Data System (ADS)

Vani, D.; Kawamura, K.; Tachibana, E.; Boreddy, S. K. R.

2015-12-01

Dicarboxylic acids (diacids) are dominant components of organic aerosols in the atmosphere. They contribute significantly to the total aerosol mass and have a serious impacts on global climate changes. However, studies on keto- and hydroxy-diacids in marine aerosols are limited. Compare to diacids, keto- and hydroxy-diacids are more hygroscopic due to the additional polar groups (OH and CO) and, hence, acts as cloud condensation nuclei (CCN). Molecular characterization of these compounds provides insight into organic aerosols sources and transformation pathways. We collected marine aerosols from remote Chichijima Island in the western North Pacific from December 2010 to November 2011 and studied for water-soluble keto- and hydroxy-diacids. Carboxyl groups were derivatized to dibutyl esters with 14% boron trifluoride/n-butanol, whereas hydroxyl groups were derivatized to trimethylsilyl ethers using N,O-Bis (trimethylsilyl) trifluoroacetamide (BSTFA). After two-step derivatization, samples were injected to GC, GC/MS and GC/TOF-MS. In the GC chromatogram, we detected several new peaks after BSTFA derivatization of dibutyl ester fraction. Based on mass spectral interpretation, we found these peaks as homologues series of hydroxy-diacids and keto-diacids. Some of these hydroxy-diacids have been individually reported in literature in the laboratory photo-oxidation experiments and forest environments samples. But, there are no evidences to prove their sources and formation mechanism in the atmosphere. Here, we report for the first time homologous series of hydroxy-diacids (hC3di-hC6di) and keto-diacid (oxaloacetic acid, enol and keto forms) in remote marine atmosphere. Molecular distributions of hydroxy-diacids generally showed the predominance of malic acid followed by tartronic acid. Both hydroxy- and keto-diacids show significant positive correlation with oxalic acid and SO42-, suggesting that they are generated in the atmosphere and play an important role in the

Crystal structures of hibiscus acid and hibiscus acid dimethyl ester isolated from Hibiscus sabdariffa (Malvaceae).

PubMed

Zheoat, Ahmed M; Gray, Alexander I; Igoli, John O; Kennedy, Alan R; Ferro, Valerie A

2017-09-01

The biologically active title compounds have been isolated from Hibiscus sabdariffa plants, hibiscus acid as a dimethyl sulfoxide monosolvate [systematic name: (2 S ,3 R )-3-hy-droxy-5-oxo-2,3,4,5-tetra-hydro-furan-2,3-di-carb-oxy-lic acid dimethyl sulfoxide monosolvate], C 6 H 6 O 7 ·C 2 H 6 OS, (I), and hibiscus acid dimethyl ester [systematic name: dimethyl (2 S ,3 R )-3-hy-droxy-5-oxo-2,3,4,5-tetra-hydro-furan-2,3-di-carboxyl-ate], C 8 H 10 O 7 , (II). Compound (I) forms a layered structure with alternating layers of lactone and solvent mol-ecules, that include a two-dimensional hydrogen-bonding construct. Compound (II) has two crystallographically independent and conformationally similar mol-ecules per asymmetric unit and forms a one-dimensional hydrogen-bonding construct. The known absolute configuration for both compounds has been confirmed.

Fatty acids in sparry calcite fracture fills and microsparite cement of septarian diagenetic concretions

NASA Astrophysics Data System (ADS)

Pearson, M. J.; Hendry, J. P.; Taylor, C. W.; Russell, M. A.

2005-04-01

Sparry calcite fracture fills and concretion body cements in concretions from the Flodigarry Shale Member of the Staffin Shale Formation, Isle of Skye, Scotland, entrap and preserve mineral and organic materials of sedimentary and diagenetic origin. Fatty acids are a major component of the lipids recovered by decarbonation and comprise mainly n-alkanoic and α-ω dicarboxylic acids. Two generations of fracture-fill calcite (early brown and later yellow) and the concretion body microspar yield significantly different fatty acid profiles. Early brown calcites yield mainly medium-chain n-alkanoic acids with strong even predominance; later yellow calcites are dominated by α-ω dicarboxylic acids with no even predominance. Both fracture fills lack the long-chain n-alkanoic and α-ω dicarboxylic acids additionally recovered from the concretion bodies. The absence of longer chain acids in the calcite spar fracture fills is inferred to result from the transport of fatty acids by septarian mineralising fluids whereby low-aqueous solubility of longer chain acids or their salts accounts for their relative immobility. Comparative experiments have been carried out using conventional solvent extraction on the concretion body and associated shales, both decarbonated and untreated. Extracted lipid yields are higher, but the fatty acids probably derive from mixed locations in the rock including both kerogen- and carbonate-associated lipid pools. Only experiments involving decarbonation yielded α-ω dicarboxylic acids in molecular distributions probably controlled mainly by fluid transport. Alkane biomarker ratios indicate very low thermal maturity has been experienced by the concretions and their host sediments. Septarian cracks lined by brown calcite formed during early burial. Microbial CO 2 from sulphate-reducing bacteria was probably the main source of mineralising carbonate. Emplacement of the later septarian fills probably involved at least one episode of fluid invasion.

Monocarboxylic and dicarboxylic acids over oceans from the East China Sea to the Arctic Ocean: Roles of ocean emissions, continental input and secondary formation.

PubMed

Hu, Qihou; Xie, Zhouqing; Wang, Xinming; Kang, Hui; Zhang, Yuqing; Ding, Xiang; Zhang, Pengfei

2018-05-30

Organic acids are major components in marine organic aerosols. Many studies on the occurrence, sources and sinks of organic acids over oceans in the low and middle latitudes have been conducted. However, the understanding of relative contributions of specific sources to organic acids over oceans, especially in the high latitudes, is still inadequate. This study measured organic acids, including C 14:0 - C 32:0 saturated monocarboxylic acids (MCAs), C 16:1 , C 18:1 and C 18:2 unsaturated MCAs, and di-C 4 - di-C 10 dicarboxylic acids (DCAs), in the marine boundary layer from the East China Sea to the Arctic Ocean during the 3rd Chinese Arctic Research Expedition (CHINARE 08). The average concentrations were 18 ± 16 ng/m 3 and 11 ± 5.4 ng/m 3 for ΣMCA and ΣDCA, respectively. The levels of saturated MCAs were much higher than those of unsaturated DCAs, with peaks at C 16:0 , C 18:0 and C 14:0 . DCAs peaked at di-C 4 , followed by di-C 9 and di-C 8 . Concentrations of MCAs and DCAs generally decreased with increasing latitudes. Sources of MCAs and DCAs were further investigated using principal component analysis with a multiple linear regression (PCA-MLR) model. Overall, carboxylic acids originated from ocean emissions, continental input (including biomass burning, anthropogenic emissions and terrestrial plant emissions), and secondary formation. All the five sources contributed to MCAs with ocean emissions as the predominant source (48%), followed by biomass burning (20%). In contrast, only 3 sources (i.e., secondary formation (50%), anthropogenic emissions (41%) and biomass burning (9%)) contributed to DCAs. Furthermore, the sources varied with regions. Over the Arctic Ocean, only secondary formation and anthropogenic emissions contributed to MCAs and DCAs. Copyright © 2018 Elsevier B.V. All rights reserved.

Calcium sensitivity of dicarboxylate transport in cultured proximal tubule cells

PubMed Central

Schiro, Faith R.; Pajor, Ana M.; Hamm, L. Lee

2011-01-01

Urinary citrate is an important inhibitor of calcium nephrolithiasis and is primarily determined by proximal tubule reabsorption. The major transporter to reabsorb citrate is Na+-dicarboxylate cotransporter (NaDC1), which transports dicarboxylates, including the divalent form of citrate. We previously found that opossum kidney (OK) proximal tubule cells variably express either divalent or trivalent citrate transport, depending on extracellular calcium. The present studies were performed to delineate the mechanism of the effect of calcium on citrate and succinate transport in these cells. Transport was measured using isotope uptake assays. In some studies, NaDC1 transport was studied in Xenopus oocytes, expressing either the rabbit or opossum ortholog. In the OK cell culture model, lowering extracellular calcium increased both citrate and succinate transport by more than twofold; the effect was specific in that glucose transport was not altered. Citrate and succinate were found to reciprocally inhibit transport at low extracellular calcium (<60 μM), but not at normal calcium (1.2 mM); this mutual inhibition is consistent with dicarboxylate transport. The inhibition varied progressively at intermediate levels of extracellular calcium. In addition to changing the relative magnitude and interaction of citrate and succinate transport, decreasing calcium also increased the affinity of the transport process for various other dicarboxylates. Also, the affinity for succinate, at low concentrations of substrate, was increased by calcium removal. In contrast, in oocytes expressing NaDC1, calcium did not have a similar effect on transport, indicating that NaDC1 could not likely account for the findings in OK cells. In summary, extracellular calcium regulates constitutive citrate and succinate transport in OK proximal tubule cells, probably via a novel transport process that is not NaDC1. The calcium effect on citrate transport parallels in vivo studies that demonstrate the

The mitochondrial dicarboxylate and 2-oxoglutarate carriers do not transport glutathione.

PubMed

Booty, Lee M; King, Martin S; Thangaratnarajah, Chancievan; Majd, Homa; James, Andrew M; Kunji, Edmund R S; Murphy, Michael P

2015-02-27

Glutathione carries out vital protective roles within mitochondria, but is synthesised in the cytosol. Previous studies have suggested that the mitochondrial dicarboxylate and 2-oxoglutarate carriers were responsible for glutathione uptake. We set out to characterise the putative glutathione transport by using fused membrane vesicles of Lactococcus lactis overexpressing the dicarboxylate and 2-oxoglutarate carriers. Although transport of the canonical substrates could be measured readily, an excess of glutathione did not compete for substrate uptake nor could transport of glutathione be measured directly. Thus these mitochondrial carriers do not transport glutathione and the identity of the mitochondrial glutathione transporter remains unknown. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Two three-dimensional coordination polymers of lead(II) with iminodiacetate and naphthalene-dicarboxylate anions: Synthesis, characterization and luminescence behavior

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

Hazari, Debdoot; Jana, Swapan Kumar; Fleck, Michel

2014-11-15

Two lead(II) compounds [Pb{sub 3}(idiac){sub 3}(phen){sub 2}(H{sub 2}O)]·2(H{sub 2}O) (1) and [Pb(ndc)]{sub n} (2), where H{sub 2}idiac=iminodiacetic acid, phen=1,10-phenanthroline and H{sub 2}ndc=naphthalene-2,6-dicarboxylic acid, have been synthesized and structurally characterized. Single crystal X-ray diffraction analysis showed that compound 1 is a discrete trinuclear complex (of two-fold symmetry) which evolves to a supramolecular 3D network via π–π interactions, while in compound 2 the naphthalene dicarboxylate anion act as a linker to form a three dimensional architecture, where the anion adopts a bis-(bidentate bridging) coordination mode connecting four Pb(II) centers. The photoluminescence property of the two complexes has been studied. - graphical abstract:more » Two new topologically different 1D coordination polymers formed by Pb{sub 4} clusters have been synthesized and characterized by x-ray analysis. The luminescence and thermal properties have been studied. - Highlights: • 1 is a trinuclear complex of Pb(II) growing to 3D network via weak interactions. • In 1, layers of (4,4) rhomboidal topology are identified. • In 2, the ndc anion adopts interesting bis-(bidentate bridging) coordination. • In 2, network is reinforced by C–H…π-ring interactions between the ndc rings.« less

Bio-inspired nitrile hydration by peptidic ligands based on L-cysteine, L-methionine or L-penicillamine and pyridine-2,6-dicarboxylic acid.

PubMed

Byrne, Cillian; Houlihan, Kate M; Devi, Prarthana; Jensen, Paul; Rutledge, Peter J

2014-12-12

Nitrile hydratase (NHase, EC 4.2.1.84) is a metalloenzyme which catalyses the conversion of nitriles to amides. The high efficiency and broad substrate range of NHase have led to the successful application of this enzyme as a biocatalyst in the industrial syntheses of acrylamide and nicotinamide and in the bioremediation of nitrile waste. Crystal structures of both cobalt(III)- and iron(III)-dependent NHases reveal an unusual metal binding motif made up from six sequential amino acids and comprising two amide nitrogens from the peptide backbone and three cysteine-derived sulfur ligands, each at a different oxidation state (thiolate, sulfenate and sulfinate). Based on the active site geometry revealed by these crystal structures, we have designed a series of small-molecule ligands which integrate essential features of the NHase metal binding motif into a readily accessible peptide environment. We report the synthesis of ligands based on a pyridine-2,6-dicarboxylic acid scaffold and L-cysteine, L-S-methylcysteine, L-methionine or L-penicillamine. These ligands have been combined with cobalt(III) and iron(III) and tested as catalysts for biomimetic nitrile hydration. The highest levels of activity are observed with the L-penicillamine ligand which, in combination with cobalt(III), converts acetonitrile to acetamide at 1.25 turnovers and benzonitrile to benzamide at 1.20 turnovers.

Biocatalytic, one-pot diterminal oxidation and esterification of n-alkanes for production of α,ω-diol and α,ω-dicarboxylic acid esters.

PubMed

van Nuland, Youri M; de Vogel, Fons A; Scott, Elinor L; Eggink, Gerrit; Weusthuis, Ruud A

2017-11-01

Direct and selective terminal oxidation of medium-chain n-alkanes is a major challenge in chemistry. Efforts to achieve this have so far resulted in low specificity and overoxidized products. Biocatalytic oxidation of medium-chain n-alkanes - with for example the alkane monooxygenase AlkB from P. putida GPo1- on the other hand is highly selective. However, it also results in overoxidation. Moreover, diterminal oxidation of medium-chain n-alkanes is inefficient. Hence, α,ω-bifunctional monomers are mostly produced from olefins using energy intensive, multi-step processes. By combining biocatalytic oxidation with esterification we drastically increased diterminal oxidation upto 92mol% and reduced overoxidation to 3% for n-hexane. This methodology allowed us to convert medium-chain n-alkanes into α,ω-diacetoxyalkanes and esterified α,ω-dicarboxylic acids. We achieved this in a one-pot reaction with resting-cell suspensions of genetically engineered Escherichia coli. The combination of terminal oxidation and esterification constitutes a versatile toolbox to produce α,ω-bifunctional monomers from n-alkanes. Copyright © 2017 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Biocatalytic ammonolysis of (5S)-4,5-dihydro-1H-pyrrole-1,5-dicarboxylic acid, 1-(1,1-dimethylethyl)-5-ethyl ester: preparation of an intermediate to the dipeptidyl peptidase IV inhibitor Saxagliptin.

PubMed

Gill, Iqbal; Patel, Ramesh

2006-02-01

An efficient biocatalytic method has been developed for the conversion of (5S)-4,5-dihydro-1H-pyrrole-1,5-dicarboxylic acid, 1-(1,1-dimethylethyl)-5-ethyl ester (1) into the corresponding amide (5S)-5-aminocarbonyl-4,5-dihydro-1H-pyrrole-1-carboxylic acid, 1-(1,1-dimethylethyl)ester (2), which is a critical intermediate in the synthesis of the dipeptidyl peptidase IV (DPP4) inhibitor Saxagliptin (3). Candida antartica lipase B mediates ammonolysis of the ester with ammonium carbamate as ammonia donor to yield up to 71% of the amide. The inclusion of Ascarite and calcium chloride as adsorbents for carbon dioxide and ethanol byproducts, respectively, increases the yield to 98%, thereby offering an efficient and practical alternative to chemical routes which yield 57-64%.

Barium coordination polymers based on fluorinated and fluorine-free benzene-dicarboxylates: Mechanochemical synthesis and spectroscopic characterization

NASA Astrophysics Data System (ADS)

Al-Terkawi, Abdal-Azim; Scholz, Gudrun; Emmerling, Franziska; Kemnitz, Erhard

2018-05-01

A series of new Ba-based coordination polymers (CPs) were mechanochemically synthesized by milling Ba-hydroxide samples with perfluorinated and fluorine-free benzene-dicarboxylic acids, including tetrafluoroisophthalic acid (H2mBDC-F4), tetrafluorophthalic acid (H2oBDC-F4), isophthalic acid (H2mBDC) and phthalic acid (H2oBDC). The new fluorinated CPs: [Ba(mBDC-F4)·0.5H2O] (1) and [Ba(oBDC-F4)·1.5H2O] (2) are compared to their nonfluorinated counterparts: [Ba(mBDC)·2.5H2O] (3), and [Ba(oBDC)·1H2O] (4). These materials are thoroughly characterized using powder X-ray diffraction. The products obtained by milling are all hydrated but vary in their water contents. Compositions and local structures are investigated by elemental analysis, thermal analysis, MAS NMR and attenuated total reflection-infrared spectroscopy. These materials exhibit high thermal stabilities but small surface areas that remain unchanged even after thermal treatments.

Method for the production of dicarboxylic acids

DOEpatents

Nghiem, N.P.; Donnelly, M.; Millard, C.S.; Stols, L.

1999-02-09

The present invention is an economical fermentation method for the production of carboxylic acids comprising the steps of (a) inoculating a medium having a carbon source with a carboxylic acid-producing organism; (b) incubating the carboxylic acid-producing organism in an aerobic atmosphere to promote rapid growth of the organism thereby increasing the biomass of the organism; (c) controllably releasing oxygen to maintain the aerobic atmosphere; (d) controllably feeding the organism having increased biomass with a solution containing the carbon source to maintain the concentration of the carbon source within the medium of about 0.5 g/l up to about 1 g/l; (e) depriving the aerobic atmosphere of oxygen to produce an anaerobic atmosphere to cause the organism to undergo anaerobic metabolism; (f) controllably feeding the organism having increased biomass a solution containing the carbon source to maintain the concentration of the carbon source within the medium of {>=}1 g/l; and (g) converting the carbon source to carboxylic acids using the anaerobic metabolism of the organism. 7 figs.

Method for the production of dicarboxylic acids

DOEpatents

Nghiem, Nhuan Phu; Donnelly, Mark; Millard, Cynthia S.; Stols, Lucy

1999-01-01

The present invention is an economical fermentation method for the production of carboxylic acids comprising the steps of a) inoculating a medium having a carbon source with a carboxylic acid-producing organism; b) incubating the carboxylic acid-producing organism in an aerobic atmosphere to promote rapid growth of the organism thereby increasing the biomass of the organism; c) controllably releasing oxygen to maintain the aerobic atmosphere; d) controllably feeding the organism having increased biomass with a solution containing the carbon source to maintain the concentration of the carbon source within the medium of about 0.5 g/L up to about 1 g/L; e) depriving the aerobic atmosphere of oxygen to produce an anaerobic atmosphere to cause the organism to undergo anaerobic metabolism; f) controllably feeding the organism having increased biomass a solution containing the carbon source to maintain the concentration of the carbon source within the medium of .gtoreq.1 g/L; and g) converting the carbon source to carboxylic acids using the anaerobic metabolism of the organism.

Development of a Δ9-Tetrahydrocannabinol Amino Acid-Dicarboxylate Prodrug With Improved Ocular Bioavailability

PubMed Central

Adelli, Goutham R.; Bhagav, Prakash; Taskar, Pranjal; Hingorani, Tushar; Pettaway, Sara; Gul, Waseem; ElSohly, Mahmoud A.; Repka, Michael A.; Majumdar, Soumyajit

2017-01-01

Purpose The aim of the present study was to evaluate the utility of the relatively hydrophilic Δ9-tetrahydrocannabinol (THC) prodrugs, mono and di-valine esters (THC-Val and THC-Val-Val) and the amino acid (valine)-dicarboxylic acid (hemisuccinate) ester (THC-Val-HS), with respect to ocular penetration and intraocular pressure (IOP) lowering activity. THC, timolol, and pilocarpine eye drops were used as controls. Methods THC-Val, THC-Val-Val, and THC-Val-HS were synthesized and chemically characterized. Aqueous solubility and in vitro transcorneal permeability of THC and the prodrugs, in the presence of various surfactants and cyclodextrins, were determined. Two formulations were evaluated for therapeutic activity in the α-chymotrypsin induced rabbit glaucoma model, and the results were compared against controls comprising of THC emulsion and marketed timolol maleate and pilocarpine eye drops. Results THC-Val-HS demonstrated markedly improved solubility (96-fold) and in vitro permeability compared to THC. Selected formulations containing THC-Val-HS effectively delivered THC to the anterior segment ocular tissues in the anesthetized rabbits: 62.1 ng/100 μL of aqueous humor (AH) and 51.4 ng/50 mg of iris ciliary bodies (IC) (total THC). The duration and extent of IOP lowering induced by THC-Val-HS was 1 hour longer and 10% greater, respectively, than that obtained with THC and was comparable with the pilocarpine eye drops. Timolol ophthalmic drops, however, exhibited a longer duration of activity. Both THC and THC-Val-HS were detected in the ocular tissues following multiple dosing of THC-Val-HS in conscious animals. The concentration of THC in the iris-ciliary bodies at the 60- and 120-minute time points (53 and 57.4 ng/50 mg) were significantly greater than that of THC-Val-HS (24.2 and 11.3 ng/50 mg). Moreover, at the two time points studied, the concentration of THC was observed to increase or stay relatively constant, whereas THC-Val-HS concentration decreased

Solvothermal synthesis and structure of 3D frameworks of Nd(III) and Y(III) with thiophene-2,5-dicarboxylate and N,N‧-diethylformamide

NASA Astrophysics Data System (ADS)

Sharma, Swati; Yawer, Mohd; Kariem, Mukaddus; Sheikh, Haq Nawaz

2016-08-01

Two new 3D MOFs [Nd2(TDA)3(DEF)2(H2O)]n (1) and [Y4(TDA)6(DEF)4]n (2) [Thiophene-2,5-dicarboxylic acid (H2TDA) and N,N‧-diethylformamide (DEF)] were synthesized by solvothermal method. They were characterized by elemental analyses, infrared spectroscopy and single crystal X-ray diffraction studies. The two MOFs (1) and (2) belong to the monoclinic system with space group P21/n and C 2 respectively. Structural characterizations by single-crystal X-ray crystallography reveal that 1 and 2 adopt three-dimensional frameworks constructed by cross-linking of rod shaped infinite chain secondary building unit (SBU) by thiophene-2,5-dicarboxylates as linker. These frameworks feature rhomboidal channels, inside which coordinated DEF/H2O solvent molecules are located. DEF plays pivotal role in reaction and design of MOFs. Thermogravimetric analysis shows that both MOFs are thermally robust.

Anticonvulsant actions of LY 367385 ((+)-2-methyl-4-carboxyphenylglycine) and AIDA ((RS)-1-aminoindan-1,5-dicarboxylic acid).

PubMed

Chapman, A G; Yip, P K; Yap, J S; Quinn, L P; Tang, E; Harris, J R; Meldrum, B S

1999-02-26

We have studied the effects in three rodent models of generalised convulsive or absence epilepsy of two antagonists of group I metabotropic glutamate receptors that are selective for the mGlu1 receptor. LY 367385 ((+)-2-methyl-4-carboxyphenylglycine) and AIDA ((RS)-1-aminoindan-1,5-dicarboxylic acid) have been administered intracerebroventricularly (i.c.v.) to DBA/2 mice and lethargic mice (lh/lh), and focally into the inferior colliculus of genetically epilepsy prone rats (GEPR). In DBA/2 mice both compounds produce a rapid, transient suppression of sound-induced clonic seizures (LY 367385: ED50 = 12 nmol, i.c.v., 5 min; AIDA: ED50 = 79 nmol, i.c.v., 15 min). In lethargic mice both compounds significantly reduce the incidence of spontaneous spike and wave discharges on the electroencephalogram, from <30 to >150 min after the administration of AIDA, 500 nmol, i.c.v., and from 30 to >150 min after the administration of LY 367385, 250 nmol, i.c.v. LY 367385, 50 nmol, suppresses spontaneous spike and wave discharges from 30 to 60 min. In genetically epilepsy prone rats both compounds reduce sound-induced clonic seizures. LY 367385, 160 nmol bilaterally, fully suppresses clonic seizures after 2-4 h. AIDA is fully effective 30 min after 100 nmol bilaterally. It is concluded that antagonists of mGlu1 receptors are potential anticonvulsant agents and that activation of mGlu1 receptors probably contributes to a variety of epileptic syndromes.

Structures and physical properties of the cocrystals of adefovir dipivoxil with dicarboxylic acids

NASA Astrophysics Data System (ADS)

Jung, Sungyup; Lee, Jonghwi; Kim, Il Won

2013-06-01

The cocrystallization of adefovir dipivoxil (AD) with suberic acid (SUB) or succinic acid (SUC) was examined. X-ray diffraction was used to determine the structures of AD/SUB and AD/SUC cocrystals. Both cocrystals were formed via multiple hydrogen bonds between the adenine part of AD and the carboxylic acid groups of SUB or SUC. Longer SUB effectively dispersed AD molecules, and AD hydrogen-bonded only to SUB. When shorter SUC was used, AD formed hydrogen bonding with both SUC and adjacent AD. As a result, the cocrystal compositions were AD/SUB=1:1 and AD/SUC=2:1. Both cocrystals displayed superior thermal stability and increased aqueous solubility. The present study demonstrated that the adenine and similar structures of active pharmaceutical ingredients could be used to produce cocrystals of improved physical properties.

Production of platform chemical itaconic acid from pentose sugars

USDA-ARS?s Scientific Manuscript database

In recent years, itaconic acid (IA), an unsaturated five carbon dicarboxylic acid, has gained importance as a fully sustainable building block chemical (platform chemical) for a wide range of applications in the manufacturing of various synthetic resins, coatings, and polymers. It is currently produ...

Carboxylic acid accelerated formation of diesters

DOEpatents

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

1998-04-28

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.

Secondary formation of oxalic acid and related organic species from biogenic sources in a larch forest at the northern slope of Mt. Fuji

NASA Astrophysics Data System (ADS)

Mochizuki, Tomoki; Kawamura, Kimitaka; Miyazaki, Yuzo; Wada, Ryuichi; Takahashi, Yoshiyuki; Saigusa, Nobuko; Tani, Akira

2017-10-01

To better understand the formation of water-soluble organic aerosols in the forest atmosphere, we measured low molecular weight (LMW) dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, unsaturated fatty acids (UFAs), and water-soluble organic carbon (WSOC) in aerosols from a Larix kaempferi forest located at the northern slope of Mt. Fuji, Japan, in summer 2012. Concentrations of dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, and WSOC showed maxima in daytime. Relative abundance of oxalic acid in LMW dicarboxylic acids was on average 52% and its average concentration was 214 ng m-3. We found that diurnal and temporal variations of oxalic acid are different from those of isoprene and α-pinene, whereas biogenic secondary organic aerosols (BSOAs) derived from isoprene and α-pinene showed similar variations with oxalic acid. The mass concentration ratios of oxalic acid/BSOAs were relatively constant, although a large variation in the concentrations of toluene that is an anthropogenic volatile organic compound was observed. These results suggest that formation of oxalic acid is associated with the oxidation of isoprene and α-pinene with O3 and other oxidants in the forest atmosphere. In addition, concentrations of UFAs were observed, for the first time, to decrease dramatically during daytime in the forest. Mass concentration ratios of azelaic acid to UFAs showed a positive correlation with O3, suggesting that UFAs are oxidized to yield azelaic acid, which may be further decomposed to oxalic acid in the forest atmosphere. We found that contributions of oxalic acid to WSOC are significantly high ranging from 3.7 to 9.7% (average 6.0%). This study demonstrates that forest ecosystem is an important source of oxalic acid and other dicarboxylic acids in the atmosphere.

An enhanced procedure for measuring organic acids and methyl esters in PM2.5

NASA Astrophysics Data System (ADS)

Liu, F.; Duan, F. K.; He, K. B.; Ma, Y. L.; Rahn, K. A.; Zhang, Q.

2015-11-01

A solid-phase extraction (SPE) pretreatment procedure allowing organic acids to be separated from methyl esters in fine aerosol has been developed. The procedure first separates the organic acids from fatty acid methyl esters (FAMEs) and other nonacid organic compounds by aminopropyl-based SPE cartridge and then quantifies them by gas chromatography/mass spectrometry. The procedure prevents the fatty acids and dimethyl phthalate from being overestimated, and so allows us to accurately quantify the C4-C11 dicarboxylic acids (DCAs) and the C8-C30 monocarboxylic acids (MCAs). Results for the extraction of DCAs, MCAs, and AMAs in eluate and FAMEs in effluate by SAX and NH2 SPE cartridges exhibited that the NH2 SPE cartridge gave higher extraction efficiency than the SAX cartridge. The recoveries of analytes ranged from 67.5 to 111.3 %, and the RSD ranged from 0.7 to 10.9 %. The resulting correlations between the aliphatic acids and FAMEs suggest that the FAMEs had sources similar to those of the carboxylic acids, or were formed by esterifying carboxylic acids, or that aliphatic acids were formed by hydrolyzing FAMEs. Through extraction and cleanup using this procedure, 17 aromatic acids in eluate were identified and quantified by gas chromatography/tandem mass spectrometry, including five polycyclic aromatic hydrocarbon (PAH): acids 2-naphthoic, biphenyl-4-carboxylic, 9-oxo-9H-fluorene-1-carboxylic, biphenyl-4,4´-dicarboxylic, and phenanthrene-1-carboxylic acid, plus 1,8-naphthalic anhydride. Correlations between the PAH acids and the dicarboxylic and aromatic acids suggested that the first three acids and 1,8-naphthalic anhydride were secondary atmospheric photochemistry products and the last two mainly primary.

Production of itaconic acid from pentose sugars by Aspergillus terreus

USDA-ARS?s Scientific Manuscript database

Itaconic acid (IA), an unsaturated 5-carbon dicarboxylic acid, is a building block platform chemical that is currently produced industrially with glucose by fermentation with Aspergillus terreus (A. terreus). However, lignocellulosic biomass has the potential to serve as a low cost source of sugars ...

Generation of gas-phase sodiated arenes such as [(Na3(C6H4)+] from benzene dicarboxylate salts.

PubMed

Attygalle, Athula B; Chan, Chang-Ching; Axe, Frank U; Bolgar, Mark

2010-01-01

Upon collision-induced activation, gaseous sodium adducts generated by electrospray ionization of disodium salts of 1,2- 1,3-, and 1,4-benzene dicarboxylic acids (m/z 233) undergo an unprecedented expulsion of CO(2) by a rearrangement process to produce an ion of m/z 189 in which all three sodium atoms are retained. When isolated in a collision cell of a tandem-in-space mass spectrometer, and subjected to collision-induced dissociation (CID), only the m/z 189 ions derived from the meta and para isomers underwent a further CO(2) loss to produce a peak at m/z 145 for a sodiated arene of formula (Na(3)C(6)H(4))(+). This previously unreported m/z 145 ion, which is useful to differentiate meta and para benzene dicarboxylates from their ortho isomer, is in fact the sodium adduct of phenelenedisodium. Moreover, the m/z 189 ion from all three isomers readily expelled a sodium radical to produce a peak at m/z 166 for a radical cation [(*C(6)H(4)CO(2)Na(2))(+)], which then eliminated CO(2) to produce a peak at m/z 122 for the distonic cation (*C(6)H(4)Na(2))(+). Copyright 2009 John Wiley & Sons, Ltd.

Carboxylic acid accelerated formation of diesters

DOEpatents

Tustin, Gerald Charles; Dickson, Todd Jay

1998-01-01

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.

Method of increasing conversion of a fatty acid to its corresponding dicarboxylic acid

DOEpatents

Craft, David L.; Wilson, C. Ron; Eirich, Dudley; Zhang, Yeyan

2004-09-14

A nucleic acid sequence including a CYP promoter operably linked to nucleic acid encoding a heterologous protein is provided to increase transcription of the nucleic acid. Expression vectors and host cells containing the nucleic acid sequence are also provided. The methods and compositions described herein are especially useful in the production of polycarboxylic acids by yeast cells.

Molecular compositions and decadal trends of dicarboxylic acids, ketoacids, α-dicarbonyls in the marine aerosols from Chichi-Jima Island in the western North Pacific

NASA Astrophysics Data System (ADS)

Kawamura, K.; Tachibana, E.

2010-12-01

A rapid industrial development in China and East Asian countries for last two decades may have seriously changed the air quality of the North Pacific. To better understand a long-term atmospheric changes of organic aerosols in the western North Pacific, we collected marine aerosol samples on weekly basis at a remote island, Chichijima (27°04'E; 142°13'N) in 2001-2010. The island is located in the boundary of westerly and easterly wind regimes. The aerosol samples were analyzed for dicarboxylic acids, ketoacids and α-dicarbonyls employing butyl ester derivatization followed by GC determination, together with total carbon (TC) and water-soluble organic carbon (WSOC). Homologous series of saturated diacids (C2-C11) were detected with a predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids. Unsaturated diacids, including maleic (M), fumaric (F), phthalic, and iso-/tere-phthalic acids, were also detected together with ketoacids and α-dicarbonyls. Concentrations of total diacids fluctuated significantly in a range of 10-600 ngm-3 with winter/spring maximum and summer minimum. The maximum was explained by a combination of enhanced emissions of polluted aerosols and their precursors in Asia and enhanced atmospheric transport to the North Pacific due to the intensified westerly winds in winter/spring. Concentration ratios of C3 to C4 diacid (range 0.2-28, av. 2.8) showed a maximum during summer, indicating more oxidation of longer-chain diacids to shorter ones. Azelaic acid (C9) that is a specific photo-oxidation product of unsaturated fatty acid such as oleic acid showed a sharp increase relative to other diacids in summer, suggesting enhanced sea-to-air emission of unsaturated fatty acids followed by photochemical oxidation during summer. On the other hand, M/F ratios (range 0-8.7, av. 1.1) significantly decreased from winter to summer due to photochemical cis-to-trans isomerization. We also discuss decadal trends in the concentrations of

Copper and manganese complexes based on 1,4-naphthalene dicarboxylic acid ligand and its derivative: Syntheses, crystal structures, and magnetic properties

NASA Astrophysics Data System (ADS)

Xing, Yubo; Liu, Yuqi; Xue, Xiaofei; Wang, Xinying; Li, Wei

2018-02-01

Three new metal-organic coordination polymers, {[Mn2(1,4-NDC)2 (C2H5OH) (DMF) (H2O)]·CH3OH}n(1), {[Mn(III)(1,4-NDC)(C2H5O)][Mn(II)(1,4-NDC)(DMF)(H2O)]}n(2) and {[Cu2(C13H9O4)4(H2O)2]}n(3) based on1,4-H2NDC and its derivative were hydrothermally synthesized (1,4-H2NDC = 1,4-naphthalene-dicarboxylic acid, C13H10O4 = 4-methyl formate-1-naphthalenecarboxylic acid), and characterized by techniques of single crystal X-ray diffraction, infrared spectra (IR), elemental analysis, powder X-ray diffraction(PXRD) and variable-temperature magnetic susceptibility measurements. X-ray crystal structure analyses reveal that complexes 1 and 2 show a same 3,5-connected fsc 3D topology network with the Schlȁfli symbol of {4·6·8}{4·66·83}. But, the valence of some Mn atom in complex 2 take place transition from the +II oxidation state to the +III oxidation state, which may be the effect of the different solvent ratio. In complex 3, the Cu⋯Cu distance of 2.620(13) Å is significantly shorter than the sum of the van der Waals radii of Cu (1.40 Å), resulting in a strong ferromagnetic interaction between the Cu(II) centers. Furthermore, the temperature-dependent magnetic susceptibility measurements exhibit overall antiferromagnetic interactions between manganese ions for complexes 1 and 2, and a strong ferromagnetic interaction between the Cu(II) centers for complex 3.

Programming of a Mn-coordinated 4-4‧-biphenyl dicarboxylic acid nanosystem on Au(1 1 1) and investigation of the non-covalent binding of C60 molecules

NASA Astrophysics Data System (ADS)

Zhang, Yan-Feng; Zhu, Na; Komeda, T.

The fabrication of Mn-based coordination networks on a Au(1 1 1) substrate with 4-4 '-biphenyl dicarboxylic acid (BDA) as the linker molecule was investigated by scanning tunneling microscopy. Intriguing structures of ladder and rectangular-shaped networks were obtained by controlling the ratios of deposited amount of BDA molecules and Mn atoms. These structures are well explained by models in which BDA molecules occupy the perimeter of the rectangles and a pair of two Mn atoms are placed at the lattice points. For the rectangular structure, further two phases of a rectangular and a square networks were identified in which the paired Mn atoms were directing an identical direction and 90° rotated in an alternate manner, respectively. In addition, it was revealed that the open space surrounded by rectangle BDA molecules could capture a dimer of C60 molecules which were deposited on the Mn-based BDA networks.

Synthesis and Pharmacological Characterization of C4-(Thiotriazolyl)-substituted-2-aminobicyclo[3.1.0]hexane-2,6-dicarboxylates. Identification of (1R,2S,4R,5R,6R)-2-Amino-4-(1H-1,2,4-triazol-3-ylsulfanyl)bicyclo[3.1.0]hexane-2,6-dicarboxylic Acid (LY2812223), a Highly Potent, Functionally Selective mGlu2 Receptor Agonist.

PubMed

Monn, James A; Prieto, Lourdes; Taboada, Lorena; Hao, Junliang; Reinhard, Matthew R; Henry, Steven S; Beadle, Christopher D; Walton, Lesley; Man, Teresa; Rudyk, Helene; Clark, Barry; Tupper, David; Baker, S Richard; Lamas, Carlos; Montero, Carlos; Marcos, Alicia; Blanco, Jaime; Bures, Mark; Clawson, David K; Atwell, Shane; Lu, Frances; Wang, Jing; Russell, Marijane; Heinz, Beverly A; Wang, Xushan; Carter, Joan H; Getman, Brian G; Catlow, John T; Swanson, Steven; Johnson, Bryan G; Shaw, David B; McKinzie, David L

2015-09-24

Identification of orthosteric mGlu(2/3) receptor agonists capable of discriminating between individual mGlu2 and mGlu3 subtypes has been highly challenging owing to the glutamate-site sequence homology between these proteins. Herein we detail the preparation and characterization of a series of molecules related to (1S,2S,5R,6S)-2-aminobicyclo[3.1.0]hexane-2,6-dicarboxylate 1 (LY354740) bearing C4-thiotriazole substituents. On the basis of second messenger responses in cells expressing other recombinant human mGlu2/3 subtypes, a number of high potency and efficacy mGlu2 receptor agonists exhibiting low potency mGlu3 partial agonist/antagonist activity were identified. From this, (1R,2S,4R,5R,6R)-2-amino-4-(1H-1,2,4-triazol-3-ylsulfanyl)bicyclo[3.1.0]hexane-2,6-dicarboxylic acid 14a (LY2812223) was further characterized. Cocrystallization of 14a with the amino terminal domains of hmGlu2 and hmGlu3 combined with site-directed mutation studies has clarified the underlying molecular basis of this unique pharmacology. Evaluation of 14a in a rat model responsive to mGlu2 receptor activation coupled with a measure of central drug disposition provides evidence that this molecule engages and activates central mGlu2 receptors in vivo.

Wormlike micelle formation by acylglutamic acid with alkylamines.

PubMed

Sakai, Kenichi; Nomura, Kazuyuki; Shrestha, Rekha Goswami; Endo, Takeshi; Sakamoto, Kazutami; Sakai, Hideki; Abe, Masahiko

2012-12-21

Rheological properties of alkyl dicarboxylic acid-alkylamine complex systems have been characterized. The complex materials employed in this study consist of an amino acid-based surfactant (dodecanoylglutamic acid, C12Glu) and a tertiary alkylamine (dodecyldimethylamine, C12DMA) or a secondary alkylamine (dodecylmethylamine, C12MA). (1)H NMR and mass spectroscopic data have suggested that C12Glu forms a stoichiometric 1:1 complex with C12DMA and C12MA. Rheological measurements have suggested that the complex systems yield viscoelastic wormlike micellar solutions and the rheological behavior is strongly dependent on the aqueous solution pH. This pH-dependent behavior results from the structural transformation of the wormlike micelles to occur in the narrow pH range 5.5-6.2 (in the case of C12Glu-C12DMA system); i.e., positive curved aggregates such as spherical or rodlike micelles tend to be formed at high pH values. Our current study offers a unique way to obtain viscoelastic wormlike micellar solutions by means of alkyl dicarboxylic acid-alkylamine complex as gemini-like amphiphiles.

Solvothermal syntheses, structures, and magnetic properties of three cobalt coordination polymers constructed from naphthalene-1,4-dicarboxylic acid and bis(imidazole) linkers

NASA Astrophysics Data System (ADS)

Dong, Jun-Liang; He, Kun-Huan; Wang, Duo-Zhi; Zhang, Ying-Hui; Wang, Dan-Hong

2018-07-01

Three new Co(II) coordination polymers with formulas of {[Co2(L1)(1,4-NDC)2]·3H2O}n (1), [Co3(L2)2(HCOO)2(1,4-NDC)2]n (2) and [Co2(L2)(μ3-OH)(1,4-NDC)1.5]n (3) (1,4-H2NDC = Naphthalene-1,4-dicarboxylic acid, L1 = di(1H-imidazol-1-yl)methane, L2 = 1,4-di(1H-imidazol-1-yl)benzene) were solvothermal synthesized from 1,4-H2NDC with the aid of three different length-controllable auxiliary ligands and fully characterized. Their structures are determined by single-crystal X-ray diffraction, IR spectra, elemental analysis, powder X-ray diffraction and thermogravimetric analysis. Complexes 1 and 3 display 3D framework structures, corresponding to a 6-connected (412·63) net, a 8-connected (424·5·63) net, respectively. However, it is noteworthy that the complex 1 displays a 2-fold interpenetrating framework structure, complex 3 possesses a self-interpenetrating framework structure. Complex 2 displays 2D 4-connected undulating plane net structure. Moreover, magnetic studies indicate antiferromagnetic interactions between the Co(II) ions in the four complexes.

Oxidative degradation of organic acids conjugated with sulfite oxidation in flue gas desulfurization

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

Lee, Y.I.

Organic acid degradation conjugated with sulfite oxidation has been studied under flue gas desulfurization (EGD) conditions. The oxidative degradation constant, k/sub 12/, is defined as the ratio of organic acid degradation rate and sulfite oxidation rate after being normalized by the concentrations of organic acid and dissolved S(IV). K/sub 12/, not significantly affected by pH or dissolved oxygen, is around 10/sup -3/ in the absence of manganese or iron. However, k/sub 12/ is increased by certain transition metals such as Co, Ni, and Fe and is decreased by Mn and halides. Lower dissolved S(IV) magnified these effects. No k/sub 12/more » greater than 4 x 10/sup -3/ or smaller than 0.1 x 10/sup -3/ has been observed. A free radical mechanism was proposed to describe the kinetics: (1) sulfate free radical is the major radical responsible to the degradation of organic acid; (2) ferrous generates sulfate radical by reacting with monoxypersulfate to enhance k/sub 12/; (3) manganous consumes sulfate radical to decrease k/sub 12/; (4) dissolved S(IV) competes with ferrous for monoxypersulfate and with manganous for sulfate radical to demonstrate the effects of dissolved S(IV) on k/sub 12/. Hydroxy and sulfonated carboxylic acids degrade approximately three times slower than saturated dicarboxylic acids; while maleic acid, an unsaturated dicarboxylic acid, degraded an order of magnitude faster. A wide spectrum of degradation products of adipic acid were found, including carbon dioxide - the major product, glutaric semialdehyde - the major retained product with low manganese, glutaric acid and valeric acids - the major retained product with high manganese, lower molecular weight mono- and dicarboxylic acids, other carbonyl compounds, and hydrocarbons.« less

Emerging biotechnologies for production of itaconic acid and its applications as a platform chemical

USDA-ARS?s Scientific Manuscript database

Recently, itaconic acid (IA), an unsaturated C5-dicarboxylic acid, has attracted much attention as a biobased building block chemical. It is produced industrially (> 80 g L**-1) from glucose by fermentation with Aspergillus terreus. The titer is low compared with citric acid production (> 200 g L**-...

Amino and fatty acids in carbonaceous meteorites

NASA Technical Reports Server (NTRS)

Kvenvolden, K. A.

1974-01-01

Analyses of two carbonaceous meteorites have provided much of the latest evidence which seems to support Oparin's theory on the origin of life. The meteorites involved are the Murray meteorite, which fell in 1950, and the Murchison meteorite, which fell in 1969. The amino acids in the two meteorites are similar in composition. Eight of the twenty amino acids found belong to amino acids present in proteins. A number of monocarboxylic and dicarboxylic fatty acids were also found in the meteorites.

Rapid radiosynthesis of [11C] and [14C]azelaic, suberic, and sebacic acids for in vivo mechanistic studies of systemic acquired resistance in plants

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

Best M.; Fowler J.; Best, M.

2011-11-25

A recent report that the aliphatic dicarboxylic acid, azelaic acid (1,9-nonanedioic acid) but not related acids, suberic acid (1,8-octanedioic acid) or sebacic (1,10-decanedioic acid) acid induces systemic acquired resistance to invading pathogens in plants stimulated the development of a rapid method for labeling these dicarboxylic acids with {sup 11}C and {sup 14}C for in vivo mechanistic studies in whole plants. {sup 11}C-labeling was performed by reaction of ammonium [{sup 11}C]cyanide with the corresponding bromonitrile precursor followed by hydrolysis with aqueous sodium hydroxide solution. Total synthesis time was 60 min. Median decay-corrected radiochemical yield for [{sup 11}C]azelaic acid was 40% relativemore » to trapped [{sup 11}C]cyanide, and specific activity was 15 GBq/{micro}mol. Yields for [{sup 11}C]suberic and sebacic acids were similar. The {sup 14}C-labeled version of azelaic acid was prepared from potassium [{sup 14}C]cyanide in 45% overall radiochemical yield. Radiolabeling procedures were verified using {sup 13}C-labeling coupled with {sup 13}C-NMR and liquid chromatography-mass spectrometry analysis. The {sup 11}C and {sup 14}C-labeled azelaic acid and related dicarboxylic acids are expected to be of value in understanding the mode-of-action, transport, and fate of this putative signaling molecule in plants.« less

Identification and Functional Characterization of a Tonoplast Dicarboxylate Transporter in Tomato (Solanum lycopersicum)

PubMed Central

Liu, Ruiling; Li, Boqiang; Qin, Guozheng; Zhang, Zhanquan; Tian, Shiping

2017-01-01

Acidity plays an important role in flavor and overall organoleptic quality of fruit and is mainly due to the presence of organic acids. Understanding the molecular basis of organic acid metabolism is thus of primary importance for fruit quality improvement. Here, we cloned a putative tonoplast dicarboxylate transporter gene (SlTDT) from tomato, and submitted it to the NCBI database (GenBank accession number: KC733165). SlTDT protein contained 13 putative transmembrane domains in silico analysis. Confocal microscopic study using green fluorescent fusion proteins revealed that SlTDT was localized on tonoplast. The expression patterns of SlTDT in tomato were analyzed by RT-qPCR. The results indicated that SlTDT expressed in leaves, roots, flowers and fruits at different ripening stages, suggesting SlTDT may be associated with the development of different tissues. To further explore the function of SlTDT, we constructed both overexpression and RNAi vectors and obtained transgenic tomato plants by agrobacterium-mediated method. Gas chromatography-mass spectrometer (GC-MS) analysis showed that overexpression of SlTDT significantly increased malate content, and reduced citrate content in tomato fruit. By contrast, repression of SlTDT in tomato reduced malate content of and increased citrate content. These results indicated that SlTDT played an important role in remobilization of malate and citrate in fruit vacuoles. PMID:28261242

Identification and Functional Characterization of a Tonoplast Dicarboxylate Transporter in Tomato (Solanum lycopersicum).

PubMed

Liu, Ruiling; Li, Boqiang; Qin, Guozheng; Zhang, Zhanquan; Tian, Shiping

2017-01-01

Acidity plays an important role in flavor and overall organoleptic quality of fruit and is mainly due to the presence of organic acids. Understanding the molecular basis of organic acid metabolism is thus of primary importance for fruit quality improvement. Here, we cloned a putative tonoplast dicarboxylate transporter gene ( SlTDT ) from tomato, and submitted it to the NCBI database (GenBank accession number: KC733165). SlTDT protein contained 13 putative transmembrane domains in silico analysis. Confocal microscopic study using green fluorescent fusion proteins revealed that SlTDT was localized on tonoplast. The expression patterns of SlTDT in tomato were analyzed by RT-qPCR. The results indicated that SlTDT expressed in leaves, roots, flowers and fruits at different ripening stages, suggesting SlTDT may be associated with the development of different tissues. To further explore the function of SlTDT , we constructed both overexpression and RNAi vectors and obtained transgenic tomato plants by agrobacterium-mediated method. Gas chromatography-mass spectrometer (GC-MS) analysis showed that overexpression of SlTDT significantly increased malate content, and reduced citrate content in tomato fruit. By contrast, repression of SlTDT in tomato reduced malate content of and increased citrate content. These results indicated that SlTDT played an important role in remobilization of malate and citrate in fruit vacuoles.

CYP86B1 Is Required for Very Long Chain ω-Hydroxyacid and α,ω-Dicarboxylic Acid Synthesis in Root and Seed Suberin Polyester1[W][OA

PubMed Central

Compagnon, Vincent; Diehl, Patrik; Benveniste, Irène; Meyer, Denise; Schaller, Hubert; Schreiber, Lukas; Franke, Rochus; Pinot, Franck

2009-01-01

Suberin composition of various plants including Arabidopsis (Arabidopsis thaliana) has shown the presence of very long chain fatty acid derivatives C20 in addition to the C16 and C18 series. Phylogenetic studies and plant genome mining have led to the identification of putative aliphatic hydroxylases belonging to the CYP86B subfamily of cytochrome P450 monooxygenases. In Arabidopsis, this subfamily is represented by CYP86B1 and CYP86B2, which share about 45% identity with CYP86A1, a fatty acid ω-hydroxylase implicated in root suberin monomer synthesis. Here, we show that CYP86B1 is located to the endoplasmic reticulum and is highly expressed in roots. Indeed, CYP86B1 promoter-driven β-glucuronidase expression indicated strong reporter activities at known sites of suberin production such as the endodermis. These observations, together with the fact that proteins of the CYP86B type are widespread among plant species, suggested a role of CYP86B1 in suberin biogenesis. To investigate the involvement of CYP86B1 in suberin biogenesis, we characterized an allelic series of cyp86B1 mutants of which two strong alleles were knockouts and two weak ones were RNA interference-silenced lines. These root aliphatic plant hydroxylase lines had a root and a seed coat aliphatic polyester composition in which C22- and C24-hydroxyacids and α,ω-dicarboxylic acids were strongly reduced. However, these changes did not affect seed coat permeability and ion content in leaves. The presumed precursors, C22 and C24 fatty acids, accumulated in the suberin polyester. These results demonstrate that CYP86B1 is a very long chain fatty acid hydroxylase specifically involved in polyester monomer biosynthesis during the course of plant development. PMID:19525321

Mannose and galactose as substrates for production of itaconic acid by Aspergillus terreus

USDA-ARS?s Scientific Manuscript database

Itaconic acid (IA), an unsaturated 5-carbon dicarboxylic acid, is a building block platform chemical that is currently produced industrially from glucose by fermentation with Aspergillus terreus. Softwood has the potential to serve as low cost source of sugars for its production. Effective utilizati...

Six uranyl-organic frameworks with naphthalene-dicarboxylic acid and bipyridyl-based spacers: syntheses, structures, and properties.

PubMed

Xu, Wei; Ren, Ya-Nan; Xie, Miao; Zhou, Lin-Xia; Zheng, Yue-Qing

2018-03-28

A new series of uranium coordination polymers have been hydrothermally synthesized by using 1,4-naphthalene dicarboxylic acid (H 2 NDC), namely, (H 3 O) 2 [(UO 2 ) 2 (NDC) 3 ]·H 2 O (1), (H 2 -bpp)[(UO 2 ) 2 (NDC) 3 ]·EtOH·5H 2 O (2), (H 2 -bpe) 2/2 [(UO 2 ) 2 (NDC) 3 ]·EtOH (3), (H 2 -bpp)[(UO 2 ) 2 (NDC) 3 ]·5H 2 O (4), (H 2 -bpp)[(UO 2 )(HNDC)(NDC)] 2 ·2H 2 O (5), and (H 2 -bpy)[(UO 2 )(NDC) 2 ] (6) [bpp = 1,3-di(4-pyridyl) propane, bpe = 4,4'-vinylenedipyridine, bpy = 4,4'-bipyridine]. Single-crystal X-ray diffraction demonstrates that complex 1 represents the uranyl-organic polycatenated framework derived from a simple two-dimensional honeycomb grid network structure via a H 2 NDC linker. Complexes 2-4 contain the dinuclear motifs of the two UO 7 pentagonal and one UO 8 hexagonal bipyramids which are linked by NDC 2- anions creating a (UO 2 ) 4 (NDC) 2 unit, and further extend to a 2D layer through NDC 2- anions. Complex 5 displays a 1D zigzag double chain structure, in which the carboxylate groups of the NDC 2- anions adopt a chelate mode and further extends to a 2D framework via hydrogen bonds. The 1D structure of complex 6 is similar to the zigzag chain of complex 5. In addition, powder X-ray diffraction, elemental analysis, IR, thermal stability and luminescence properties of all complexes have also been investigated in this paper. The photocatalytic properties of the six complexes for the degradation of tetracycline hydrochloride (TC) under UV irradiation have been examined. Moreover, density functional theory (DFT) calculations were carried out to explore the electronic structural and bonding properties of the uranyl complexes 1-6.

[Biosynthesis of adipic acid].

PubMed

Han, Li; Chen, Wujiu; Yuan, Fei; Zhang, Yuanyuan; Wang, Qinhong; Ma, Yanhe

2013-10-01

Adipic acid is a six-carbon dicarboxylic acid, mainly for the production of polymers such as nylon, chemical fiber and engineering plastics. Its annual demand is close to 3 million tons worldwide. Currently, the industrial production of adipic acid is based on the oxidation of aromatics from non-renewable petroleum resources by chemo-catalytic processes. It is heavily polluted and unsustainable, and the possible alternative method for adipic acid production should be developed. In the past years, with the development of synthetic biology and metabolic engineering, green and clean biotechnological methods for adipic acid production attracted more attention. In this study, the research advances of adipic acid and its precursor production are reviewed, followed by addressing the perspective of the possible new pathways for adipic acid production.

A Strategy Combining Higher Energy C-Trap Dissociation with Neutral Loss- and Product Ion-Based MSn Acquisition for Global Profiling and Structure Annotation of Fatty Acids Conjugates

NASA Astrophysics Data System (ADS)

Bi, Qi-rui; Hou, Jin-jun; Yang, Min; Shen, Yao; Qi, Peng; Feng, Rui-hong; Dai, Zhuo; Yan, Bing-peng; Wang, Jian-wei; Shi, Xiao-jian; Wu, Wan-ying; Guo, De-an

2017-03-01

Fatty acids conjugates (FACs) are ubiquitous but found in trace amounts in the natural world. They are composed of multiple unknown substructures and side chains. Thus, FACs are difficult to be analyzed by traditional mass spectrometric methods. In this study, an integrated strategy was developed to global profiling and targeted structure annotation of FACs in complex matrix by LTQ Orbitrap. Dicarboxylic acid conjugated bufotoxins (DACBs) in Venenum bufonis (VB) were used as model compounds. The new strategy (abbreviated as HPNA) combined higher-energy C-trap dissociation (HCD) with product ion- (PI), neutral loss- (NL) based MSn (n ≥ 3) acquisition in both positive-ion mode and negative-ion mode. Several advantages are presented. First, various side chains were found under HCD in negative-ion mode, which included both known and unknown side chains. Second, DACBs with multiple side chains were simultaneously detected in one run. Compared with traditional quadrupole-based mass method, it greatly increased analysis throughput. Third, the fragment ions of side chain and steroids substructure could be obtained by PI- and NL-based MSn acquisition, respectively, which greatly increased the accuracy of the structure annotation of DACBs. In all, 78 DACBs have been discovered, of which 68 were new compounds; 25 types of substructure formulas and seven dicarboxylic acid side chains were found, especially five new side chains, including two saturated dicarboxylic acids [(azelaic acid (C9) and sebacic acid (C10)] and three unsaturated dicarboxylic acids (u-C8, u-C9, and u-C10). All these results greatly enriched the structures of DACBs in VB.

A 3D metal-organic framework with a pcu net constructed from lead(II) and thiophene-2, 5-dicarboxylic acid: Synthesis, structure and ferroelectric property

NASA Astrophysics Data System (ADS)

Lin, Jian-Di; Rong, Cheng; Lv, Ri-Xin; Wang, Zu-Jian; Long, Xi-Fa; Guo, Guo-Cong; Pan, Chun-Yang

2018-01-01

Self-assembly reaction of Pb(NO3)2 with thiophene-2, 5-dicarboxylic acid (H2TDC) led to an acentric three-dimensional (3D) metal-organic framework under solvothermal conditions, namely, Pb(TDC) (1). The 3D framework of 1 is a pillared-layer structure with the I2O1 type which is composed of a 2D inorganic Pb-O-Pb substructural layer and two independent μ6-TDC2- anions pillars. This 3D framework shows a six-connected pcu topological net according to the topological analysis. Compound 1 crystallizes in an acentric space group and displays potential ferroelectric property which could be due to the swing of the thiophene rings. The remnant polarization (Pr), coercive field (Ec) and saturation spontaneous polarization (Ps) of 1 are ca. 0.034 μC cm-2, 15.7 kV cm-1 and 0.0997 μC cm-2, respectively. Among the H2TDC-based MOFs, the present compound is the first example which shows ferroelectric property. In addition, 1 also exhibits photoluminescent property which can be attributed to ligand-to-metal charge transfer.

Enhanced concentrations of citric acid in spring aerosols collected at the Gosan background site in East Asia

NASA Astrophysics Data System (ADS)

Jung, Jinsang; Kawamura, Kimitaka

2011-09-01

In order to investigate water-soluble dicarboxylic acids and related compounds in the aerosol samples under the Asian continent outflow, total suspended particle (TSP) samples ( n = 32) were collected at the Gosan site in Jeju Island over 2-5 days integration during 23 March-1 June 2007 and 16-24 April 2008. The samples were analyzed for water-soluble dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls using a capillary gas chromatography technique. We found elevated concentrations of atmospheric citric acid (range: 20-320 ng m -3) in the TSP samples during mid- to late April of 2007 and 2008. To specify the sources of citric acid, dicarboxylic acids and related compounds were measured in the pollen sample collected at the Gosan site (Pollen_Gosan), authentic pollen samples from Japanese cedar ( Cryptomeria) (Pollen_cedar) and Japanese cypress ( Chamaecyparis obtusa) (Pollen_cypress), and tangerine fruit produced from Jeju Island. Citric acid (2790 ng in unit mg of pollen mass) was found as most abundant species in the Pollen_Gosan, followed by oxalic acid (2390 ng mg -1). Although citric acid was not detected in the Pollen_cedar and Pollen_cypress as major species, it was found as a dominant species in the tangerine juice while malic acid was detected as major species in the tangerine peel, followed by oxalic and citric acids. Since Japanese cedar trees are planted around tangerine farms to prevent strong winds from the Pacific Ocean, citric acid that may be directly emitted from tangerine is likely adsorbed on pollens emitted from Japanese cedar and then transported to the Gosan site. Much lower malic/citric acid ratios obtained under cloudy condition than clear condition suggest that malic acid may rapidly decompose to lower molecular weight compounds such as oxalic and malonic acids (

Polymerization of beta-amino acids in aqueous solution

NASA Technical Reports Server (NTRS)

Liu, R.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

1998-01-01

We have compared carbonyl diimidazole (CDI) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as activating agents for the oligomerization of negatively-charged alpha- and beta-amino acids in homogeneous aqueous solution. alpha-Amino acids can be oligomerized efficiently using CDI, but not by EDAC. beta-Amino acids can be oligomerized efficiently using EDAC, but not by CDI. Aspartic acid, an alpha- and beta-dicarboxylic acid is oligomerized efficiently by both reagents. These results are explained in terms of the mechanisms of the reactions, and their relevance to prebiotic chemistry is discussed.

Trans-hemispheric contribution of C2-C10 α, ω-dicarboxylic acids, and related polar compounds to water-soluble organic carbon in the western Pacific aerosols in relation to photochemical oxidation reactions

NASA Astrophysics Data System (ADS)

SempéRé, Richard; Kawamura, Kimitaka

2003-06-01

Marine aerosol samples were collected during a western Pacific cruise covering the latitude range between 35°N and 40°S (140°E-180°E). They were analyzed for total carbon (TC), total nitrogen (TN), water-soluble organic carbon (WSOC) along with the molecular distributions of C2-C10 α, ω-dicarboxylic acids, and related polar compounds, mainly, ω-oxocarboxylic acids (C2-C9) and α-dicarbonyls (C2-C3). Oxalic acid (C2) was the most abundant followed by malonic (C3) and succinic (C4) acids. The total diacid concentration range was 7-605 ng m-3 (av. 85 ng m-3) and the diacid-carbon accounted for 2-15% (average 8%) of WSOC which comprised 29-55% (average 40%) of TC. Dry depositions of total diacids over the northern and southern Pacific Ocean were estimated to be 256-1907 μg m-2 yr-1 (average 735; n = 4) and 22-396 μg m-2 yr-1 (average 134; n = 14), respectively, whereas the air-to-sea flux of oxalic acid was 18-1351 μg m-2 yr-1 (average 466 μg m-2 yr-1) and 7.5-275 μg m-2 yr-1 (average 75 μg m-2 yr-1) in the Northern and Southern Hemispheres. We observed that the concentration ratios of diacid-C/WSOC, azelaic acid (C9)/ω-oxononanoic acid, maleic acid (iC4cis)/fumaric (iC4trans) acid and succinic acid (C4)/total diacids were correlated with air temperature. These findings showed that the intensity of photochemical oxidation reactions and thus the variation in sunlight intensity characterized here by air temperature, significantly control the molecular distribution of water-soluble organic compounds during the long-range transport of anthropogenic and/or biogenic higher molecular weight organic compounds.

Efficiencies of acid catalysts in the hydrolysis of lignocellulosic biomass over a range of combined severity factors

Treesearch

Jae-Won Lee; Thomas W. Jeffries

2011-01-01

Dicarboxylic organic acids have properties that differ from those of sulfuric acid during hydrolysis of lignocellulose. To investigate the effects of different acid catalysts on the hydrolysis and degradation of biomass compounds over a range of thermochemical pretreatments, maleic, oxalic and sulfuric acids were each used at the same combined severity factor (CSF)...

Molecular distributions and stable carbon isotopic compositions of dicarboxylic acids and related compounds in aerosols from Sapporo, Japan: Implications for photochemical aging during long-range atmospheric transport

NASA Astrophysics Data System (ADS)

Aggarwal, Shankar G.; Kawamura, Kimitaka

2008-07-01

Molecular and stable carbon isotopic (δ13C value) compositions of dicarboxylic acids, ketoacids, and dicarbonyls in aerosol samples (i.e., total suspended particles) collected in Sapporo, northern Japan during spring and summer were determined to better understand the photochemical aging of organic aerosols during long-range transport from East Asia and Siberia. Their molecular distributions were characterized by the predominance of oxalic acid (C2) followed by malonic (C3) or occasionally succinic (C4) acids. Concentrations of total diacids ranged from 106-787 ng m-3 with ketoacids (13-81 ng m-3) and dicarbonyls (2.6-28 ng m-3) being less abundant. Water-soluble organic carbon (WSOC) comprised 23-69% of aerosol organic carbon (OC). OC to elemental carbon (EC) ratios were high (3.6-19, mean: 8.7). The ratios of C3/C4 and WSOC/OC did not show significant diurnal changes, suggesting that the Sapporo aerosols were not seriously affected by local photochemical processes and instead they were already aged. δ13C values of the dominant diacids (C2 - C4) ranged from -14.0 to -25.3‰. Largest δ13C values (-14.0 to -22.4‰, mean: -18.8‰) were obtained for C2, whereas smallest values (-25.1 to -31.4‰, mean: -28.1‰) were for azelaic acid (C9). In general, δ13C values of C2 - C4 diacids became less negative with aerosol aging (i.e., WSOC/OC), presumably due to isotopic fractionation during photochemical degradation of diacids. By comparing the δ13C values of diacids in the Sapporo aerosols with different air mass source regions, we suggest that although initial δ13C values of diacids depend on their precursor sources, the enrichment in 13C can be ascribed to aerosol photochemical aging.

By-products of electrochemical synthesis of suberic acid

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

Shirobokova, O.I.; Adamov, A.A.; Freidlin, G.N.

By-products of the electrochemical synthesis of dimethyl suberate from glutaric anhydride were studied. This is isolated by thermal dehydration of a mixture of lower dicarboxylic acids that are wastes from the production of adipic acid. To isolate the by-products, they used the methods of vacuum rectification and preparative gas-liquid chromatography, and for their identification, PMR, IR spectroscopy, gas-liquid chromatography, and other known physicochemical methods of investigation.

Thermokinetic profile of NDM-1 and its inhibition by small carboxylic acids

PubMed Central

Wang, Qian; He, Yuan; Lu, Rui; Wang, Wen-Ming; Yang, Ke-Wu; Fan, Hai Ming; Jin, Yi; Blackburn, G. Michael

2018-01-01

The New Delhi metallo-β-lactamase (NDM-1) is an important clinical target for antimicrobial research, but there are insufficient clinically useful inhibitors and the details of NDM-1 enzyme catalysis remain unclear. The aim of this work is to provide a thermodynamic profile of NDM-1 catalysed hydrolysis of β-lactams using an isothermal titration calorimetry (ITC) approach and to apply this new method to the identification of new low-molecular-weight dicarboxylic acid inhibitors. The results reveal that hydrolysis of penicillin G and imipenem by NDM-1 share the same thermodynamic features with a significant intrinsic enthalpy change and the release of one proton into solution, while NDM-1 hydrolysis of cefazolin exhibits a different mechanism with a smaller enthalpy change and the release of two protons. The inhibitory constants of four carboxylic acids are found to be in the micromolar range. The compounds pyridine-2,6-dicarboxylic acid and thiazolidine-2,4-dicarboxylic acid show the best inhibitory potency and are confirmed to inhibit NDM-1 using a clinical strain of Escherichia coli. The pyridine compound is further shown to restore the susceptibility of this E. coli strain to imipenem, at an inhibitor concentration of 400 μM, while the thiazoline compound also shows a synergistic effect with imipenem. These results provide valuable information to enrich current understanding on the catalytic mechanism of NDM-1 and to aid the future optimisation of β-lactamase inhibitors based on these scaffolds to tackle the problem of antibiotic resistance. PMID:29507059

Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids

Treesearch

Liheng Chen; Junyong Zhu; Carlos Baez; Peter Kitin; Thomas Elder

2016-01-01

Here we report the production of highly thermal stable and functional cellulose nanocrystals (CNC) and nanofibrils (CNF) by hydrolysis using concentrated organic acids. Due to their low water solubility, these solid organic acids can be easily recovered after hydrolysis reactions through crystallization at a lower or ambient temperature. When dicarboxylic acids were...

Molecular distribution, seasonal variation, chemical transformation and sources of dicarboxylic acids and related compounds in atmospheric aerosols at remote marine Gosan site, Jeju Island

NASA Astrophysics Data System (ADS)

Kundu, S.; Kawamura, K.; Lee, M.

2009-12-01

: A homologous series of C2-C12 α, ω-dicarboxylic acids, ω-oxocarboxylic acids (C2-C9), pyruvic acid and α-dicarbonyls (C2-C3) were detected in atmospheric aerosols collected between April 2003 and April 2004 from remote marine Gosan site (33°29‧ N, 126°16‧ E) located in Jeju Island, South Korea. They were determined using a GC-FID and GC/MS. Total diacid concentration ranged from 130 to 1911 ng m-3 (av. 642 ng m-3), whereas total oxoacid concentration ranged from 7 to 155 ng m-3 (av. 43 ng m-3), and pyruvic acid and α-dicarbonyls ranged from 0.5 to 15 ng m-3 (av. 5 ng m-3) and 2-108 ng m-3 (av. 17.3 ng m-3), respectively. Oxalic (C2) acid was the most abundant in all seasons followed by malonic (C3) or succinic (C4) acid, and phthalic (Ph) acid. The concentration of diacids decreased with an increase in carbon number except for azelaic (C9) acid, which was more abundant than suberic (C8) acid. Glyoxylic acid was predominant ω-oxoacid contributing to 92% of total ω-oxoacid. Total diacids, oxoacids and dicarbonyls showed maximum concentrations in spring and occasionally in winter, while minimum concentrations were observed in summer. Air mass trajectory analysis suggests that either spring or winter maxima can be explained by strong continental outflow associated with cold front passages, while summer minima are associated with warm southerly flows, which transport clean marine air from low latitudes to Jeju Island. The comparison between total diacid concentration level of this study and other study results of urban and remote sites of East Asia reveals that Gosan site is more heavily influenced by the continental outflow from China. The seasonal variation of malonic/succinic (C3/C4), malic/succinic (hC4/C4), fumaric/maleic (F/M), oxalic/pyruvic (C2/Py) and oxalic/Glyoxal (C2/Gly) ratios showed maxima in summer due to an enhanced photo-production and degradation of diacids and related compounds. Throughout all seasons C3/C4 ratio at Gosan site, located

cis,cis-Muconic acid: separation and catalysis to bio-adipic acid for nylon-6,6 polymerization

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

Vardon, Derek R.; Rorrer, Nicholas A.; Salvachúa, Davinia

cis,cis-Muconic acid is a polyunsaturated dicarboxylic acid that can be produced renewably via the biological conversion of sugars and lignin-derived aromatic compounds. Subsequently, muconic acid can be catalytically converted to adipic acid -- the most commercially significant dicarboxylic acid manufactured from petroleum. Nylon-6,6 is the major industrial application for adipic acid, consuming 85% of market demand; however, high purity adipic acid (99.8%) is required for polymer synthesis. As such, process technologies are needed to effectively separate and catalytically transform biologically derived muconic acid to adipic acid in high purity over stable catalytic materials. To that end, this study: (1) demonstratesmore » bioreactor production of muconate at 34.5 g L-1 in an engineered strain of Pseudomonas putida KT2440, (2) examines the staged recovery of muconic acid from culture media, (3) screens platinum group metals (e.g., Pd, Pt, Rh, Ru) for activity and leaching stability on activated carbon (AC) and silica supports, (4) evaluates the time-on-stream performance of Rh/AC in a trickle bed reactor, and (5) demonstrates the polymerization of bio-adipic acid to nylon-6,6. Separation experiments confirmed AC effectively removed broth color compounds, but subsequent pH/temperature shift crystallization resulted in significant levels of Na, P, K, S and N in the crystallized product. Ethanol dissolution of muconic acid precipitated bulk salts, achieving a purity of 99.8%. Batch catalysis screening reactions determined that Rh and Pd were both highly active compared to Pt and Ru, but Pd leached significantly (1-9%) from both AC and silica supports. Testing of Rh/AC in a continuous trickle bed reactor for 100 h confirmed stable performance after 24 h, although organic adsorption resulted in reduced steady-state activity. Lastly, polymerization of bio-adipic acid with hexamethyldiamine produced nylon-6,6 with comparable properties to its petrochemical

Structural modulation and luminescent properties of four Cd{sup II} coordination architectures based on 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole and flexible/rigid dicarboxylate ligands

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

Xia, Liang; Dong, Wen-Wen, E-mail: dongww1@126.com; Ye, Xiao

To systematically investigate the influence of the flexible or rigid auxiliary ligands on the structures and properties of transition metal compounds, we synthesized four new d{sup 10} coordination polymers (CPs) from 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (4-Hpzpt) and flexible/rigid dicarboxylate ligands, [Cd(4-pzpt){sub 2}]{sub n} (1), [Cd{sub 3}(4-pzpt){sub 2}(suc){sub 2}]{sub n} (2), [Cd{sub 2}(4-Hpzpt)(nbc){sub 2}(H{sub 2}O)]{sub n} (3) and ([Cd{sub 2}(4-pzpt){sub 2}(tfbdc)(H{sub 2}O){sub 4}]·H{sub 2}O){sub n} (4) (H{sub 2}suc=1,2-ethanedicarboxylic acid, H{sub 2}nbc=hthalene-1,4-dicarboxylic acid, H{sub 2}tfbdc =2,3,5,6-tetrafluoroterephthalic acid). Single crystal X-ray analysis indicates that compound 1 shows a 4{sup 4}-sql layer, which is extended to a 3D network via nonclassical C–H{sup …}N hydrogen bonds. Compound 2more » possesses a 6-connected pcu-4{sup 12}0.6{sup 3} net composed of trinuclear Cd{sup II}-clusters. Compound 3 represents a rare 3D (3,4,4,5)-connected topology with a Schläfli symbol of (4·6·7)(4·5{sup 3}·7{sup 2})(5{sup 3}·6·7·9)(4{sup 2}·5{sup 5}·6·7{sup 2}). Compound 4 exhibits a 2D+2D→2D parallel interpenetrated 6{sup 3}-hcb network. The adjacent 2D networks are interdigitated with each other to form the resulting 3D supramolecular architecture through classical O–H{sup …}N and O–H{sup …}O hydrogen bonds. Structural diversities indicate that the nature of flexible/rigid-dicarboxlates plays crucial roles in modulating structures of these compounds. Moreover, the luminescent properties of them have been briefly investigated. - Graphical abstract: Four new Cd{sup II} coordination architectures constructed from the primary ligand 4-Hpzpt and flexible/rigid dicarboxylate coligands. Structural diversities indicate that the nature of flexible/rigid-dicarboxlates plays crucial roles in modulating structures of these compounds. And more, the thermal stability and luminescence are discussed. - Highlights

Molecular complexes of alprazolam with carboxylic acids, boric acid, boronic acids, and phenols. Evaluation of supramolecular heterosynthons mediated by a triazole ring.

PubMed

Varughese, Sunil; Azim, Yasser; Desiraju, Gautam R

2010-09-01

A series of molecular complexes, both co-crystals and salts, of a triazole drug-alprazolam-with carboxylic acids, boric acid, boronic acids, and phenols have been analyzed with respect to heterosynthons present in the crystal structures. In all cases, the triazole ring behaves as an efficient hydrogen bond acceptor with the acidic coformers. The hydrogen bond patterns exhibited with aromatic carboxylic acids were found to depend on the nature and position of the substituents. Being a strong acid, 2,6-dihydroxybenzoic acid forms a salt with alprazolam. With aliphatic dicarboxylic acids alprazolam forms hydrates and the water molecules play a central role in synthon formation and crystal packing. The triazole ring makes two distinct heterosynthons in the molecular complex with boric acid. Boronic acids and phenols form consistent hydrogen bond patterns, and these are seemingly independent of the substitutional effects. Boronic acids form noncentrosymmetric cyclic synthons, while phenols form O--H...N hydrogen bonds with the triazole ring.

Identification of EayjjPB encoding a dicarboxylate transporter important for succinate production under aerobic and anaerobic conditions in Enterobacter aerogenes.

PubMed

Fukui, Keita; Nanatani, Kei; Hara, Yoshihiko; Tokura, Mitsunori; Abe, Keietsu

2018-05-01

Enterobacter aerogenes, a gram-negative, rod-shaped bacterium, is an effective producer of succinate from glucose via the reductive tricarboxylic acid cycle under anaerobic conditions. However, to date, succinate-exporter genes have not been identified in E. aerogenes, although succinate exporters have a large impact on fermentative succinate production. Recently, we genetically identified yjjP and yjjB, as genes encoding a succinate transporter in Escherichia coli. Evaluation of the yjjPB homologs in E. aerogenes (EayjjPB genes) showed that succinate accumulation increased from 4.1 g L -1 to 9.1 g L -1 when the EayjjPB genes were expressed under aerobic conditions. Under anaerobic conditions, succinate yield increased from 53% to 60% by EayjjPB expression and decreased to 48% by deletion of EayjjPB. Furthermore, the production levels of fumarate and malate, which are intermediates of the succinate-biosynthesis pathway, were also increased by EayjjPB expression. A complementation assay conducted in Corynebacterium glutamicum strain AJ110655ΔsucE1 demonstrated that both EaYjjP and EaYjjB are required for the restoration of succinate production. Taken together, these results suggest that EaYjjPB function as a dicarboxylate transporter in E. aerogenes and that the products of both genes are required for dicarboxylate transport. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Two new coordination polymers constructed by naphthalene-1,4-dicarboxylic acid and 2,4-diamino-6-methyl-triazine

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

Li, Yamin, E-mail: liyamin@henu.edu.cn; Xiao, Changyu; Zhang, Xudong

2013-08-15

Two new transition metal coordination complexes, ([MnO(nda)](H{sub 2}dmt)(H{sub 2}O)){sub n} (1), [Ag{sub 5}(nda){sub 2.5}(dmt)]{sub n} (2), (H{sub 2}nda=naphthalene-1,4-dicarboxylic acid, dmt=2,4-diamine-6-methyl-1,3,5-triazine) have been hydrothermally synthesized by the reactions of H{sub 2}nda and dmt with the homologous MnCl{sub 2}·4H{sub 2}O and AgNO{sub 3}, respectively, and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis, thermogravimetric analysis (TGA). The compound 1 exhibits a 3D network comprising 1D metal chain (MnO(CO{sub 2}){sub 2}){sub n} connected by the ligand nda{sup 2−}, featuring a four-connected uninodal diamond -like topology. In compound 2, it is firstly observed that decanuclear silver units as secondary building units to constructmore » 3D network by the ligands dmt and nda{sup 2−}, with a rare 2-nodal (3,8)-connected tfz-d topology ((4{sup 3}){sub 2}(4{sup 6}.6{sup 18}.8{sup 4})). The interactions within each Mn(II)—Mn(II) pair of compound 1 are antiferromagnetic (g=2.07, J=−1.42(1) cm{sup −1}, zj′=−0.73(2) cm{sup −1}). In addition, compound 2 exhibits photoluminescent property at about 472 nm (λ{sub ex}=394 nm). - Graphical abstract: Two new transition metal coordination complexes 1–2 have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis thermogravimetric analysis (TGA). Highlights: • The compound 1 exhibits a 3D network with four-connected uninodal diamond-like topology. • The first 3D network of 2 with a rare tfz-d topology consists of decanuclear silver clusters as secondary building units. • The magnetic measurement indicates the compound 1 shows antiferromagnetic interactions. • The photoluminescent property of 2 has been measured.« less

Furan-based benzene mono- and dicarboxylic acid derivatives as multiple inhibitors of the bacterial Mur ligases (MurC-MurF): experimental and computational characterization.

PubMed

Perdih, Andrej; Hrast, Martina; Pureber, Kaja; Barreteau, Hélène; Grdadolnik, Simona Golič; Kocjan, Darko; Gobec, Stanislav; Solmajer, Tom; Wolber, Gerhard

2015-06-01

Bacterial resistance to the available antibiotic agents underlines an urgent need for the discovery of novel antibacterial agents. Members of the bacterial Mur ligase family MurC-MurF involved in the intracellular stages of the bacterial peptidoglycan biosynthesis have recently emerged as a collection of attractive targets for novel antibacterial drug design. In this study, we have first extended the knowledge of the class of furan-based benzene-1,3-dicarboxylic acid derivatives by first showing a multiple MurC-MurF ligase inhibition for representatives of the extended series of this class. Steady-state kinetics studies on the MurD enzyme were performed for compound 1, suggesting a competitive inhibition with respect to ATP. To the best of our knowledge, compound 1 represents the first ATP-competitive MurD inhibitor reported to date with concurrent multiple inhibition of all four Mur ligases (MurC-MurF). Subsequent molecular dynamic (MD) simulations coupled with interaction energy calculations were performed for two alternative in silico models of compound 1 in the UMA/D-Glu- and ATP-binding sites of MurD, identifying binding in the ATP-binding site as energetically more favorable in comparison to the UMA/D-Glu-binding site, which was in agreement with steady-state kinetic data. In the final stage, based on the obtained MD data novel furan-based benzene monocarboxylic acid derivatives 8-11, exhibiting multiple Mur ligase (MurC-MurF) inhibition with predominantly superior ligase inhibition over the original series, were discovered and for compound 10 it was shown to possess promising antibacterial activity against S. aureus. These compounds represent novel leads that could by further optimization pave the way to novel antibacterial agents.

Furan-based benzene mono- and dicarboxylic acid derivatives as multiple inhibitors of the bacterial Mur ligases (MurC-MurF): experimental and computational characterization

NASA Astrophysics Data System (ADS)

Perdih, Andrej; Hrast, Martina; Pureber, Kaja; Barreteau, Hélène; Grdadolnik, Simona Golič; Kocjan, Darko; Gobec, Stanislav; Solmajer, Tom; Wolber, Gerhard

2015-06-01

Bacterial resistance to the available antibiotic agents underlines an urgent need for the discovery of novel antibacterial agents. Members of the bacterial Mur ligase family MurC-MurF involved in the intracellular stages of the bacterial peptidoglycan biosynthesis have recently emerged as a collection of attractive targets for novel antibacterial drug design. In this study, we have first extended the knowledge of the class of furan-based benzene-1,3-dicarboxylic acid derivatives by first showing a multiple MurC-MurF ligase inhibition for representatives of the extended series of this class. Steady-state kinetics studies on the MurD enzyme were performed for compound 1, suggesting a competitive inhibition with respect to ATP. To the best of our knowledge, compound 1 represents the first ATP-competitive MurD inhibitor reported to date with concurrent multiple inhibition of all four Mur ligases (MurC-MurF). Subsequent molecular dynamic (MD) simulations coupled with interaction energy calculations were performed for two alternative in silico models of compound 1 in the UMA/ d-Glu- and ATP-binding sites of MurD, identifying binding in the ATP-binding site as energetically more favorable in comparison to the UMA/ d-Glu-binding site, which was in agreement with steady-state kinetic data. In the final stage, based on the obtained MD data novel furan-based benzene monocarboxylic acid derivatives 8- 11, exhibiting multiple Mur ligase (MurC-MurF) inhibition with predominantly superior ligase inhibition over the original series, were discovered and for compound 10 it was shown to possess promising antibacterial activity against S. aureus. These compounds represent novel leads that could by further optimization pave the way to novel antibacterial agents.

Kinetic and molecular orbital analyses of dicarboxylic acylcarnitine methylesterification show that derivatization may affect the screening of newborns by tandem mass spectrometry.

PubMed

Maeda, Yasuhiro; Nakajima, Yoko; Gotoh, Kana; Hotta, Yuji; Kataoka, Tomoya; Sugiyama, Naruji; Shirai, Naohiro; Ito, Tetsuya; Kimura, Kazunori

2016-01-01

Newborns are routinely screened for organic acidemias by acylcarnitine analysis. We previously reported the partial catalytic methylesterification of dicarboxylic acylcarnitines by benzenesulfonic acid moiety in the solid extraction cartridge during extraction from serum. Since the diagnosis of organic acidemias by tandem mass spectrometry is affected by the higher molecular weight of these derivatized acylcarnitines, we investigated the methylesterification conditions. The kinetic constants for the methylesterification of carboxyl groups on the acyl and carnitine sides of carnitine were 2.5 and 0.24h(-1), respectively. The physical basis underlying this difference in methylesterification rates was clarified theoretically, illustrating that methylesterification during extraction proceeds easily and must be prevented. Copyright © 2015 Elsevier Ltd. All rights reserved.

Amylose-dicarboxylic acid inclusion complexes: Characterization and comparison to monocarboxylic acid complexes

USDA-ARS?s Scientific Manuscript database

One of the main components in starch, amylose is an essentially linear polymer composed of glucose connected through alpha-1,4-bonds. Amylose is well known to form helical inclusion complexes with various types of ligands such as iodine, medium and long chain fatty acids, alcohols, lactones, and fl...

Azelaic acid (15% gel) in the treatment of acne rosacea.

PubMed

Gupta, Aditya K; Gover, Melissa D

2007-05-01

In December of 2002, the FDA approved azelaic acid 15% gel for the topical treatment of inflammatory papules and pustules of mild to moderate rosacea. Azelaic acid is a saturated dicarboxylic acid, which is naturally occurring and has been used in the treatment of rosacea, acne, and melasma. The 15% gel has a high efficacy and is generally well tolerated, with the local irritation (burning, stinging, itching, and scaling) being typically mild and transient. Azelaic acid 15% gel is considered effective and safe as a therapy for inflammatory papulo-pustular rosacea and is suitable for use on all skin types.

Tris(5,6-dimethyl-1H-benzimidazole-κN(3))(pyridine-2,6-dicarboxyl-ato-κ(3)O(2),N,O(6))nickel(II).

PubMed

Li, Yue-Hua; Li, Feng-Feng; Liu, Xin-Hua; Zhao, Ling-Yan

2012-06-01

The title mononuclear complex, [Ni(C(7)H(3)NO(4))(C(9)H(10)N(2))(3)], shows a central Ni(II) atom which is coordinated by two carboxyl-ate O atoms and the N atom from a pyridine-2,6-dicarboxyl-ate ligand and by three N atoms from different 5,6-dimethyl-1H--benzimidazole ligands in a distorted octa-hedral geometry. The crystal structure shows intermolecular N-H⋯O hydrogen bonds.

ON THE FORMATION OF BENZOIC ACID AND HIGHER-ORDER BENZENE CARBOXYLIC ACIDS IN INTERSTELLAR MODEL ICE GRAINS

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

McMurtry, Brandon M.; Saito, Sean E. J.; Turner, A

With a binary ice mixture of benzene (C{sub 6}H{sub 6}) and carbon dioxide (CO{sub 2}) at 10 K under contamination-free ultrahigh vacuum conditions, the formation of benzene carboxylic acids in interstellar ice grains was studied. Fourier transform infrared spectroscopy was used to probe for the formation of new species during the chemical processing of the ice mixture and during the following temperature-programmed desorption. Newly formed benzene carboxylic acid species, i.e., benzoic acid, as well as meta - and para -benzene dicarboxylic acid, were assigned using newly emerging bands in the infrared spectrum; a reaction mechanism, along with rate constants, wasmore » proposed utilizing the kinetic fitting of the coupled differential equations.« less

Glutaric aciduria type I and methylmalonic aciduria: simulation of cerebral import and export of accumulating neurotoxic dicarboxylic acids in in vitro models of the blood-brain barrier and the choroid plexus.

PubMed

Sauer, Sven W; Opp, Silvana; Mahringer, Anne; Kamiński, Marcin M; Thiel, Christian; Okun, Jürgen G; Fricker, Gert; Morath, Marina A; Kölker, Stefan

2010-06-01

Intracerebral accumulation of neurotoxic dicarboxylic acids (DCAs) plays an important pathophysiological role in glutaric aciduria type I and methylmalonic aciduria. Therefore, we investigated the transport characteristics of accumulating DCAs - glutaric (GA), 3-hydroxyglutaric (3-OH-GA) and methylmalonic acid (MMA) - across porcine brain capillary endothelial cells (pBCEC) and human choroid plexus epithelial cells (hCPEC) representing in vitro models of the blood-brain barrier (BBB) and the choroid plexus respectively. We identified expression of organic acid transporters 1 (OAT1) and 3 (OAT3) in pBCEC on mRNA and protein level. For DCAs tested, transport from the basolateral to the apical site (i.e. efflux) was higher than influx. Efflux transport of GA, 3-OH-GA, and MMA across pBCEC was Na(+)-dependent, ATP-independent, and was inhibited by the OAT substrates para-aminohippuric acid (PAH), estrone sulfate, and taurocholate, and the OAT inhibitor probenecid. Members of the ATP-binding cassette transporter family or the organic anion transporting polypeptide family, namely MRP2, P-gp, BCRP, and OATP1B3, did not mediate transport of GA, 3-OH-GA or MMA confirming the specificity of efflux transport via OATs. In hCPEC, cellular import of GA was dependent on Na(+)-gradient, inhibited by NaCN, and unaffected by probenecid suggesting a Na(+)-dependent DCA transporter. Specific transport of GA across hCPEC, however, was not found. In conclusion, our results indicate a low but specific efflux transport for GA, 3-OH-GA, and MMA across pBCEC, an in vitro model of the BBB, via OAT1 and OAT3 but not across hCPEC, an in vitro model of the choroid plexus. Copyright 2010 Elsevier B.V. All rights reserved.

Efficacy of Lactic Acid, Lactic Acid-Acetic Acid Blends, and Peracetic Acid To Reduce Salmonella on Chicken Parts under Simulated Commercial Processing Conditions.

PubMed

Ramirez-Hernandez, Alejandra; Brashears, Mindy M; Sanchez-Plata, Marcos X

2018-01-01

The poultry processing industry has been undergoing a series of changes as it modifies processing practices to comply with new performance standards for chicken parts and comminuted poultry products. The regulatory approach encourages the use of intervention strategies to prevent and control foodborne pathogens in poultry products and thus improve food safety and protect human health. The present studies were conducted to evaluate the efficacy of antimicrobial interventions for reducing Salmonella on inoculated chicken parts under simulated commercial processing conditions. Chicken pieces were inoculated by immersion in a five-strain Salmonella cocktail at 6 log CFU/mL and then treated with organic acids and oxidizing agents on a commercial rinsing conveyor belt. The efficacy of spraying with six different treatments (sterile water, lactic acid, acetic acid, buffered lactic acid, acetic acid in combination with lactic acid, and peracetic acid) at two concentrations was evaluated on skin-on and skin-off chicken thighs at three application temperatures. Skinless chicken breasts were used to evaluate the antimicrobial efficacy of lactic acid and peracetic acid. The color stability of treated and untreated chicken parts was assessed after the acid interventions. The lactic acid and buffered lactic acid treatments produced the greatest reductions in Salmonella counts. Significant differences between the control and water treatments were identified for 5.11% lactic acid and 5.85% buffered lactic acid in both skin-on and skin-off chicken thighs. No significant effect of treatment temperature for skin-on chicken thighs was found. Lactic acid and peracetic acid were effective agents for eluting Salmonella cells attached to chicken breasts.

Synthesis and characterization of new polyamides derived from alanine and valine derivatives

PubMed Central

2012-01-01

Background Many efforts have been recently devoted to design, investigate and synthesize biocompatible, biodegradable polymers for applications in medicine for either the fabrication of biodegradable devices or as drug delivery systems. Many of them consist of condensation of polymers having incorporated peptide linkages susceptible to enzymatic cleavage. Polyamides (PAs) containing α-amino acid residues such as L-leucine, L-alanine and L-phenylalanine have been reported as biodegradable materials. Furthermore, polyamides (PAs) derived from C10 and C14 dicarboxylic acids and amide-diamines derived from 1,6-hexanediamine or 1,12-dodecanediamine and L-phenylalanine, L-valyl-L-phenylalanine or L-phenylalanyl-L-valine residues have been reported as biocompatible polymers. We have previously described the synthesis and thermal properties of a new type of polyamides-containing amino acids based on eight new symmetric meta-oriented protected diamines derived from coupling of amino acids namely; Fomc-glycine, Fmoc-alanine, Fomc-valine and Fomc-leucine with m-phenylene diamine or 2,6-diaminopyridine. Results revealed that incorporation of pyridine onto the polymeric backbone of all series decreases the thermal stability. Here we describe another family of polyamides based on benzene dicarboxylic acid, pyridine dicarboxylic acid, and α-amino acid linked to benzidine and 4,4′-oxydianiline to study the effect of the dicarboxylic acid as well as the amino acids on the nature and thermal stability of the polymers. Results We report here the preparation of a new type of polyamides based on benzene dicarboxylic acid, pyridine dicarboxylic acid, and α-amino acid linked to benzidine and 4,4′-oxydianiline to study the effect of the dicarboxylic acid as well as the amino acids on the nature and thermal stability of polymers. The thermal properties of the polymers were evaluated by different techniques. Results revealed that structure-thermal property correlation based on

Host cells and methods for producing diacid compounds

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

Steen, Eric J.; Fortman, Jeffrey L.; Dietrich, Jeffrey A.

The present invention provides for a method of producing one or more fatty acid derived dicarboxylic acids in a genetically modified host cell which does not naturally produce the one or more derived fatty acid derived dicarboxylic acids. The invention provides for the biosynthesis of dicarboxylic acid ranging in length from C3 to C26. The host cell can be further modified to increase fatty acid production or export of the desired fatty acid derived compound, and/or decrease fatty acid storage or metabolism.

Tailored and integrated production of carboxylated cellulose nanocrystals (CNC) with nanofibrils (CNF) through maleic acid hydrolysis

Treesearch

Ruibin Wang; Liheng Chen; J.Y. Zhu; Rendang Yang

2017-01-01

This study demonstrates the feasibility of tailored and integrated production of carboxylated cellulose nanocrystals (CNC) with nanofibrils (CNF) from bleached pulp fibers through hydrolysis using a recyclable dicarboxylic acid. Hydrolysis experiments were conducted using ranges of 15–75 wt% maleic acid concentrations, 60–120°C temperatures, and 5–300 min reaction...

Molecular and polymeric uranyl and thorium hybrid materials featuring methyl substituted pyrazole dicarboxylates and heterocyclic 1,3-diketones

NASA Astrophysics Data System (ADS)

Carter, Korey P.; Kerr, Andrew T.; Taydakov, Ilya V.; Cahill, Christopher L.

2018-02-01

A series of seven novel f-element bearing hybrid materials have been prepared from either methyl substituted 3,4 and 4,5-pyrazoledicarboxylic acids, or heterocyclic 1,3- diketonate ligands using hydrothermal conditions. Compounds 1, [UO2(C6H4N2O4)2(H2O)], and 3, [Th(C6H4N2O4)4(H2O)5]·H2O feature 1-Methyl-1H-pyrazole-3,4-dicarboxylate ligands (SVI-COOH 3,4), whereas 2, [UO2(C6H4N2O4)2(H2O)], and 4, [Th(C6H5N2O4)(OH)(H2O)6]2·2(C6H5N2O4)·3H2O feature 1-Methyl-1H-pyrazole-4,5-dicarboxylate moieties (SVI-COOH 4,5). Compounds 5, [UO2(C13H15N4O2)2(H2O)]·2H2O and 6, [UO2(C11H11N4O2)2(H2O)]·4.5H2O feature 1,3-bis(4-N1-methyl-pyrazolyl)propane-1,3-dione and 1,3-bis(4-N1,3-dimethyl-pyrazolyl)propane-1,3-dione respectively, whereas the heterometallic 7, [UO2(C11H11N4O2)2(CuCl2)(H2O)]·2H2O is formed by using 6 as a metalloligand starting material. Single crystal X-ray diffraction indicates that all coordination to either [UO2]2+ or Th(IV) metal centers is through O-donation as anticipated. Room temperature, solid-state luminescence studies indicate characteristic uranyl emissive behavior for 1 and 2, whereas those for 5 and 6 are weak and poorly resolved.

Differentiation of DctA and DcuS function in the DctA/DcuS sensor complex of Escherichia coli: function of DctA as an activity switch and of DcuS as the C4-dicarboxylate sensor.

PubMed

Steinmetz, Philipp Aloysius; Wörner, Sebastian; Unden, Gottfried

2014-10-01

The C4-dicarboxylate responsiveness of the sensor kinase DcuS is only provided in concert with C4-dicarboxylate transporters DctA or DcuB. The individual roles of DctA and DcuS for the function of the DctA/DcuS sensor complex were analysed. (i) Variant DctA(S380D) in the C4-dicarboxylate site of DctA conferred C4-dicarboxylate sensitivity to DcuS in the DctA/DcuS complex, but was deficient for transport and for growth on C4-dicarboxylates. Consequently transport activity of DctA is not required for its function in the sensor complex. (ii) Effectors like fumarate induced expression of DctA/DcuS-dependent reporter genes (dcuB-lacZ) and served as substrates of DctA, whereas citrate served only as an inducer of dcuB-lacZ without affecting DctA function. (iii) Induction of dcuB-lacZ by fumarate required 33-fold higher concentrations than for transport by DctA (Km  = 30 μM), demonstrating the existence of different fumarate sites for both processes. (iv) In titration experiments with increasing dctA expression levels, the effect of DctA on the C4-dicarboxylate sensitivity of DcuS was concentration dependent. The data uniformly show that C4-dicarboxylate sensing by DctA/DcuS resides in DcuS, and that DctA serves as an activity switch. Shifting of DcuS from the constitutive ON to the C4-dicarboxylate responsive state, required presence of DctA but not transport by DctA. © 2014 John Wiley & Sons Ltd.

Different water clusters dependent on long-chain dicarboxylates in two Ag(I) coordination polymers: Synthesis, structure and thermal stability

NASA Astrophysics Data System (ADS)

Sun, Di; Liu, Fu-Jing; Hao, Hong-Jun; Huang, Rong-Bin; Zheng, Lan-Sun

2011-10-01

Two mixed-ligand Ag(I) coordination polymers (CPs), [Ag 2(bipy) 2(sub)·5H 2O] n ( 1), [Ag 2(bipy) 2(aze)·3H 2O] n ( 2), (bipy = 4,4'-bipyridine, H 2sub = suberic acid, H 2aze = azelaic acid) have been synthesized and structurally characterized by elemental analysis, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric (TG) analysis, and single crystal X-ray diffraction. Both 1 and 2 are two-dimensional (2D) sheets based on infinite [Ag(bipy)] n double chain incorporating Ag⋯Ag interactions. Interestingly, two different water clusters are encapsulated in the voids between the sheets of 1 and 2. For 1, one water decamer (H 2O) 10 based on a cyclic water tetramer was hydrogen-bonded with the host 2D sheet. While, one water hexamer (H 2O) 6 also based on a cyclic water tetramer was observed in 2. Comparing the experimental results, it is comprehensible that the dicarboxylates play a crucial role in the formation of the different water clusters. Moreover, the thermal stabilities of them were also discussed.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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.

1D helix, 2D brick-wall and herringbone, and 3D interpenetration d10 metal-organic framework structures assembled from pyridine-2,6-dicarboxylic acid N-oxide.

PubMed

Wen, Li-Li; Dang, Dong-Bin; Duan, Chun-Ying; Li, Yi-Zhi; Tian, Zheng-Fang; Meng, Qing-Jin

2005-10-03

Five novel interesting d(10) metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4'-bpy)2(H2O)2.3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi).0.5H2O]n (bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)(1.5).1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 4(1) helices running along the c-axis with a pitch of 10.090 Angstroms. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, both distributed in a rectangular grid fashion. Compounds 1-5, with systematic variation in dimensionality from 1D to 2D to 3D, are the first examples of d(10) metal coordination polymers into which pyridinedicarboxylic acid N-oxide has been introduced. In addition, polymers 1, 4, and 5 display strong blue fluorescent emissions in the solid state. Polymer 3 exhibits a strong SHG response, estimated to be approximately 0.9 times that of urea.

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

PubMed

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

2014-11-26

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.

Water oxidation catalyzed by mononuclear ruthenium complexes with a 2,2'-bipyridine-6,6'-dicarboxylate (bda) ligand: how ligand environment influences the catalytic behavior.

PubMed

Staehle, Robert; Tong, Lianpeng; Wang, Lei; Duan, Lele; Fischer, Andreas; Ahlquist, Mårten S G; Sun, Licheng; Rau, Sven

2014-02-03

A new water oxidation catalyst [Ru(III)(bda)(mmi)(OH2)](CF3SO3) (2, H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; mmi = 1,3-dimethylimidazolium-2-ylidene) containing an axial N-heterocyclic carbene ligand and one aqua ligand was synthesized and fully characterized. The kinetics of catalytic water oxidation by 2 were measured using stopped-flow technique, and key intermediates in the catalytic cycle were probed by density functional theory calculations. While analogous Ru-bda water oxidation catalysts [Ru(bda)L2] (L = pyridyl ligands) are supposed to catalyze water oxidation through a bimolecular coupling pathway, our study points out that 2, surprisingly, undergoes a single-site water nucleophilic attack (acid-base) pathway. The diversion of catalytic mechanisms is mainly ascribed to the different ligand environments, from nonaqua ligands to an aqua ligand. Findings in this work provide some critical proof for our previous hypothesis about how alternation of ancillary ligands of water oxidation catalysts influences their catalytic efficiency.

Progress of succinic acid production from renewable resources: Metabolic and fermentative strategies.

PubMed

Jiang, Min; Ma, Jiangfeng; Wu, Mingke; Liu, Rongming; Liang, Liya; Xin, Fengxue; Zhang, Wenming; Jia, Honghua; Dong, Weiliang

2017-12-01

Succinic acid is a four-carbon dicarboxylic acid, which has attracted much interest due to its abroad usage as a precursor of many industrially important chemicals in the food, chemicals, and pharmaceutical industries. Facing the shortage of crude oil supply and demand of sustainable development, biological production of succinic acid from renewable resources has become a topic of worldwide interest. In recent decades, robust producing strain selection, metabolic engineering of model strains, and process optimization for succinic acid production have been developed. This review provides an overview of succinic acid producers and cultivation technology, highlight some of the successful metabolic engineering approaches. Copyright © 2017 Elsevier Ltd. All rights reserved.

Uptake of Alkylamines on Dicarboxylic Acids Relevant to Secondary Organic Aerosol Formation

NASA Astrophysics Data System (ADS)

Marrero-Ortiz, W.; Secrest, J.; Zhang, R.

2017-12-01

Aerosols play a critical role in climate directly by scattering and absorbing solar radiation, and indirectly by functioning as cloud condensation nuclei (CCN); both represent the largest uncertainties in climate predictions. New particle formation contributes significantly to CCN production; however, the mechanisms related to particle nucleation and growth processes are not well understood. Organic acids are atmospherically abundant, and their neutralization by low molecular weight amines may result in the formation of stable low volatility aminium salt products contributing to the growth of secondary organic aerosols and even the alteration of the aerosol properties. The acid-base neutralization of particle phase succinic acid and tartaric acid by low molecular weight aliphatic amines, i.e. methylamine, dimethylamine, and trimethylamine, has been investigated by employing a low-pressure fast flow reactor at 298K with an ion drift - chemical ionization mass spectrometer (ID-CIMS). The heterogeneous uptake is time dependent and influenced by organic acids functionality, alkylamines basicity, and steric effect. The implications of our results to atmospheric nanoparticle growth will be discussed.

Hydrothermal synthesis and structural characterization of a novel three-dimensional supramolecular framework constructed by zinc salt and pyridine-2,5-dicarboxylate

NASA Astrophysics Data System (ADS)

Wang, Xinlong; Qin, Chao; Wang, Enbo; Hu, Changwen; Xu, Lin

2004-07-01

A novel metal-organic coordination polymer, [Zn(PDB)(H 2O) 2] 4 n (H 2PDB=pyridine-2,5-dicarboxylic acid), has been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. Colorless crystals crystallized in the triclinic system, space group P-1, a=7.0562(14) Å, b=7.38526(15) Å, c=18.4611(4) Å, α=90.01(3)°, β=96.98(3)°, γ=115.67(3)°, V=859.1(3) Å 3, Z=1 and R=0.0334. The structure of the compound exhibits a novel three-dimensional supramolecular network, mainly based on multipoint hydrogen bonds originated from within and outside of a large 24-membered ring. Interestingly, the three-dimensional network consists of one-dimensional parallelogrammic channels in which coordinated water molecules point into the channel wall.

Rat urinary metabolites of [9,10-methylene-14C] sterculic acid.

PubMed

Eisele, T A; Yoss, J K; Nixon, J E; PAwlowski, N E; Libbey, L M; Sinnhuber, R O

1977-07-20

1. The metabolism of [9,10-methylene-14C] sterculic acid was studied in corn oil and Stercula foetida oil fed rats. The majority of the radioactivity was excreted into the urine as short chain dicarboxylic acids. The main urinary metabolites were cis-3,4-methylene adipic acid, cis-3,4-methylene suberic acid, trans-3,4-methylene adipic acid, cis-3,4-methylene pimelic acid, and cis-3,4-methylene azelic acid. 2. Formation of these urinary metabolites requires alpha-, beta-, and omega-oxidation plus reduction of the cyclopropene ring to a cyclopropane ring. Sterculic acid must be transported through both mitochondrial and microsomal systems. 3. Other non-radioactive urinary compounds were also identified. A proposed pathway for the metabolism of sterculic acid and possible detrimental effects caused by these metabolites is discussed.

Production of polymalic acid and malic acid by Aureobasidium pullulans fermentation and acid hydrolysis.

PubMed

Zou, Xiang; Zhou, Yipin; Yang, Shang-Tian

2013-08-01

Malic acid is a dicarboxylic acid widely used in the food industry and also a potential C4 platform chemical that can be produced from biomass. However, microbial fermentation for direct malic acid production is limited by low product yield, titer, and productivity due to end-product inhibition. In this work, a novel process for malic acid production from polymalic acid (PMA) fermentation followed by acid hydrolysis was developed. First, a PMA-producing Aureobasidium pullulans strain ZX-10 was screened and isolated. This microbe produced PMA as the major fermentation product at a high-titer equivalent to 87.6 g/L of malic acid and high-productivity of 0.61 g/L h in free-cell fermentation in a stirred-tank bioreactor. Fed-batch fermentations with cells immobilized in a fibrous-bed bioreactor (FBB) achieved the highest product titer of 144.2 g/L and productivity of 0.74 g/L h. The fermentation produced PMA was purified by adsorption with IRA-900 anion-exchange resins, achieving a ∼100% purity and a high recovery rate of 84%. Pure malic acid was then produced from PMA by hydrolysis with 2 M sulfuric acid at 85°C, which followed the first-order reaction kinetics. This process provides an efficient and economical way for PMA and malic acid production, and is promising for industrial application. Copyright © 2013 Wiley Periodicals, Inc.

Impaired Malate and Fumarate Accumulation Due to the Mutation of the Tonoplast Dicarboxylate Transporter Has Little Effects on Stomatal Behavior.

PubMed

Medeiros, David B; Barros, Kallyne A; Barros, Jessica Aline S; Omena-Garcia, Rebeca P; Arrivault, Stéphanie; Sanglard, Lílian M V P; Detmann, Kelly C; Silva, Willian Batista; Daloso, Danilo M; DaMatta, Fábio M; Nunes-Nesi, Adriano; Fernie, Alisdair R; Araújo, Wagner L

2017-11-01

Malate is a central metabolite involved in a multiplicity of plant metabolic pathways, being associated with mitochondrial metabolism and playing significant roles in stomatal movements. Vacuolar malate transport has been characterized at the molecular level and is performed by at least one carrier protein and two channels in Arabidopsis ( Arabidopsis thaliana ) vacuoles. The absence of the Arabidopsis tonoplast Dicarboxylate Transporter (tDT) in the tdt knockout mutant was associated previously with an impaired accumulation of malate and fumarate in leaves. Here, we investigated the consequences of this lower accumulation on stomatal behavior and photosynthetic capacity as well as its putative metabolic impacts. Neither the stomatal conductance nor the kinetic responses to dark, light, or high CO 2 were highly affected in tdt plants. In addition, we did not observe any impact on stomatal aperture following incubation with abscisic acid, malate, or citrate. Furthermore, an effect on photosynthetic capacity was not observed in the mutant lines. However, leaf mitochondrial metabolism was affected in the tdt plants. Levels of the intermediates of the tricarboxylic acid cycle were altered, and increases in both light and dark respiration were observed. We conclude that manipulation of the tonoplastic organic acid transporter impacted mitochondrial metabolism, while the overall stomatal and photosynthetic capacity were unaffected. © 2017 American Society of Plant Biologists. All Rights Reserved.

Structural modulation and luminescent properties of four CdII coordination architectures based on 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole and flexible/rigid dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Xia, Liang; Dong, Wen-Wen; Ye, Xiao; Zhao, Jun; Li, Dong-Sheng

2016-10-01

To systematically investigate the influence of the flexible or rigid auxiliary ligands on the structures and properties of transition metal compounds, we synthesized four new d10 coordination polymers (CPs) from 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (4-Hpzpt) and flexible/rigid dicarboxylate ligands, [Cd(4-pzpt)2]n (1), [Cd3(4-pzpt)2(suc)2]n (2), [Cd2(4-Hpzpt)(nbc)2(H2O)]n (3) and {[Cd2(4-pzpt)2(tfbdc)(H2O)4]·H2O}n (4) (H2suc=1,2-ethanedicarboxylic acid, H2nbc=hthalene-1,4-dicarboxylic acid, H2tfbdc =2,3,5,6-tetrafluoroterephthalic acid). Single crystal X-ray analysis indicates that compound 1 shows a 44-sql layer, which is extended to a 3D network via nonclassical C-H…N hydrogen bonds. Compound 2 possesses a 6-connected pcu-4120.63 net composed of trinuclear CdII-clusters. Compound 3 represents a rare 3D (3,4,4,5)-connected topology with a Schläfli symbol of (4·6·7)(4·53·72)(53·6·7·9)(42·55·6·72). Compound 4 exhibits a 2D+2D→2D parallel interpenetrated 63-hcb network. The adjacent 2D networks are interdigitated with each other to form the resulting 3D supramolecular architecture through classical O-H…N and O-H…O hydrogen bonds. Structural diversities indicate that the nature of flexible/rigid-dicarboxlates plays crucial roles in modulating structures of these compounds. Moreover, the luminescent properties of them have been briefly investigated.

Sulphate transport by H+ symport and by the dicarboxylate carrier in mitochondria.

PubMed Central

Saris, N E

1980-01-01

1. Swelling of mitochondria was induced in non-respiring mitochondria by 30 mM or more Na2SO4 or by respiration in the presence of K2SO4. Respiration-drive swelling resulted in loss of respiratory control. Sulphate, when present at 10 mM concentration, promoted the release of accumulated Ca2+. 2. Swelling was prevented by N-ethylmaleimide and formaldehyde, known inhibitors of the phosphate carrier. Sulphate-induced swelling was more sensitive to the inhibitors than was phosphate-induced swelling. At lower concentration of sulphate, 5 mM, an alkalinisation of the medium was observed in addition of sulphate, indicating H+-sulphate symport. There was competition between sulphate and phosphate for transport by this mechanism. It is suggested that sulphate may be transported, though at a comparatively slow rate, by the phosphate carrier. 3. Uptake of sulphate was stimulated when preceded by energy-dependent accumulation of Ba2+, especially when acetate was also present, indicating precipitation of BaSO4 in the matrix. Using this system the influx of sulphate was studied at lower concentrations, 10 mM or less. the contributions of the H+ symporter (sensitive to N-ethylmaleimide) and the dicarboxylate carrier (sensitive to butylmalonate) could then be studied. The dicarboxylate carrier had a lower Km and was mainly responsible for sulphate transport at lower concentration range. At 10 mM-sulphate the transport rates by the two systems appeared to be similar; at still higher concentrations the H+ symporter may become more important. PMID:7236245

Structure of the d-alanylgriseoluteic acid biosynthetic protein EhpF, an atypical member of the ANL superfamily of adenylating enzymes

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

Bera, Asim K.; Atanasova, Vesna; Gamage, Swarna

2010-06-01

The structure of EhpF from P. agglomerans has been solved alone and in complex with phenazine-1,6-dicarboxylate. Apo EhpF was solved and refined in two different space groups at 1.95 and 2.3 Å resolution and the EhpF–phenazine-1,6-dicarboxylate complex structure was determined at 2.8 Å resolution. The structure of EhpF, a 41 kDa protein that functions in the biosynthetic pathway leading to the broad-spectrum antimicrobial compound d-alanylgriseoluteic acid (AGA), is reported. A cluster of approximately 16 genes, including ehpF, located on a 200 kbp plasmid native to certain strains of Pantoea agglomerans encodes the proteins that are required for the conversion ofmore » chorismic acid to AGA. Phenazine-1,6-dicarboxylate has been identified as an intermediate in AGA biosynthesis and deletion of ehpF results in accumulation of this compound in vivo. The crystallographic data presented here reveal that EhpF is an atypical member of the acyl-CoA synthase or ANL superfamily of adenylating enzymes. These enzymes typically catalyze two-step reactions involving adenylation of a carboxylate substrate followed by transfer of the substrate from AMP to coenzyme A or another phosphopantetheine. EhpF is distinguished by the absence of the C-terminal domain that is characteristic of enzymes from this family and is involved in phosphopantetheine binding and in the second half of the canonical two-step reaction that is typically observed. Based on the structure of EhpF and a bioinformatic analysis, it is proposed that EhpF and EhpG convert phenazine-1,6-dicarboxylate to 6-formylphenazine-1-carboxylate via an adenylyl intermediate.« less

Uptake of 4-chloro-2-methylphenoxyacetic acid (MCPA) from the apical membrane of Caco-2 cells by the monocarboxylic acid transporter

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

Kimura, Osamu; Tsukagoshi, Kensuke; Endo, Tetsuya

2008-03-15

The cellular uptake mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA), a phenoxyacetic acid derivative, was investigated using Caco-2 epithelial cells. The cells were incubated with 50 {mu}M MCPA at pH 6.0 and 37 deg. C, and the uptake of MCPA from the apical membranes was measured. The uptake of MCPA was significantly decreased by incubation at low temperature (4 {sup o}C) and markedly increased by lowering the extracellular pH. Pretreatment with a protonophore, carbonylcyanide-p-(trifluoromethoxy)phenylhydrazone (25 {mu}M), or metabolic inhibitors, 2,4-dinitrophenol (1 mM) and sodium azide (10 mM), significantly decreased the uptake of MCPA by 53%, 45% and 48%, respectively. Coincubation of MCPAmore » with 10 mM L-lactic acid or {alpha}-cyano-4-hydroxycinnamate, which is a substrate or an inhibitor of the monocarboxylic acid transporters (MCTs), significantly decreased the uptake of MCPA by 31% and 20%, respectively, and coincubation with benzoic acid profoundly decreased the uptake by 68%. In contrast, coincubation with succinic acid (a dicarboxylic acid) did not affect the uptake. Kinetic analysis of initial MCPA uptake suggested that MCPA is taken up via a carrier-mediated process [K{sub m} = 1.37 {+-} 0.15 mM, V{sub max} = 115 {+-} 6 nmol (mg protein){sup -1} (3 min){sup -1}]. Lineweaver-Burk plots show that benzoic acid competitively inhibits the uptake of MCPA with a K{sub i} value of 4.68 {+-} 1.76 mM. A trans-stimulation effect on MCPA uptake was found in cells preloaded with benzoic acid. These results suggest that the uptake of MCPA from the apical membrane of Caco-2 cells is mainly mediated by common MCTs along with benzoic acid but also in part by L-lactic acid.« less

Effect of 2 ppm ozone exposure on rat lung lipid fatty acids

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

Rabinowitz, J.L.; Bassett, D.J.

Based on in vitro studies, the initial damage to lung cells by ozone exposure is believed to result in part from the breakdown of lipid polyunsaturated fatty acids to aldehydes, ozonides, and peroxides. The present study measured lipid breakdown products in lungs isolated from rats pretreated with (1-/sup 14/C)acetate 12 h before exposure for 4 h to either air or 2 ppm ozone. Lipid fatty acid breakdown was indicated by a 112% increase in thiobarbituric acid-reactive substances on ozone exposure and by changes in chemical and radioactive measurements of mono- and dicarboxylic acids formed by treatment of lipid fractions withmore » hydrogen peroxide. Ozone exposure resulted in a 63% increase in recovery of short-chain fatty acids accounted for by increased recoveries of malonic acid by 37%, hexanoic acid by 47%, nonanoic acid by 118%, and azelaic acid by 107%. Recovery of glutaric acid was enhanced 15-fold by ozone exposure. Although decreases in tissue arachidonic acid could not be detected, oleic acid was significantly decreased by 36%. Recovery of radiolabel as short-chain fatty acids was increased by 65% on ozone exposure and was mainly accounted for by enhanced labeling of nonanoic and glutaric acid fractions. The failure to observe significant increases in /sup 14/C recovery in the other fractions suggested ozone-induced breakdown of unlabeled fatty acids. These results demonstrate the cleavage of unsaturated fatty acid double bonds following in vivo exposure of lungs to ozone. Breakdown of arachidonic and oleic acids was specifically identified by increased recoveries of glutaric and nonanoic acids, respectively.« less

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

PubMed

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

2004-09-15

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

The unusual canangafruticosides A-E: five monoterpene glucosides, two monoterpenes and a monoterpene glucoside diester of the aryldihydronaphthalene lignan dicarboxylic acid from leaves of Cananga odorata var. fruticosa.

PubMed

Nagashima, Jiro; Matsunami, Katsuyoshi; Otsuka, Hideaki; Lhieochaiphant, Duangporn; Lhieochaiphant, Sorasak

2010-09-01

From the leaves of Cananga odorata var. fruticosa, five unusual monoterpene glucosides, named canangafruticosides A-E (1-5), along with two unusual non-glucosidic monoterpenes (6, 7) were isolated. An aryldihydronaphthalene-type lignan dicarboxylate (8) was also isolated, with two moles of canangafruticoside A (1) on its ester moiety. This lignan also showed strong blue fluorescence emission under basic conditions. The structures of these compounds were elucidated by means of spectroscopic methods, with their absolute configurations determined by application of the modified Mosher's method to a compound chemically derived from canangafruticoside E. (c) 2010 Elsevier Ltd. All rights reserved.

Attenuation of excitatory amino acid toxicity by metabotropic glutamate receptor agonists and aniracetam in primary cultures of cerebellar granule cells.

PubMed

Pizzi, M; Fallacara, C; Arrighi, V; Memo, M; Spano, P F

1993-08-01

Activation of glutamate ionotropic receptors represents the primary event in the neurotoxicity process triggered by excitatory amino acids. We demonstrate here that the concentration-dependent stimulation of metabotropic glutamate receptor (mGluR) by the selective agonist trans-1-aminocyclopentane-1,3-dicarboxylate or by quisqualate counteracts both glutamate- and kainate-induced neurotoxicity in primary cultures of rat cerebellar granule cells. The mGluR-evoked responses are potentiated by aniracetam, which per se also elicits neuroprotection. Aniracetam concentration-dependently counteracted glutamate-, kainate-, or alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid-induced cell death and greatly facilitated neuroprotective response achieved by different concentrations of both quisqualate and trans-1-aminocyclopentane-1,3-dicarboxylate. In addition, aniracetam potentiated the mGluR-coupled stimulation of phospholipase C, as revealed by the measurement of 3H-inositol phosphate formation. Thus, mGluRs could be a suitable target for novel pharmacological strategies pointing to the treatment of neurodegenerative diseases.

Structures and standard molar enthalpies of formation of a series of Ln(III)–Cu(II) heteronuclear compounds with pyrazine-2,3-dicarboxylic acid

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

Yang, Qi; Xie, Gang; Wei, Qing

2014-07-01

Fifteen lanthanide–copper heteronuclear compounds, formulated as [CuLn{sub 2}(pzdc){sub 4}(H{sub 2}O){sub 6}]·xH{sub 2}O (1–6(x=2), 8(x=3), 9–10(x=4)); [CuLn{sub 2}(pzdc){sub 4}(H{sub 2}O){sub 4}]·xH{sub 2}O (7, 12–13, 15(x=4), 14(x=5), 11(x=8)) (Ln(III)=La(1); Ce(2); Pr(3); Nd(4); Sm(5); Eu(6); Gd(7); Tb(8); Dy(9); Ho(10); Er(11); Tm(12); Yb(13); Lu(14); Y(15); H{sub 2}pzdc (C{sub 6}H{sub 4}N{sub 2}O{sub 4})=pyrazine-2,3-dicarboxylic acid) have been hydrothermally synthesized. All compounds were characterized by element analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. X-ray diffraction analyses confirm that all compounds are isostructural and feature a 3D brick-like framework structure with (4.6{sup 2}){sub 2}(4{sup 2}.6{sup 2}.8{sup 2})(6{sup 3}){sup 2}(6{sup 5}.8){sub 2} topology. Using 1 mol cm{supmore » −3} HCl(aq) as calorimetric solvent, with an isoperibol solution–reaction calorimeter, the standard molar enthalpies of formation of all compounds were determined by a designed thermochemical cycle. In addition, solid state luminescence properties of compounds 5, 6, 8 and 9 were studied in the solid state. - Graphical abstract: According to Hess' rule, the standard molar enthalpies of formation of Ln–Cu heterometallic coordination compounds were determined by a designed thermochemical cycle. - Highlights: • Fifteen lanthanide–copper heteronuclear isostructural compounds. • Structurally characterization by IR, X-ray diffraction and thermal analysis. • The standard molar enthalpy of formation. • Isoperibol solution–reaction calorimetry.« less

Aqueous infrared carboxylate absorbances: Aliphatic di-acids

USGS Publications Warehouse

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

1998-01-01

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.

Molecular properties of the SLC13 family of dicarboxylate and sulfate transporters

PubMed Central

Pajor, Ana M.

2006-01-01

The SLC13 gene family consists of five members in humans, with corresponding orthologs from different vertebrate species. All five genes code for sodium-coupled transporters that are found on the plasma membrane. Two of the transporters, NaS1 and NaS2, carry substrates such as sulfate, selenate and thiosulfate. The other members of the family (NaDC1, NaDC3, and NaCT) are transporters for di- and tri-carboxylates including succinate, citrate and α-ketoglutarate. The SLC13 transporters from vertebrates are electrogenic and they produce inward currents in the presence of sodium and substrate. Substrate-independent leak currents have also been described. Structure–function studies have identified the carboxy terminal half of these proteins as the most important for determining function. Transmembrane helices 9 and 10 may form part of the substrate permeation pathway and participate in conformational changes during the transport cycle. This review also discusses new members of the SLC13 superfamily that exhibit both sodium-dependent and sodium-independent transport mechanisms. The Indy protein from Drosophila, involved in determining lifespan, and the plant vacuolar malate transporter are both sodium-independent dicarboxylate transporters, possibly acting as exchangers. The purpose of this review is to provide an update on new advances in this gene family, particularly on structure–function studies and new members of the family. PMID:16211368

Hydrolysis of dilute acid-pretreated cellulose under mild hydrothermal conditions.

PubMed

Chimentão, R J; Lorente, E; Gispert-Guirado, F; Medina, F; López, F

2014-10-13

The hydrolysis of dilute acid-pretreated cellulose was investigated in a conventional oven and under microwave heating. Two acids--sulfuric and oxalic--were studied. For both hydrothermal conditions (oven and microwave) the resultant total organic carbon (TOC) values obtained by the hydrolysis of the cellulose pretreated with sulfuric acid were higher than those obtained by the hydrolysis of the cellulose pretreated with oxalic acid. However, the dicarboxylic acid exhibited higher hydrolytic efficiency towards glucose. The hydrolysis of cellulose was greatly promoted by microwave heating. The Rietveld method was applied to fit the X-ray patterns of the resultant cellulose after hydrolysis. Oxalic acid preferentially removed the amorphous region of the cellulose and left the crystalline region untouched. On the other hand, sulfuric acid treatment decreased the ordering of the cellulose by partially disrupting its crystalline structure. Copyright © 2014 Elsevier Ltd. All rights reserved.

75 FR 37795 - Certain New Chemicals; Receipt and Status Information

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-30

...-methyl-, polymer with alkyl 2- propenoates, ethenyl acetate and methyl-2- methyl-2-propenoate P-10-0389...), polymers with cycloaliphatic diamine, alkyldiisocyanate, alpha-hydro-omega- hydroxy(alkyldiyl) and... dicarboxylic acid, polymer with cycloaliphatic diamine, aliphatic diisocyanate, aliphatic dicarboxylic acid...

Mechanism of Inactivation of γ-Aminobutyric Acid Aminotransferase by (1S,3S)-3-Amino-4-difluoromethylene-1-cyclopentanoic Acid (CPP-115)

PubMed Central

2016-01-01

γ-Aminobutyric acid aminotransferase (GABA-AT) is a pyridoxal 5′-phosphate (PLP)-dependent enzyme that degrades GABA, the principal inhibitory neurotransmitter in mammalian cells. When the concentration of GABA falls below a threshold level, convulsions can occur. Inhibition of GABA-AT raises GABA levels in the brain, which can terminate seizures as well as have potential therapeutic applications in treating other neurological disorders, including drug addiction. Among the analogues that we previously developed, (1S,3S)-3-amino-4-difluoromethylene-1-cyclopentanoic acid (CPP-115) showed 187 times greater potency than that of vigabatrin, a known inactivator of GABA-AT and approved drug (Sabril) for the treatment of infantile spasms and refractory adult epilepsy. Recently, CPP-115 was shown to have no adverse effects in a Phase I clinical trial. Here we report a novel inactivation mechanism for CPP-115, a mechanism-based inactivator that undergoes GABA-AT-catalyzed hydrolysis of the difluoromethylene group to a carboxylic acid with concomitant loss of two fluoride ions and coenzyme conversion to pyridoxamine 5′-phosphate (PMP). The partition ratio for CPP-115 with GABA-AT is about 2000, releasing cyclopentanone-2,4-dicarboxylate (22) and two other precursors of this compound (20 and 21). Time-dependent inactivation occurs by a conformational change induced by the formation of the aldimine of 4-aminocyclopentane-1,3-dicarboxylic acid and PMP (20), which disrupts an electrostatic interaction between Glu270 and Arg445 to form an electrostatic interaction between Arg445 and the newly formed carboxylate produced by hydrolysis of the difluoromethylene group in CPP-115, resulting in a noncovalent, tightly bound complex. This represents a novel mechanism for inactivation of GABA-AT and a new approach for the design of mechanism-based inactivators in general. PMID:25616005

Mechanism of Inactivation of γ-Aminobutyric Acid Aminotransferase by (1 S ,3 S )-3-Amino-4-difluoromethylene-1-cyclopentanoic Acid (CPP-115)

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

Lee, Hyunbeom; Doud, Emma H.; Wu, Rui

gamma-Aminobutyric acid aminotransferase (GABA-AT) is a pyridoxal 5'-phosphate (PLP)-dependent enzyme that degrades GABA, the principal inhibitory neurotransmitter in mammalian cells. When the concentration of GABA falls below a threshold level, convulsions can occur. Inhibition of GABA-AT raises GABA levels in the brain, which can terminate seizures as well as have potential therapeutic applications in treating other neurological disorders, including drug addiction. Among the analogues that we previously developed, (1S,3S)-3-amino-4-difluoromethylene-1-cyclopentanoic acid (CPP-115) showed 187 times greater potency than that of vigabatrin, a known inactivator of GABA-AT and approved drug (Sabril) for the treatment of infantile spasms and refractory adult epilepsy. Recently,more » CPP-115 was shown to have no adverse effects in a Phase I clinical trial. Here we report a novel inactivation mechanism for CPP-115, a mechanism-based inactivator that undergoes GABA-AT-catalyzed hydrolysis of the difluoromethylene group to a carboxylic acid with concomitant loss of two fluoride ions and coenzyme conversion to pyridoxamine 5'-phosphate (PMP). The partition ratio for CPP-115 with GABA-AT is about 2000, releasing cyclopentanone-2,4-dicarboxylate (22) and two other precursors of this compound (20 and 21). Time-dependent inactivation occurs by a conformational change induced by the formation of the aldimine of 4-aminocyclopentane-1,3-dicarboxylic acid and PMP (20), which disrupts an electrostatic interaction between Glu270 and Arg445 to form an electrostatic interaction between Arg445 and the newly formed carboxylate produced by hydrolysis of the difluoromethylene group in CPP-115, resulting in a noncovalent, tightly bound complex. This represents a novel mechanism for inactivation of GABA-AT and a new approach for the design of mechanism-based inactivators in general.« less

Mechanism of inactivation of γ-aminobutyric acid aminotransferase by (1S,3S)-3-amino-4-difluoromethylene-1-cyclopentanoic acid (CPP-115).

PubMed

Lee, Hyunbeom; Doud, Emma H; Wu, Rui; Sanishvili, Ruslan; Juncosa, Jose I; Liu, Dali; Kelleher, Neil L; Silverman, Richard B

2015-02-25

γ-Aminobutyric acid aminotransferase (GABA-AT) is a pyridoxal 5'-phosphate (PLP)-dependent enzyme that degrades GABA, the principal inhibitory neurotransmitter in mammalian cells. When the concentration of GABA falls below a threshold level, convulsions can occur. Inhibition of GABA-AT raises GABA levels in the brain, which can terminate seizures as well as have potential therapeutic applications in treating other neurological disorders, including drug addiction. Among the analogues that we previously developed, (1S,3S)-3-amino-4-difluoromethylene-1-cyclopentanoic acid (CPP-115) showed 187 times greater potency than that of vigabatrin, a known inactivator of GABA-AT and approved drug (Sabril) for the treatment of infantile spasms and refractory adult epilepsy. Recently, CPP-115 was shown to have no adverse effects in a Phase I clinical trial. Here we report a novel inactivation mechanism for CPP-115, a mechanism-based inactivator that undergoes GABA-AT-catalyzed hydrolysis of the difluoromethylene group to a carboxylic acid with concomitant loss of two fluoride ions and coenzyme conversion to pyridoxamine 5'-phosphate (PMP). The partition ratio for CPP-115 with GABA-AT is about 2000, releasing cyclopentanone-2,4-dicarboxylate (22) and two other precursors of this compound (20 and 21). Time-dependent inactivation occurs by a conformational change induced by the formation of the aldimine of 4-aminocyclopentane-1,3-dicarboxylic acid and PMP (20), which disrupts an electrostatic interaction between Glu270 and Arg445 to form an electrostatic interaction between Arg445 and the newly formed carboxylate produced by hydrolysis of the difluoromethylene group in CPP-115, resulting in a noncovalent, tightly bound complex. This represents a novel mechanism for inactivation of GABA-AT and a new approach for the design of mechanism-based inactivators in general.

Mechanism of Inactivation of γ-Aminobutyric Acid Aminotransferase by (1 S ,3 S)-3-Amino-4-difluoromethylene-1-cyclopentanoic Acid (CPP-115)

DOE PAGES

Lee, Hyunbeom; Doud, Emma H.; Wu, Rui; ...

2015-01-23

γ-Aminobutyric acid aminotransferase (GABA-AT) is a pyridoxal 5'-phosphate (PLP)-dependent enzyme that degrades GABA, the principal inhibitory neurotransmitter in mammalian cells. When the concentration of GABA falls below a threshold level, convulsions can occur. Inhibition of GABA-AT raises GABA levels in the brain, which can terminate seizures as well as have potential therapeutic applications in treating other neurological disorders, including drug addiction. Among the analogues that we previously developed, (1S,3S)-3-amino-4-difluoromethylene-1-cyclopentanoic acid (CPP-115) showed 187 times greater potency than that of vigabatrin, a known inactivator of GABA-AT and approved drug (Sabril) for the treatment of infantile spasms and refractory adult epilepsy. Recently,more » CPP-115 was shown to have no adverse effects in a Phase I clinical trial. Here we report a novel inactivation mechanism for CPP-115, a mechanism-based inactivator that undergoes GABA-AT-catalyzed hydrolysis of the difluoromethylene group to a carboxylic acid with concomitant loss of two fluoride ions and coenzyme conversion to pyridoxamine 5'-phosphate (PMP). The partition ratio for CPP-115 with GABA-AT is about 2000, releasing cyclopentanone-2,4-dicarboxylate (22) and two other precursors of this compound (20 and 21). Time-dependent inactivation occurs by a conformational change induced by the formation of the aldimine of 4-aminocyclopentane-1,3-dicarboxylic acid and PMP (20), which disrupts an electrostatic interaction between Glu270 and Arg445 to form an electrostatic interaction between Arg445 and the newly formed carboxylate produced by hydrolysis of the difluoromethylene group in CPP-115, resulting in a noncovalent, tightly bound complex. Ultimately, this represents a novel mechanism for inactivation of GABA-AT and a new approach for the design of mechanism-based inactivators in general.« less

Polyestercarbonates which exhibit improved processibility

DOEpatents

Krabbenhoft, Herman Otto

1999-01-01

The invention relates to a polyestercarbonate polymer which comprises repeating units of a mono-unsaturated aliphatic dicarboxylic acid having about 12 to about 20 carbon atoms. Preferred dicarboxylic acids for incorporation into the polymer are cis-octadec-9-enedioic acid or trans-octadec-9-enedioic acid. The use of these mono-unsaturated acids results in polymers with lower glass transition temperatures, and enhances processibility.

Laboratory study of the effect of oxalic acid on the cloud condensation nuclei activity of mineral dust aerosol

NASA Astrophysics Data System (ADS)

Gierlus, Kelly M.; Laskina, Olga; Abernathy, Tricia L.; Grassian, Vicki H.

2012-01-01

Dicarboxylic acids, which make up a significant portion of the atmospheric organic aerosol, are emitted directly through biomass burning as well as produced through the oxidation of volatile organic compounds. Oxalic acid, the most abundant of the dicarboxylic acids, has been shown by recent field studies to be present in mineral dust aerosol particles. The presence of these internally mixed organic compounds can alter the water absorption and cloud condensation nuclei (CCN) abilities of mineral particles in the Earth's atmosphere. The University of Iowa's Multi-Analysis Aerosol Reactor System ( MAARS) was used to measure the CCN activity of internally mixed particles that were generated from a mixture of either calcite or polystyrene latex spheres (PSLs) in an aqueous solution of oxalic acid. Although PSL is not a mineral dust component, it is used here as a non-reactive, insoluble particle. CCN measurements indicate that the internally mixed oxalate/calcite particles showed nearly identical CCN activity compared to the original calcite particles whereas oxalic acid/PSL internally mixed particles showed much greater CCN activity compared to PSL particles alone. This difference is due to the reaction of calcite with oxalic acid, which produces a relatively insoluble calcium oxalate coating on the particle surface and not a soluble coating as it does on the PSL particle. Our results suggest that atmospheric processing of mineral dust aerosol through heterogeneous processes will likely depend on the mineralogy and the specific chemistry involved. Increase in the CCN activity by incorporation of oxalic acid are only expected for unreactive insoluble dust particles that form a soluble coating.

Self-assembly of metal-organic supramolecules: from a metallamacrocycle and a metal-organic coordination cage to 1D or 2D coordination polymers based on flexible dicarboxylate ligands.

PubMed

Dai, Fangna; Dou, Jianmin; He, Haiyan; Zhao, Xiaoliang; Sun, Daofeng

2010-05-03

To assemble metal-organic supramolecules such as a metallamacrocycle and metal-organic coordination cage (MOCC), a series of flexible dicarboxylate ligands with the appropriate angle, 2,2'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H(2)L(1)), 2,2'-(2,5-dimethyl-1,4-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H(2)L(2)), 2,2'-(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(sulfanediyl)dinicotinic acid (H(2)L(3)), and 2,2'-(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H(2)L(4)), have been designed and synthesized. Using these flexible ligands to assemble with metal ions, six metal-organic supramolecules, Cd(2)(L(1))(2)(dmf)(4)(H(2)O)(2).H(2)O (1), Mn(3)((1)L(2))(2)((2)L(2))(dmf)(2)(H(2)O)(2).5dmf (2), Cu(4)(L(3))(4)(H(2)O)(4).3dmf (3), Cu(4)(L(4))(4)(dmf)(2)(EtOH)(2).8dmf.6H(2)O (4), Mn(4)(L(4))(4)(dmf)(4)(H(2)O)(4).6dmf.H(2)O (5), and Mn(3)(L(4))(3)(dmf)(4).2dmf.3H(2)O (6), possessing a rectangular macrocycle, MOCCs or their extensions, and 1D or 2D coordination polymers, have been isolated. All complexes have been characterized by single-crystal X-ray diffraction, elemental analysis, and thermogravimetric analysis. Complex 1 is a discrete rectangular macrocycle, while complex 2 is a 2D macrocycle-based coordination polymer in which the L(2) ligand adopts both syn and anti conformations. Complexes 3-5 are discrete MOCCs in which two binuclear metal clusters are engaged by four organic ligands. The different geometries of the secondary building units (SBUs) and the axial coordinated solvates on the SBUs result in their different symmetries. Complex 6 is a 1D coordination polymer, extended from a MOCC made up of two metal ions and three L(4) ligands. All of the flexible dicarboxylate ligands adopt a syn conformation except that in complex 2, indicating that the syn conformational ligand is helpful for the formation of a metallamacrocycle and a MOCC. The magnetic properties of complexes 5

Larvicidal activity of bis(2-ethylhexyl) benzene-1,2-dicarboxylate from Sterculia guttata seeds against two mosquito species.

PubMed

Katade, Sushama R; Pawar, Pushpa V; Tungikar, Vijay B; Tambe, Amruta S; Kalal, Kamlakar M; Wakharkar, Radhika D; Deshpande, Nirmala R

2006-01-01

The larvicidal activities of various fractions of the hexane extract of the seeds of Sterculia guttata against larvae of Aedes aegypti and Culex quinquefasciatus were determined. Bis(2-ethylhexyl) benzene-1,2-dicarboxylate (1) was identified as one of the active principles, displaying chronic toxicity against both types of larvae, with LD50 values of 79 and 64 ppm, respectively.

Anaerobic Fermentation for Production of Carboxylic Acids as Bulk Chemicals from Renewable Biomass.

PubMed

Wang, Jufang; Lin, Meng; Xu, Mengmeng; Yang, Shang-Tian

Biomass represents an abundant carbon-neutral renewable resource which can be converted to bulk chemicals to replace petrochemicals. Carboxylic acids have wide applications in the chemical, food, and pharmaceutical industries. This chapter provides an overview of recent advances and challenges in the industrial production of various types of carboxylic acids, including short-chain fatty acids (acetic, propionic, butyric), hydroxy acids (lactic, 3-hydroxypropionic), dicarboxylic acids (succinic, malic, fumaric, itaconic, adipic, muconic, glucaric), and others (acrylic, citric, gluconic, pyruvic) by anaerobic fermentation. For economic production of these carboxylic acids as bulk chemicals, the fermentation process must have a sufficiently high product titer, productivity and yield, and low impurity acid byproducts to compete with their petrochemical counterparts. System metabolic engineering offers the tools needed to develop novel strains that can meet these process requirements for converting biomass feedstock to the desirable product.

40 CFR 180.509 - Mefenpyr-diethyl; tolerance for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

... of the herbicide safener, mefenpyr-diethyl, 1-(2,4-dichlorophenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylic acid, diethyl ester and its 2,4-dichlorophenyl-pyrazoline metabolites, when applied... agricultural commodities: Commodity Parts per million Barley, grain 0.05 Barley, hay 0.2 Barley, straw 0.5...

Sequential Mixed Cultures: From Syngas to Malic Acid

PubMed Central

Oswald, Florian; Dörsam, Stefan; Veith, Nicolas; Zwick, Michaela; Neumann, Anke; Ochsenreither, Katrin; Syldatk, Christoph

2016-01-01

Synthesis gas (syngas) fermentation using acetogenic bacteria is an approach for production of bulk chemicals like acetate, ethanol, butanol, or 2,3-butandiol avoiding the fuel vs. food debate by using carbon monoxide, carbon dioxide, and hydrogen from gasification of biomass or industrial waste gases. Suffering from energetic limitations, yields of C4-molecules produced by syngas fermentation are quite low compared with ABE fermentation using sugars as a substrate. On the other hand, fungal production of malic acid has high yields of product per gram metabolized substrate but is currently limited to sugar containing substrates. In this study, it was possible to show that Aspergilus oryzae is able to produce malic acid using acetate as sole carbon source which is a main product of acetogenic syngas fermentation. Bioreactor cultivations were conducted in 2.5 L stirred tank reactors. During the syngas fermentation part of the sequential mixed culture, Clostridium ljungdahlii was grown in modified Tanner medium and sparged with 20 mL/min of artificial syngas mimicking a composition of clean syngas from entrained bed gasification of straw (32.5 vol-% CO, 32.5 vol-% H2, 16 vol-% CO2, and 19 vol-% N2) using a microsparger. Syngas consumption was monitored via automated gas chromatographic measurement of the off-gas. For the fungal fermentation part gas sparging was switched to 0.6 L/min of air and a standard sparger. Ammonia content of medium for syngas fermentation was reduced to 0.33 g/L NH4Cl to meet the requirements for fungal production of dicarboxylic acids. Malic acid production performance of A. oryzae in organic acid production medium and syngas medium with acetate as sole carbon source was verified and gave YP∕S values of 0.28 g/g and 0.37 g/g respectively. Growth and acetate formation of C. ljungdahlii during syngas fermentation were not affected by the reduced ammonia content and 66 % of the consumed syngas was converted to acetate. The overall conversion

Modification of wheat starch with succinic acid/acetic anhydride and azelaic acid/acetic anhydride mixtures I. Thermophysical and pasting properties.

PubMed

Subarić, Drago; Ačkar, Durđica; Babić, Jurislav; Sakač, Nikola; Jozinović, Antun

2014-10-01

The aim of this research was to investigate the influence of modification with succinic acid/acetic anhydride and azelaic acid/acetic anhydride mixtures on thermophysical and pasting properties of wheat starch. Starch was isolated from two wheat varieties and modified with mixtures of succinic acid and acetic anhydride, and azelaic acid and acetic anhydride in 4, 6 and 8 % (w/w). Thermophysical, pasting properties, swelling power, solubility and amylose content of modified starches were determined. The results showed that modifications with mixtures of afore mentioned dicarboxylic acids with acetic anhydride decreased gelatinisation and pasting temperatures. Gelatinisation enthalpy of Golubica starch increased, while of Srpanjka starch decreased by modifications. Retrogradation after 7 and 14 day-storage at 4 °C decreased after modifications of both starches. Maximum, hot and cold paste viscosity of both starches increased, while stability during shearing at high temperatures decreased. % setback of starches modified with azelaic acid/acetic anhydride mixture decreased. Swelling power and solubility of both starches increased by both modifications.

Tuning different kinds of entangled metal-organic frameworks by modifying the spacer group of aliphatic dicarboxylate ligands and the reactant ratio.

PubMed

Yang, Jin-Xia; Zhai, Ji-Quan; Zhang, Xin; Qin, Ye-Yan; Yao, Yuan-Gen

2016-01-14

Taking advantage of the conformational flexibility of the bpp ligand and aliphatic dicarboxylic acids, six interesting entangled coordination polymers, {[Cd(fum)(bpp)(H2O)]·(H2O)}n (), {[Cd(fum)(bpp)2]·(H2O)5}n (), {[Cd2(suc)1.5(bpp)2(NO3)(H2O)2]·6H2O}n (), {[Cd(suc)(bpp)2]·(H2O)1.5}n (), {[Cd2(glu)2(bpp)3]·10H2O}n (), and {Cd(adp)(bpp)(H2O)}n () have been prepared and structurally characterized (bpp = 1,3-bi(4-pyridyl)propane, fum = fumaric, suc = succinate, glu = glutaric, adp = adipic). Compounds and are comprised of undulated 2D 4(4)-sql networks. In the structure of compound , two identical undulated layers are parallelly interpenetrated with each other to give a 2D → 2D interpenetrating framework. For , the dangling arms projected from 2D layers are intercalated into the neighboring sheets, producing a 2D → 3D polythreading framework. Compound shows a rare example of a 2D self-penetrating framework with a (3,4)-connected (4(2)·6(3)·8)(4(2)·6) topology. Compound presents an unusual 2D self-threading network with a novel 4-connected {4(2)·6(3)·8} topology. Compound displays a 3D self-penetrating system based on a 2D → 3D parallel polycatenation array. Compound exhibits an unprecedented 3D self-penetrating structure having both 1D + 1D → 1D polycatenation and 3D + 3D → 3D interpenetration characteristics. A comparison of these six compounds demonstrates that both the different spacer lengths of the aliphatic dicarboxylates and reactant ratios appear to play a significant role in the assembly of entangled frameworks. In addition, thermal stabilities and photoluminescence properties of have been examined in the solid state at room temperature.

A prodrug approach to enhance azelaic acid percutaneous availability.

PubMed

Al-Marabeh, Sara; Khalil, Enam; Khanfar, Mohammad; Al-Bakri, Amal G; Alzweiri, Muhammed

2017-06-01

Azelaic acid is a dicarboxylic acid compound used in treatment of acne vulgaris. However, high concentration (ca 20%) is needed to guarantee the drug availability in the skin. The latter increases the incidence of side effects such as local irritation. The prodrug strategy to enhance azelaic acid diffusion through skin was not reported before. Thus, a lipophilic prodrug of azelaic acid (diethyl azelate [DEA]) was synthesized and investigated to improve percutaneous availability of azelaic acid, with a subsequent full physical, chemical, and biological characterization. Expectedly, DEA exhibited a significant increase in diffusion compared to azelaic acid through silicone membrane. In contrast, the diffusion results through human stratum corneum (SC) displayed weaker permeation for DEA with expected retention in the SC. Therefore, a desorption study of DEA from SC was conducted to examine the reservoir behavior in SC. Results showed an evidence of sustained release behavior of DEA from SC. Consequently, enhancement of keratolytic effect is expected due to azelaic acid produced from enzymatic conversion of DEA released from SC.

Amino Acid Transporters and Release of Hydrophobic Amino Acids in the Heterocyst-Forming Cyanobacterium Anabaena sp. Strain PCC 7120.

PubMed

Pernil, Rafael; Picossi, Silvia; Herrero, Antonia; Flores, Enrique; Mariscal, Vicente

2015-04-23

Anabaena sp. strain PCC 7120 is a filamentous cyanobacterium that can use inorganic compounds such as nitrate or ammonium as nitrogen sources. In the absence of combined nitrogen, it can fix N2 in differentiated cells called heterocysts. Anabaena also shows substantial activities of amino acid uptake, and three ABC-type transporters for amino acids have been previously characterized. Seven new loci encoding predicted amino acid transporters were identified in the Anabaena genomic sequence and inactivated. Two of them were involved in amino acid uptake. Locus alr2535-alr2541 encodes the elements of a hydrophobic amino acid ABC-type transporter that is mainly involved in the uptake of glycine. ORF all0342 encodes a putative transporter from the dicarboxylate/amino acid:cation symporter (DAACS) family whose inactivation resulted in an increased uptake of a broad range of amino acids. An assay to study amino acid release from Anabaena filaments to the external medium was set up. Net release of the alanine analogue α-aminoisobutyric acid (AIB) was observed when transport system N-I (a hydrophobic amino acid ABC-type transporter) was engaged in the uptake of a specific substrate. The rate of AIB release was directly proportional to the intracellular AIB concentration, suggesting leakage from the cells by diffusion.

A new pseudopolymorph of diphenic acid and 4,4‧-bipyridine co-crystal: Structural and theoretical study

NASA Astrophysics Data System (ADS)

Soleimannejad, Janet; Nazarnia, Esfandiar; Stoeckli-Evans, Helen

2014-11-01

A new pseudopolymorph (B; tetragonal, I41/acd) of the cocrystal biphenyl-2,2‧-dicarboxylic acid (diphenic acid) and 4,4‧-bipyridine was synthesized. Its solid-state structure and supramolecular synthons responsible for extending the supramolecular network have been compared with those of the previously reported polymorph (A; triclinic, P1bar). DFT calculations at the B3LYP/6-311G++ (2d,2p) level have been performed. Energies of the intermolecular hydrogen bonds in the crystal structure were calculated and their electronic aspects were investigated by NBO and AIM analysis.

The microsomal dicarboxylyl-CoA synthetase.

PubMed Central

Vamecq, J; de Hoffmann, E; Van Hoof, F

1985-01-01

Dicarboxylic acids are products of the omega-oxidation of monocarboxylic acids. We demonstrate that in rat liver dicarboxylic acids (C5-C16) can be converted into their CoA esters by a dicarboxylyl-CoA synthetase. During this activation ATP, which cannot be replaced by GTP, is converted into AMP and PPi, both acting as feedback inhibitors of the reaction. Thermolabile at 37 degrees C, and optimally active at pH 6.5, dicarboxylyl-CoA synthetase displays the highest activity on dodecanedioic acid (2 micromol/min per g of liver). Cell-fractionation studies indicate that this enzyme belongs to the hepatic microsomal fraction. Investigations about the fate of dicarboxylyl-CoA esters disclosed the existence of an oxidase, which could be measured by monitoring the production of H2O2. In our assay conditions this H2O2 production is dependent on and closely follows the CoA consumption. It appears that the chain-length specificity of the handling of dicarboxylic acids by this catabolic pathway (activation to acyl-CoA and oxidation with H2O2 production) parallels the pattern of the degradation of exogenous dicarboxylic acids in vivo. PMID:4062873

Conversion of the sensor kinase DcuS of Escherichia coli of the DcuB/DcuS sensor complex to the C4 -dicarboxylate responsive form by the transporter DcuB.

PubMed

Wörner, Sebastian; Strecker, Alexander; Monzel, Christian; Zeltner, Matthias; Witan, Julian; Ebert-Jung, Andrea; Unden, Gottfried

2016-12-01

The sensor kinase DcuS of Escherichia coli co-operates under aerobic conditions with the C 4 -dicarboxylate transporter DctA to form the DctA/DcuS sensor complex. Under anaerobic conditions C 4 -dicarboxylate transport in fumarate respiration is catalyzed by C 4 -dicarboxylate/fumarate antiporter DcuB. (i) DcuB interacted with DcuS as demonstrated by a bacterial two-hybrid system (BACTH) and by co-chromatography of the solubilized membrane-proteins (mHPINE assay). (ii) In the DcuB/DcuS complex only DcuS served as the sensor since mutations in the substrate site of DcuS changed substrate specificity of sensing, and substrates maleate or 3-nitropropionate induced DcuS response without affecting the fumarate site of DcuB. (iii) The half-maximal concentration for induction of DcuS by fumarate (1 to 2 mM) and the corresponding K m for transport (50 µM) differ by a factor of 20 to 40. Therefore, the fumarate sites are different in transport and sensing. (iv) Increasing levels of DcuB converted DcuS from the permanent ON (DcuB deficient) state to the fumarate responsive form. Overall, the data show that DcuS and DcuB form a DcuB/DcuS complex representing the C 4 -dicarboxylate responsive form, and that the sensory site of the complex is located in DcuS whereas DcuB is required for converting DcuS to the sensory competent state. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Current advance in biological production of malic acid using wild type and metabolic engineered strains.

PubMed

Dai, Zhongxue; Zhou, Huiyuan; Zhang, Shangjie; Gu, Honglian; Yang, Qiao; Zhang, Wenming; Dong, Weiliang; Ma, Jiangfeng; Fang, Yan; Jiang, Min; Xin, Fengxue

2018-06-01

Malic acid (2-hydroxybutanedioic acid) is a four-carbon dicarboxylic acid, which has attracted great interest due to its wide usage as a precursor of many industrially important chemicals in the food, chemicals, and pharmaceutical industries. Several mature routes for malic acid production have been developed, such as chemical synthesis, enzymatic conversion and biological fermentation. With depletion of fossil fuels and concerns regarding environmental issues, biological production of malic acid has attracted more attention, which mainly consists of three pathways, namely non-oxidative pathway, oxidative pathway and glyoxylate cycle. In recent decades, metabolic engineering of model strains, and process optimization for malic acid production have been rapidly developed. Hence, this review comprehensively introduces an overview of malic acid producers and highlight some of the successful metabolic engineering approaches. Copyright © 2018 Elsevier Ltd. All rights reserved.

Biosynthesis of adipic acid via microaerobic hydrogenation of cis,cis-muconic acid by oxygen-sensitive enoate reductase.

PubMed

Sun, Jing; Raza, Muslim; Sun, Xinxiao; Yuan, Qipeng

2018-06-06

Adipic acid (AA) is an important dicarboxylic acid used for the manufacture of nylon and polyurethane plastics. In this study, a novel adipic acid biosynthetic pathway was designed by extending the cis,cis-muconic acid (MA) biosynthesis through biohydrogenation. Enoate reductase from Clostridium acetobutylicum (CaER), an oxygen-sensitive reductase, was demonstrated to have in vivo enzyme activity of converting cis,cis-muconic acid to adipic acid under microaerobic condition. Engineered Escherichia coli strains were constructed to express the whole pathway and accumulated 5.8 ± 0.9 mg/L adipic acid from simple carbon sources. Considering the different oxygen demands between cis,cis-muconic acid biosynthesis and its degradation, a co-culture system was constructed. To improve production, T7 promoter instead of lac promoter was used for higher level expression of the key enzyme CaER and the titer of adipic acid increased to 18.3 ± 0.6 mg/L. To decrease the oxygen supply to downstream strains expressing CaER, Vitreoscilla hemoglobin (VHb) was introduced to upstream strains for its ability on oxygen obtaining. This attempt further improved the production of this novel pathway and 27.6 ± 1.3 mg/L adipic acid was accumulated under microaerobic condition. Copyright © 2018. Published by Elsevier B.V.

Dicarboxylic acids, metals and isotopic compositions of C and N in atmospheric aerosols from inland China: implications for dust and coal burning emission and secondary aerosol formation

NASA Astrophysics Data System (ADS)

Wang, G.; Xie, M.; Hu, S.; Tachibana, E.; Kawamura, K.

2010-03-01

Dicarboxylic acids (C2-C10), metals, elemental carbon (EC), organic carbon (OC), and stable isotopic compositions of total carbon (TC) and total nitrogen (TN) were determined for PM10 samples collected at three urban and one suburban sites of Baoji, an inland city of China, during winter and spring 2008. Oxalic acid (C2) was the dominant diacid, followed by succinic (C4) and malonic (C3) acids. Total diacids in the urban and suburban areas are 1546±203 and 1728±495 ng m-3 during winter and 1236±335 and 1028±193 ng m-3 during spring. EC in the urban and the suburban atmospheres are 17±3.8 and 8.0±2.1 μg m-3 during winter and 20±5.9 and 7.1±2.7 μg m-3 during spring whereas OC at the urban and suburban sites are 74±14 and 51±7.9 μg m-3 in winter and 51±20 and 23±6.1 μg m-3 in spring. Secondary organic carbon (SOC) accounted for 38±16% of OC in winter and 28±18% of OC in spring, suggesting an enhanced photochemical production of secondary organic aerosols in winter under an inversion layer development. Total metal elements in winter and spring are 34±10 and 61±27 μg m-3 in the urban air and 18±7 and 32±23 μg m-3 in the suburban air. A linear correlation (r2>0.8 in winter and r2>0.6 in spring) was found between primary organic carbon (POC) and Ca2+/Fe, together with a strong dependence of pH value on water-soluble inorganic carbon, suggesting fugitive dust as a major source of the airborne particles. Polycyclic aromatic hydrocarbons (PAHs), sulfate, and Pb in the samples well correlated each other (r2>0.6) in winter samples, suggesting an importance of emissions from coal burning for house heating. Stable carbon isotope compositions of TC (δ13C) became higher with an increase in the concentration ratios of C2/OC due to aerosol aging. In contrast, nitrogen isotope compositions of TN (δ15N) became lower with an increases in the mass ratios of NH4+/PM10 and NO3-/PM10 due to an enhanced adsorption and/or condensation of NH3 and HNO3 from gas phase

Dicarboxylic acids, metals and isotopic compositions of C and N in atmospheric aerosols from inland China: implications for dust and coal burning emission and secondary aerosol formation

NASA Astrophysics Data System (ADS)

Wang, G.; Xie, M.; Hu, S.; Gao, S.; Tachibana, E.; Kawamura, K.

2010-07-01

Dicarboxylic acids (C2-C10), metals, elemental carbon (EC), organic carbon (OC), and stable isotopic compositions of total carbon (TC) and total nitrogen (TN) were determined for PM10 samples collected at three urban and one suburban sites of Baoji, an inland city of China, during winter and spring 2008. Oxalic acid (C2) was the dominant diacid, followed by succinic (C4) and malonic (C3) acids. Total diacids in the urban and suburban areas were 1546±203 and 1728±495 ng m-3 during winter and 1236±335 and 1028±193 ng m-3 during spring. EC in the urban and the suburban atmospheres were 17±3.8 and 8.0±2.1 μg m-3 during winter and 20±5.9 and 7.1±2.7 μg m-3 during spring, while OC at the urban and suburban sites were 74±14 and 51±7.9 μg m-3 in winter and 51±20 and 23±6.1 μg m-3 in spring. Secondary organic carbon (SOC) accounted for 38±16% of OC in winter and 28±18% of OC in spring, suggesting an enhanced photochemical production of secondary organic aerosols in winter under an inversion layer development. Total metal elements in winter and spring were 34±10 and 61±27 μg m-3 in the urban air and 18±7 and 32±23 μg m-3 in the suburban air. A linear correlation (r2>0.8 in winter and r2>0.6 in spring) was found between primary organic carbon (POC) and Ca2+/Fe, together with a strong dependence of pH value of sample extracts on water-soluble inorganic carbon, suggesting fugitive dust as an important source of the airborne particles. Polycyclic aromatic hydrocarbons (PAHs), sulfate, and Pb in the samples well correlated each other (r2>0.6) in winter, indicating an importance of emissions from coal burning for house heating. Stable carbon isotope compositions of TC (δ13C) became higher with an increase in the concentration ratios of C2/OC due to aerosol aging. In contrast, nitrogen isotope compositions of TN (δ15N) became lower with an increases in the mass ratios of NH4+/PM10 and NO3-/PM10, which is possibly caused by an enhanced adsorption and

Pretreatment of solid carbonaceous material with dicarboxylic aromatic acids to prevent scale formation

DOEpatents

Brunson, Roy J.

1982-01-01

Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a pretreating agent selected from the group consisting of phthalic acid, phthalic anhydride, pyromellitic acid and pyromellitic anhydride. The pretreatment is believed to convert the scale-forming components to the corresponding phthalate and/or pyromellitate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 1 to about 2 atmospheres. Temperature during pretreatment will generally be within the range from about 5.degree. to about 80.degree. C.

Gas adsorption and structural diversity in a family of Cu(II) pyridyl-isophthalate metal-organic framework materials

NASA Astrophysics Data System (ADS)

Gould, Jamie A.; Athwal, Harprit Singh; Blake, Alexander J.; Lewis, William; Hubberstey, Peter; Champness, Neil R.; Schröder, Martin

2017-01-01

A family of Cu(II)-based metal-organic frameworks (MOFs) has been synthesized using three pyridyl-isophthalate ligands, H2L1 (4'-(pyridin-4-yl)biphenyl-3,5-dicarboxylic acid), H2L2 (4''-(pyridin-4-yl)-1,1':4',1''-terphenyl-3,5-dicarboxylic acid) and H2L3 (5-[4-(pyridin-4-yl)naphthalen-1-yl]benzene-1,3-dicarboxylic acid). Although in each case the pyridyl-isophthalate ligands adopt the same pseudo-octahedral [Cu2(O2CR)4N2] paddlewheel coordination modes, the resulting frameworks are structurally diverse, particularly in the case of the complex of Cu(II) with H2L3, which leads to three distinct supramolecular isomers, each derived from Kagomé and square nets. In contrast to [Cu(L2)] and the isomers of [Cu(L3)], [Cu(L1)] exhibits permanent porosity. Thus, the gas adsorption properties of [Cu(L1)] were investigated with N2, CO2 and H2, and the material exhibits an isosteric heat of adsorption competitive with leading MOF sorbents for CO2. [Cu(L1)] displays high H2 adsorption, with the density in the pores approaching that of liquid H2. This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

Fluoranthene metabolism and associated proteins in Mycobacterium sp. JS14.

PubMed

Lee, Sung-Eun; Seo, Jong-Su; Keum, Young-Soo; Lee, Kwang-Jun; Li, Qing X

2007-06-01

Fluoranthene is a polycyclic aromatic hydrocarbon (PAH) commonly present in PAH-contaminated soils. We studied fluoranthene catabolism and associated proteins in Mycobacterium sp. JS14, a bacterium isolated from a PAH-contaminated soil in Hilo (HI, USA). Fluoranthene degrades in at least three separated pathways via 1-indanone, 2',3'-dihydroxybiphenyl-2,3,-dicarboxylic acid, and naphthalene-1,8-dicarboxylic acid. Part of the diverse catabolism is converged into phthalate catabolism. An increased expression of 25 proteins related to fluoranthene catabolism is found with 1-D PAGE or 2-DE and nano-LC-MS/MS. Detection of fluoranthene catabolism associated proteins coincides well with its multiple degradation pathways that are mapped via metabolites identified. Among the up-regulated proteins, PAH ring-hydroxylating dioxygenase alpha-subunit and beta-subunit and 2,3-dihydroxybiphenyl 1,2-dioxygenase are notably induced. The up-regulation of trans-2-carboxybenzalpyruvate hydratase suggests that some of fluoranthene metabolites may be further degraded through aromatic dicarboxylic acid pathways. Catalase and superoxide dismutase were up-regulated to control unexpected oxidative stress during the fluoranthene catabolism. The up-regulation of chorismate synthase and nicotine-nucleotide phosphorylase may be necessary for sustaining shikimate pathway and pyrimidine biosynthesis, respectively. A fluoranthene degradation pathway for Mycobacterium sp. JS14 was proposed and confirmed by proteomic study by identifying almost all the enzymes required during the initial steps of fluoranthene degradation.

Discrete hexamer water clusters and 2D water layer trapped in three luminescent Ag/tetramethylpyrazine/benzene-dicarboxylate hosts: 1D chain, 2D layer and 3D network

NASA Astrophysics Data System (ADS)

Mei, Hong-Xin; Zhang, Ting; Huang, Hua-Qi; Huang, Rong-Bin; Zheng, Lan-Sun

2016-03-01

Three mix-ligand Ag(I) coordination compounds, namely, {[Ag10(tpyz) 5(L1) 5(H2 O)2].(H2 O)4}n (1, tpyz = 2,3,4,5-tetramethylpyrazine, H2 L1 = phthalic acid), [Ag4(tpyz) 2(L2) 2(H2 O)].(H2 O)5}n (2, H2 L2 = isophthalic acid) {[Ag2(tpyz) 2(L3) (H2 O)4].(H2 O)8}n (3, H2 L3 = terephthalic acid), have been synthesized and characterized by elemental analysis, IR, PXRD and X-ray single-crystal diffraction. 1 exhibits a 2D layer which can be simplified as a (4,4) net. 2 is a 3D network which can be simplified as a (3,3)-connected 2-nodal net with a point symbol of {102.12}{102}. 3 consists of linear [Ag(tpyz) (H2 O)2]n chain. Of particular interest, discrete hexamer water clusters were observed in 1 and 2, while a 2D L10(6) water layer exists in 3. The results suggest that the benzene dicarboxylates play pivotal roles in the formation of the different host architectures as well as different water aggregations. Moreover, thermogravimetric analysis (TGA) and emissive behaviors of these compounds were investigated.

Simultaneous determination of trace concentrations of aldehydes and carboxylic acids in particulate matter.

PubMed

Rousová, Jana; Chintapalli, Manikyala R; Lindahl, Anastasia; Casey, Jana; Kubátová, Alena

2018-04-06

Carboxylic acids and aldehydes are present in ambient air particulate matter (PM) originating from both primary emission and secondary production in air and may, due to their polarity have, an impact on formation of cloud condensation nuclei. Their simultaneous determination may provide improved understanding of atmospheric processes. We developed a new analytical method allowing for a single step determination of majority of carboxylic acids and aldehydes (+95 compounds). This sample preparation employed O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA·HCl) in methanol to yield oximes (for aldehydes) and methyl esters (for majority of acids); with the limits of detection of 0.02-1 ng per injection, corresponding to approximately 0.4-20 μg/g PM . Subsequent trimethylsilylation with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) was employed only for aromatic acids, which were not completely esterified, and for hydroxyl groups. Our method, in contrast to previous primarily qualitative studies, based on derivatization with an aqueous PFBHA followed by BSTFA derivatization, is less labor-intesive and reduces sample losses caused by an evaporation. The method was tested with a broad range of functionalized compounds (95), including monocarboxylic, dicarboxylic and aromatic acids, ketoacids, hydroxyacids and aldehydes. The developed protocol was applied to wood smoke (WS) and urban air standard reference material 1648b (UA) PM. The observed concentrations of aldehydes were 10-3000 μg/g PM in WS PM and 10-900 μg/g PM in UA PM, while those of acids were 20-1800 μg/g PM in WS PM and 15-1200 μg/g PM in UA PM. The most prominent aldehydes were syringaldehyde and vanillin in WS PM and glyoxal in UA PM. The most abundant acids in both PM samples were short-chain dicarboxylic acids (≤C 10 ). WS PM had a high abundance of hydroxyacids (vanillic and malic acids) as well as ketoacids (glutaric and oxalacetic) while UA PM also featured a high abundance of

Condensation of anhydrides or dicarboxylic acids with compounds containing active methylene groups. Part 1: Condensation of phthalic anhydride with acetoacetic and malonic ester

NASA Technical Reports Server (NTRS)

Oshkaya, V. P.; Vanag, G. Y.

1985-01-01

Phthalic anhydride was condensed with acetoacetic ester in acetic anhydride and triethylamine solution, and when phthalyl chloride was reacted with sodium acetoacetic ester compounds were formed of the phthalide and indandione series: phthalylacetoacetic ester and a derivative of indan-1,3-dione which after boiling with hydrochloric acid yielded indan-1,3-dione. Phthalylmalonic ester was obtained from phthalic anhydride and malonic ester in the presence of triethylamine.

Syntheses, structures and properties of three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers based on 2,2'-dipyridyl-5,5'-dicarboxylate ligands.

PubMed

Zhao, Junwei; Cheng, Yamin; Shang, Sensen; Zhang, Fang; Chen, Li; Chen, Lijuan

2013-12-01

Three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers [Ln(III)Cu2(I)(Hbpdc)4] · Cl · xH2O [Ln(III) = La(III), x = 8 (1); Ln(III) = Pr(III), x=9 (2); Ln(III) = Eu(III), x = 8 (3)] (H2bpdc = 2,2'-bipyridyl-5,5'-dicarboxylic acid) have been prepared under hydrothermal conditions and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, IR spectra, X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. X-ray diffraction indicates that the isomorphic 1-3 display the two-dimensional sheet structure constructed from [Cu(I)(Hbpdc)2](-) fragments through Ln(3+) connectors. Moreover, the solid-state photoluminescence measurements of 3 indicate that the Eu(III) ions, Hbpdc(-) ligands and Cu(I) cations make contributions to its luminescent properties simultaneously. Copyright © 2013 Elsevier B.V. All rights reserved.

Formal [4+2] cycloaddition of di-tert-butyl 2-ethoxycyclobutane-1,1-dicarboxylate with ketones or aldehydes and tandem lactonization.

PubMed

Okado, Ryohei; Nowaki, Aya; Matsuo, Jun-Ichi; Ishibashi, Hiroyuki

2012-01-01

A catalytic amount of tin(IV) chloride catalyzed formal [4+2] cycloaddition reaction of di-tert-butyl 2-ethoxycyclobutane-1,1-carboxylate with ketones or aldehydes to give diethyl 6-ethoxydihydro-2H-pyran-3,3(4H)-dicarboxylates, whereas two equivalents of trimethylsilyl triflate promoted tandem [4+2] cycloaddition and lactonization to afford 3-oxo-2,6-dioxabicyclo[2.2.2]octane-4-carboxylate esters.

Kinetics of Maleic Acid and Aluminum Chloride Catalyzed Dehydration and Degradation of Glucose

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

Zhang, Ximing; Hewetson, Barron B.; Mosier, Nathan S.

We report the positive effect of maleic acid, a dicarboxylic acid, on the selectivity of hexose dehydration to 5-hydroxymethyfurfural (HMF) and subsequent hydrolysis to levulinic and formic acids. We also describe the kinetic analysis of a Lewis acid (AlCl3) alone and in combination with HCl or maleic acid to catalyze the isomerization of glucose to fructose, dehydration of fructose to HMF, hydration of HMF to levulinic and formic acids, and degradation of these compounds to humins. The results show that AlCl3 significantly enhances the rate of glucose conversion to HMF and levulinic acid in the presence of both maleic acidmore » and HCl. In addition, the degradation of HMF to humins, rather than levulinic and formic acids, is reduced by 50% in the presence of maleic acid and AlCl3 compared to HCl combined with AlCl3. The results suggest different reaction mechanisms for the dehydration of glucose and rehydration of HMF between maleic acid and HCl.« less

Syntheses, structures and magnetic properties of four coordination polymers based on nitrobenzene dicarboxylate and various N-donor coligands

NASA Astrophysics Data System (ADS)

Li, Gui-Lian; Yin, Wei-Dong; Liu, Guang-Zhen; Ma, Lu-Fang; Wang, Li-Ya

2014-12-01

Four new coordination polymers {[Ni(4-Nbdc)(bpa)(H2O)]}n (1), {[Co(4-Nbdc)(bpp) (H2O)]}n (2), {[Ni(4-Nbdc)(bpp)(H2O)]·H2O}n (3), and {[Mn2(3-Nbdc)2(bib)3]·2H2O}n (4) (4-Nbdc=4-nitrobenzene-1,2-dicarboxylate, 3-Nbdc=3-nitrobenzene-1,2-dicarboxylate, bpa=1,2-bi(4-pyridyl)ethane, bpp=1,3-bis(4-pyridyl)propane, and bib=1,4-bis(1-imidazoly)benzene), were synthesized by hydrothermal reactions, and characterized by single-crystal X-ray diffractions, elemental analysis, FT-IR, PXRD, TGA and magnetic analysis. Complexes 1 and 2 display quasi-trapezoidal chain and brick-wall layer, and both of them contain metal-carboxylate binuclear units. Complexes 3 and 4 exhibit three-dimensional frameworks with the (66) dia topology and (44.610.8)(44.62) fsc topology, and both of them contain metal-carboxylate chains. The carboxyl groups with syn-anti coordination mode mediate effectively the weak ferromagnetic coupling interaction within Ni(II)-carboxylate binuclear in 1 (J=1.27 cm-1) and Ni(II)-carboxylate chain in 3 (J=1.44 cm-1), respectively, and the carboxyl groups with anti-anti coordination mode leads to the classic antiferromagnetic coupling interaction within Mn(II)-carboxylate chain in 4 (J=-0.77 cm-1).

A Novel Coordination Polymer Constructed by Hetero-Metal Ions and 2,3-Pyridine Dicarboxylic Acid: Synthesis and Structure of [NiNa2(PDC)2(μ-H2O)(H2O)2] n

NASA Astrophysics Data System (ADS)

Dou, Ming-Yu; Lu, Jing

2017-12-01

A novel coordination polymer containing hetero-metal ions, [NiNa2(PDC)2(μ-H2O)(H2O)2] n , where PDC is 2,3-pyridine dicarboxylate ion, has been synthesized. In the structure, the PDC ligand chelates and bridges two Ni(II) and two Na(I) centers. Two kinds of metal centers are connected by μ4-PDC and μ2-H2O to form 2D coordination layers. Hydrogen bonds between coordination water molecules and carboxylate oxygen atoms further link these 2D coordination layers to form 3D supramolecular network.

Solid-state NMR studies of theophylline co-crystals with dicarboxylic acids.

PubMed

Pindelska, Edyta; Sokal, Agnieszka; Szeleszczuk, Lukasz; Pisklak, Dariusz Maciej; Kolodziejski, Waclaw

2014-11-01

In this work, three polycrystalline materials containing co-crystals of theophylline with malonic, maleic, and glutaric acids were studied using (13)C, (15)N and (1)H solid-state NMR and FT-IR spectroscopy. The NMR assignments were supported by gauge including projector augmented waves (GIPAW) calculations of chemical shielding, performed using X-ray determined geometry. The experimental (13)C cross polarization/magic angle spinning (CP/MAS) NMR results and the calculated isotropic chemical shifts were in excellent agreement. A rapid and convenient method for theophylline co-crystals crystal structure analysis has been proposed for co-crystals, which are potentially new APIs. Copyright © 2014 Elsevier B.V. All rights reserved.

Theoretical study of the hydrolysis mechanism of 2-pyrone-4,6-dicarboxylate (PDC) catalyzed by LigI.

PubMed

Zhang, Shujun; Ma, Guangcai; Liu, Yongjun; Ling, Baoping

2015-09-01

2-Pyrone-4,6-dicarboxylate lactonase (LigI) is the first identified enzyme from amidohydrolase superfamily that does not require a divalent metal ion for catalytic activity. It catalyzes the reversible hydrolysis of 2-pyrone-4,6-dicarboxylate (PDC) to 4-oxalomesaconate (OMA) and 4-carboxy-2-hydroxymuconate (CHM) in the degradation of lignin. In this paper, a combined quantum mechanics and molecule mechanics (QM/MM) approach was employed to study the reaction mechanism of LigI from Sphingomonas paucimobilis. According to the results of our calculations, the whole catalytic reaction contains three elementary steps, including the nucleophilic attack, the cleavage of CO of lactone (substrate) and the intramolecular proton transfer. The intermediate has two intramolecular proton transfer pathways, due to which, two final hydrolysis products can be obtained. The energy profile indicates that 4-carboxy-2-hydroxymuconate (CHM) is the main hydrolysis product, therefore, the isomerization between 4-carboxy-2-hydroxymuconate (CHM) and 4-oxalomesaconate (OMA) is suggested to occur in solvent. During the catalytic reaction, residue Asp248 acts as a general base to activate the hydrolytic water molecule. Although His31, His33 and His180 do not directly participate in the chemical process, they play assistant roles by forming electrostatic interactions with the substrate and its involved species in activating the carbonyl group of the substrate and stabilizing the intermediates and transition states. Copyright © 2015 Elsevier Inc. All rights reserved.

Curcumin improves alcoholic fatty liver by inhibiting fatty acid biosynthesis.

PubMed

Guo, Chang; Ma, Jingfan; Zhong, Qionghong; Zhao, Mengyuan; Hu, Tianxing; Chen, Tong; Qiu, Longxin; Wen, Longping

2017-08-01

Alcoholic fatty liver is a threat to human health. It has been long known that abstinence from alcohol is the most effective therapy, other effective therapies are not available for the treatment in humans. Curcumin has a great potential for anti-oxidation and anti-inflammation, but the effect on metabolic reconstruction remains little known. Here we performed metabolomic analysis by gas chromatography/mass spectrometry and explored ethanol pathogenic insight as well as curcumin action pattern. We identified seventy-one metabolites in mouse liver. Carbohydrates and lipids were characteristic categories. Pathway analysis results revealed that ethanol-induced pathways including biosynthesis of unsaturated fatty acids, fatty acid biosynthesis and pentose and glucuronate interconversions were suppressed by curcumin. Additionally, ethanol enhanced galactose metabolism and pentose phosphate pathway. Glyoxylate and dicarboxylate metabolism and pyruvate metabolism were inhibited in mice fed ethanol diet plus curcumin. Stearic acid, oleic acid and linoleic acid were disease biomarkers and therapical biomarkers. These results reflect the landscape of hepatic metabolism regulation. Our findings illustrate ethanol pathological pathway and metabolic mechanism of curcumin therapy. Copyright © 2017. Published by Elsevier Inc.

Synthesis and Preclinical Evaluation of Radioiodinated Hypericin Dicarboxylic Acid as a Necrosis Avid Agent in Rat Models of Induced Hepatic, Muscular, and Myocardial Necroses.

PubMed

Li, Jindian; Zhang, Jian; Yang, Shengwei; Jiang, Cuihua; Zhang, DongJian; Jin, Qiaomei; Wang, Qin; Wang, Cong; Ni, Yicheng; Yin, Zhiqi; Song, Shaoli

2016-01-04

Myocardial infarction (MI) leads to substantial morbidity and mortality around the world. Accurate assessment of myocardial viability is essential to assist therapies and improve patient outcomes. (131)I-hypericin dicarboxylic acid ((131)I-HDA) was synthesized and evaluated as a potential diagnostic agent for earlier assessment of myocardium viability compared to its preceding counterpart (131)I-hypericin ((131)I-Hyp) with strong hydrophobic property, long plasma half-life, and high uptake in mononuclear phagocyte system (MPS). Herein, HDA was synthesized and characterized, and self-aggregation constant Kα was analyzed by spectrophotometry. Plasma half-life was determined in healthy rats by γ-counting. (131)I-HDA and (131)I-Hyp were prepared with iodogen as oxidant. In vitro necrosis avidity of (131)I-HDA and (131)I-Hyp was evaluated in necrotic cells induced by hyperthermia. Biodistribution was determined in rat models of induced necrosis using γ-counting, autoradiography, and histopathology. Earlier imaging of necrotic myocardium to assess myocardial viability was performed in rat models of reperfused myocardium infarction using single photon emission computed tomography/computed tomography (SPECT/CT). As a result, the self-aggregation constant Kα of HDA was lower than that of Hyp (105602 vs 194644, p < 0.01). (131)I-HDA displayed a shorter blood half-life compared with (131)I-Hyp (9.21 vs 31.20 h, p < 0.01). The necrotic-viable ratio in cells was higher with (131)I-HDA relative to that with (131)I-Hyp (5.48 vs 4.63, p < 0.05). (131)I-HDA showed a higher necrotic-viable myocardium ratio (7.32 vs 3.20, p < 0.01), necrotic myocardium-blood ratio (3.34 vs 1.74, p < 0.05), and necrotic myocardium-lung ratio (3.09 vs 0.61, p < 0.01) compared with (131)I-Hyp. (131)I-HDA achieved imaging of necrotic myocardium at 6 h postinjection (p.i.) with SPECT/CT, earlier than what (131)I-Hyp did. Therefore, (131)I-HDA may serve as a promising necrosis-avid diagnostic agent for

Pimelic acid, the first precursor of the Bacillus subtilis biotin synthesis pathway, exists as the free acid and is assembled by fatty acid synthesis.

PubMed

Manandhar, Miglena; Cronan, John E

2017-05-01

Biotin synthetic pathways are readily separated into two stages, synthesis of the seven carbon α, ω-dicarboxylic acid pimelate moiety and assembly of the fused heterocyclic rings. The biotin pathway genes responsible for pimelate moiety synthesis vary widely among bacteria whereas the ring synthesis genes are highly conserved. Bacillus subtilis seems to have redundant genes, bioI and bioW, for generation of the pimelate intermediate. Largely consistent with previous genetic studies it was found that deletion of bioW caused a biotin auxotrophic phenotype whereas deletion of bioI did not. BioW is a pimeloyl-CoA synthetase that converts pimelic acid to pimeloyl-CoA. The essentiality of BioW for biotin synthesis indicates that the free form of pimelic acid is an intermediate in biotin synthesis although this is not the case in E. coli. Since the origin of pimelic acid in Bacillus subtilis is unknown, 13 C-NMR studies were carried out to decipher the pathway for its generation. The data provided evidence for the role of free pimelate in biotin synthesis and the involvement of fatty acid synthesis in pimelate production. Cerulenin, an inhibitor of the key fatty acid elongation enzyme, FabF, markedly decreased biotin production by B. subtilis resting cells whereas a strain having a cerulenin-resistant FabF mutant produced more biotin. In addition, supplementation with pimelic acid fully restored biotin production in cerulenin-treated cells. These results indicate that pimelic acid originating from fatty acid synthesis pathway is a bona fide precursor of biotin in B. subtilis. © 2017 John Wiley & Sons Ltd.

Long Chain Saturated and Unsaturated Carboxylic Acids: Filling a Large Gap of Knowledge in Their Enthalpies of Formation.

PubMed

Rogers, Donald W; Zavitsas, Andreas A

2017-01-06

Despite their abundance in nature and their importance in biology, medicine, nutrition, and in industry, gas phase enthalpies of formation of many long chain saturated and unsaturated fatty acids and of dicarboxylic acids are either unavailable or have been estimated with large uncertainties. Available experimental values for stearic acid show a spread of 68 kJ mol -1 . This work fills the knowledge gap by obtaining reliable values by quantum theoretical calculations using G4 model chemistry. Compounds with up to 20 carbon atoms are treated. The theoretical results are in excellent agreement with well established experimental values when such values exist, and they provide a large number of previously unavailable values.

Molecular structure, vibrational spectroscopic (FT-IR, FT-Raman), UV-vis spectra, first order hyperpolarizability, NBO analysis, HOMO and LUMO analysis, thermodynamic properties of benzophenone 2,4-dicarboxylic acid by ab initio HF and density functional method

NASA Astrophysics Data System (ADS)

Chaitanya, K.

2012-02-01

The FT-IR (4000-450 cm -1) and FT-Raman spectra (3500-100 cm -1) of benzophenone 2,4-dicarboxylic acid (2,4-BDA) have been recorded in the condensed state. Density functional theory calculation with B3LYP/6-31G(d,p) basis set have been used to determine ground state molecular geometries (bond lengths and bond angles), harmonic vibrational frequencies, infrared intensities, Raman activities and bonding features of the title compounds. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability ( β0) and related properties ( β, α0 and Δ α) of 2,4-BDA is calculated using HF/6-31G(d,p) method on the finite-field approach. The stability of molecule has been analyzed by using NBO analysis. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics. The calculated HOMO and LUMO energies show that charge transfer occurs within these molecules. Mulliken population analysis on atomic charges is also calculated. Because of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated. Finally, the UV-vis spectra and electronic absorption properties were explained and illustrated from the frontier molecular orbitals.

Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2016-11-01

In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L) 2] catalysts (bdaH 2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda 2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF 3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10 –4more » M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10 –6 M), the RDS was a bimolecular step with k H/k D ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF 3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.« less

37 CFR 1.823 - Requirements for nucleotide and/or amino acid sequences as part of the application.

Code of Federal Regulations, 2011 CFR

2011-07-01

... and/or amino acid sequences as part of the application. 1.823 Section 1.823 Patents, Trademarks, and... Amino Acid Sequences § 1.823 Requirements for nucleotide and/or amino acid sequences as part of the... incorporation-by-reference of the Sequence Listing as required by § 1.52(e)(5). The presentation of the...

37 CFR 1.823 - Requirements for nucleotide and/or amino acid sequences as part of the application.

Code of Federal Regulations, 2013 CFR

2013-07-01

... and/or amino acid sequences as part of the application. 1.823 Section 1.823 Patents, Trademarks, and... Amino Acid Sequences § 1.823 Requirements for nucleotide and/or amino acid sequences as part of the... incorporation-by-reference of the Sequence Listing as required by § 1.52(e)(5). The presentation of the...

37 CFR 1.823 - Requirements for nucleotide and/or amino acid sequences as part of the application.

Code of Federal Regulations, 2012 CFR

2012-07-01

... and/or amino acid sequences as part of the application. 1.823 Section 1.823 Patents, Trademarks, and... Amino Acid Sequences § 1.823 Requirements for nucleotide and/or amino acid sequences as part of the... incorporation-by-reference of the Sequence Listing as required by § 1.52(e)(5). The presentation of the...

37 CFR 1.823 - Requirements for nucleotide and/or amino acid sequences as part of the application.

Code of Federal Regulations, 2010 CFR

2010-07-01

... and/or amino acid sequences as part of the application. 1.823 Section 1.823 Patents, Trademarks, and... Amino Acid Sequences § 1.823 Requirements for nucleotide and/or amino acid sequences as part of the... incorporation-by-reference of the Sequence Listing as required by § 1.52(e)(5). The presentation of the...

37 CFR 1.823 - Requirements for nucleotide and/or amino acid sequences as part of the application.

Code of Federal Regulations, 2014 CFR

2014-07-01

... and/or amino acid sequences as part of the application. 1.823 Section 1.823 Patents, Trademarks, and... Amino Acid Sequences § 1.823 Requirements for nucleotide and/or amino acid sequences as part of the... incorporation-by-reference of the Sequence Listing as required by § 1.52(e)(5). The presentation of the...

Particulate organic acids in the atmosphere of Italian cities: Are they environmentally relevant?

NASA Astrophysics Data System (ADS)

Balducci, Catia; Cecinato, Angelo

2010-02-01

Mono- and dicarboxylic n-alkyl acids were extensively investigated in downtown Rome, Italy, and in Montelibretti, ˜30 km NE of the city, during 2005-2007. Congeners ranging from lauric to mellisic, and from succinic to α,ω-docosanedioic acids were evaluated as well as phthalic, palmitoleic and oleic acids, by solvent extraction of airborne particulates followed by derivatization with propanol in the presence of boron trifluoride, and gas chromatographic-mass spectrometric analysis. Shorter measurements were made in Milan, in Taranto, at suburban and rural sites of Italy, and in the polar regions, from 1996 to 2005. The predominance of palmitic and stearic acids observed elsewhere was confirmed, and the behaviour of azelaic and phthalic acids resulted strongly dependent upon the year season. In the urban sites, among the long-chain compounds, the lignoceric acid was usually the most abundant, while the cerotic, montanic and mellisic homologues cumulatively never exceeded 8% of the total. Unlike other contaminants, the concentrations of organic acids remained fairly invariant over the last decade, suggesting that more attention must be paid to them in the future.

Site-specific ligation of anthracene-1,8-dicarboxylates to an Mn12 core: a route to the controlled functionalisation of single-molecule magnets.

PubMed

Pacchioni, Mirko; Cornia, Andrea; Fabretti, Antonio C; Zobbi, Laura; Bonacchi, Daniele; Caneschi, Andrea; Chastanet, Guillaume; Gatteschi, Dante; Sessoli, Roberta

2004-11-21

A novel single-molecule magnet of the Mn12 family, [Mn12O12(O2CC6H5)8(L)4(H2O)4].8CH2Cl2, has been synthesised by site-specific ligand exchange using a tailor-made dicarboxylate (L2-), which leads to selective occupation of axial binding sites.

Dipropyl 3,6-diphenyl-1,2-dihydro-1,2,4,5-tetrazine-1,2-dicarboxylate.

PubMed

Rao, Guo-Wu; Hu, Wei-Xiao

2003-05-01

The title compound, C(22)H(24)N(4)O(4), was prepared from propyl chloroformate and 3,6-diphenyl-1,2-dihydro-s-tetrazine. This reaction yields the title compound rather than dipropyl 3,6-diphenyl-1,4-dihydro-s-tetrazine-1,4-dicarboxylate. The 2,3-diazabutadiene group in the central six-membered ring is not planar; the C=N double-bond length is 1.285 (2) A, and the average N-N single-bond length is 1.401 (3) A, indicating a lack of conjugation. The ring has a twist conformation, in which adjacent N atoms lie +/- 0.3268 (17) A from the plane of the ring. The molecule has twofold crystallographic symmetry.

Dicarboxylic acid anhydride condensation with compounds containing active methylene groups. 4: Some 4-nitrophthalic anhydride condensation reactions

NASA Technical Reports Server (NTRS)

Oskaja, V.; Rotberg, J.

1985-01-01

By 4-nitrophthalic anhydride condensation with acetoacetate in acetic anhydride and triethylamine solution with subsequent breakdown of the intermediate condensation product, 5-nitroindanedione-1,3 was obtained. A 4-nitrophthalic anhydride with acetic anhydride, according to reaction conditions, may yield two products: in the presence of potassium acetate and at high temperatures 4-(or 5-)-nitro-2-acetylbenzoic acid is formed: in the presence of triethylamine and at room temperature 5-( or 6-)-nitrophthalic acetic acid is isolated. A 4-nitrophthalic anhydride and malonic acid in pyridine solution according to temperature yield either 5-( or 6-)-nitrophthalic acetic acid or 4-(or 5-)-nitro-2-acetylbenzoic acid.

Gas adsorption properties of highly porous metal-organic frameworks containing functionalized naphthalene dicarboxylate linkers.

PubMed

Sim, Jaeung; Yim, Haneul; Ko, Nakeun; Choi, Sang Beom; Oh, Youjin; Park, Hye Jeong; Park, SangYoun; Kim, Jaheon

2014-12-28

Three functionalized metal-organic frameworks (MOFs), MOF-205-NH2, MOF-205-NO2, and MOF-205-OBn, formulated as Zn4O(BTB)4/3(L), where BTB is benzene-1,3,5-tribenzoate and L is 1-aminonaphthalene-3,7-dicarboxylate (NDC-NH2), 1-nitronaphthalene-3,7-dicarboxylate (NDC-NO2) or 1,5-dibenzyloxy-2,6-naphthalenedicarboxylate (NDC-(OBn)2), were synthesized and their gas (H2, CO2, or CH4) adsorption properties were compared to those of the un-functionalized, parent MOF-205. Ordered structural models for MOF-205 and its derivatives were built based on the crystal structures and were subsequently used for predicting porosity properties. Although the Brunauer-Emmett-Teller (BET) surface areas of the three MOF-205 derivatives were reduced (MOF-205, 4460; MOF-205-NH2, 4330; MOF-205-NO2, 3980; MOF-205-OBn, 3470 m(2) g(-1)), all three derivatives were shown to have enhanced H2 adsorption capacities at 77 K and CO2 uptakes at 253, 273, and 298 K respectively at 1 bar in comparison with MOF-205. The results indicate the following trend in H2 adsorption: MOF-205 < MOF-205-NO2 < MOF-205-NH2 < MOF-205-OBn. MOF-205-OBn showed good ideal adsorbed solution theory (IAST) selectivity values of 6.5 for CO2/N2 (15/85 in v/v) and 2.7 for CO2/CH4 (50/50 in v/v) at 298 K. Despite the large reduction (-22%) in the surface area, MOF-205-OBn displayed comparable total volumetric CO2 (at 48 bar) and CH4 (at 35 bar) storage capacities with those of MOF-205 at 298 K: MOF-205-OBn, 305 (CO2) and 112 (CH4) cm(3) cm(-3), and for MOF-205, 307 (CO2) and 120 (CH4) cm(3) cm(-3), respectively.

A three-dimensional coordination polymer based on 1,2,3-triazole-4,5-dicarboxylic acid (H{sub 3}tda): ([Cd{sub 12}(tda){sub 8}(H{sub 2}O){sub 11}] · (H{sub 2}O)6.25){sub n}

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

Zhou, Xin-Hui, E-mail: iamxhzhou@njupt.edu.cn; Chen, Qiang

The title coordination polymer ([Cd{sub 12}(tda){sub 8}(H{sub 2}O){sub 11}] · (H{sub 2}O){sub 6.25}){sub n} (H{sub 3}tda = 1,2,3-triazole-4,5-dicarboxylic acid), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex crystallizes in orthorhombic sp. gr. Pmn2{sub 1} with Z = 4. The Cd{sub 2} unit doublebridged by one carboxylate oxygen atom and two neighboring nitrogen atoms from the tda{sup 3–} ligands are linked by the tda{sup 3–}ligands to lead to the 2D (4,4) network in the ac plane. The almost coplanar Cd{sub 2}(μ{sub 5}-tda){sub 2} unit comprised of two Cd ions double-bridged by two tda{sup 3–} ligands through themore » neighboring nitrogen atoms is connected with the other four Cd{sub 2}(μ{sub 5}-tda){sub 2} units form the undulating 2D network in the ac plane. The (4,4) networks and undulating 2D networks are alternatively connected along the b axis by the tda{sup 3–} ligands coordinating to the Cd ions to form the 3D framework.« less

Two- and three-dimensional networks of gadolinium(III) with dicarboxylate ligands: synthesis, crystal structure, and magnetic properties.

PubMed

Cañadillas-Delgado, Laura; Pasan, Jorge; Fabelo, Oscar; Hernandez-Molina, María; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

2006-12-25

Four gadolinium(III) complexes with dicarboxylate ligands of formulas [Gd2(mal)3(H2O)5]n.2nH2O (1), [Gd2(mal)3(H2O)6]n (2), [NaGd(mal)(ox)(H2O)3]n (3), and [Gd2(ox)3(H2O)6]n.2.5nH2O (4) (mal = malonate; ox = oxalate) have been prepared, and their magnetic properties have been investigated as a function of the temperature. The structures of 1-3 have been determined by X-ray diffraction methods. The crystal structure of 4 was already known, and it is made of hexagonal layers of Gd atoms that are bridged by bis-bidentate oxalate. Compound 1 is isostructural with the europium(III) malonate complex [Eu2(mal)3(H2O)5]n.2nH2O,1 whose structure was reported elsewhere. The Gd atoms in 1 define a two-dimensional network where a terminal bidentate and bridging bidentate/bis-monodentate and tris-bidentate coordination modes of malonate occur. Compound 2 has a three-dimensional structure with a structural phase transition at 226 K, which involves a change of the space group from I2/a to Ia. Although its structure at room temperature was already known, that below 226 K was not. Pairs of Gd atoms with a double oxo-carboxylate bridge occur in both phases, and the main differences between both structures deal with the Gd environment and the H-bond pattern. 3 is also a three-dimensional compound, and it was obtained by reacting Gd(III) ions with malonic acid in a silica gel medium. Oxalic acid results as an oxidized product of the malonic acid, and single crystals of the heteroleptic complex were produced. The Gd atoms in 3 are connected through bis-bidentate oxalate and carboxylate-malonate bridges in the anti-anti and anti-syn coordination modes. Compounds 1 and 2 exhibit weak but significant ferromagnetic couplings between the Gd(III) ions through the single (1) and double (2) oxo-carboxylate bridges, whereas antiferromagnetic interactions across the bis-bidentate oxalate account for the overall antiferromagnetic behavior observed in 3 and 4.

Glutamic acid is an active site residue of angiotensin I-converting enzyme. Use of the Lossen rearrangement for identification of dicarboxylic acid residues.

PubMed

Harris, R B; Wilson, I B

1983-01-25

A set of chemical reactions was used to show that one glutamic acid residue at the active site of bovine lung angiotensin I-converting enzyme is esterified with the alkylating agent p-[N,N-bis(chloroethyl)amino] phenylbutyryl-L-Pro (chlorambucyl-L-Pro), an affinity label for this enzyme (Harris, R. B., and Wilson, I. B. (1982) J. Biol. Chem. 257, 811-815). The same procedure was used to confirm that a glutamic acid residue of carboxypeptidase A alpha is esterified by reaction with bromoacetyl-N-methyl-L-phenylalanine (Haas, G. M., and Neurath, H. (1971) Biochemistry 10, 3535-3546). In the procedure described in this paper, the esterified residue at the active site is converted to the hydroxamic acid by reaction with hydroxylamine and the hydroxamic acid is subject to the Lossen rearrangement. If a glutamic acid residue was esterified, 1 eq of 2,4-diaminobutyric acid will be formed. Aspartyl esters will give 2,3-diaminopropionic acid. The diamino acids can be quantitatively measured using the short column of an amino acid analyzer if the amount of lysine and histidine is largely decreased by modification with suitable side chain protecting groups. With carboxypeptidase A, the reactions were done on the whole undigested enzyme. With the converting enzyme, we first cleaved the esterified enzyme with cyanogen bromide. Twenty-nine cleavage peptides were separated on high performance liquid chromatography and one of these contained all of the bound radioactive inhibitor. This active site peptide was then subjected to the derivatization and Lossen procedures, and 1 eq of 2,4-diaminobutyric acid was obtained.

Seasonal characteristics of oxalic acid and related SOA in the free troposphere of Mt. Hua, central China: implications for sources and formation mechanisms.

PubMed

Meng, Jingjing; Wang, Gehui; Li, Jianjun; Cheng, Chunlei; Ren, Yanqin; Huang, Yao; Cheng, Yuting; Cao, Junji; Zhang, Ting

2014-09-15

PM10 aerosols from the summit of Mt. Hua (2060 m a.s.l) in central China during the winter and summer of 2009 were analyzed for dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls. Molecular composition of dicarboxylic acids (C2-C11) in the free tropospheric aerosols reveals that oxalic acid (C2, 399 ± 261 ng m(-3) in winter and 522 ± 261 ng m(-3) in summer) is the most abundant species in both seasons, followed by malonic (C3) and succinic (C4) acids, being consistent with that on ground levels. Most of the diacids are more abundant in summer than in winter, but adipic (C6) and phthalic (Ph) acids are twice lower in summer, suggesting more significant impact of anthropogenic pollution on the wintertime alpine atmosphere. Moreover, glyoxal (Gly) and methylglyoxal (mGly) are also lower in summer (12 ± 6.1 ng m(-3)) than in winter (22 ± 13 ng m(-3)). As both dicarbonyls are a major precursor of C2, their seasonal variation patterns, which are opposite to those of the diacids, indicate that the mountain troposphere is more oxidative in summer. C2 showed strong linear correlations with levoglucosan in winter and oxidation products of isoprene and monoterpene in summer. PCA analysis further suggested that the wintertime C2 and related SOA in the Mt. Hua troposphere mostly originate from photochemical oxidations of anthropogenic pollutants emitted from biofuel and coal combustion in lowland regions. On contrast, the summertime C2 and related SOA mostly originate from further oxidation of the mountainous isoprene and monoterpene oxidation products. The AIM model calculation results showed that oxalic acid concentration well correlated with particle acidity (R(2)=0.60) but not correlated with particle liquid water content, indicating that particle acidity favors the organic acid formation because aqueous-phase C2 production is the primary mechanism of C2 formation in ambient aerosols and is driven by acid-catalyzed oxidation. Copyright © 2014 Elsevier B.V. All

The Organic Content of the Tagish Lake Meteorite

NASA Technical Reports Server (NTRS)

Pizzarello, Sandra; Huang, Yongsong; Becker, Luann; Poreda, Robert J.; Nieman, Ronald A.; Cooper, George; Williams, Michael

2001-01-01

The Tagish Lake meteorite felt last year on a frozen take in Canada and may provide the most pristine material of its kind. Analyses have now shown this carbonaceous chondrite to contain a suite of soluble organic compounds (approximately 100 parts per million) that includes mono- and dicarboxylic acids, dicarboximides, pyridine carboxylic acids, a sulfonic acid, and both aliphatic and aromatic hydrocarbons. The insoluble carbon exhibits exclusive aromatic character, deuterium enrichment, and fullerenes containing 'planetary' helium and argon. The findings provide insight into an outcome of early solar chemical evolution that differs from any seen so far in meteorites.

Assembly and property research on seven 0D–3D complexes derived from imidazole dicarboxylate and 1,2-bi(pyridin-4-yl)ethene

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

Mu, Bao; Li, Qian; Lv, Lei

2015-03-15

The hydrothermal reaction of transition metals, 1H-imidazole-4,5-dicarboxylic acid (H{sub 3}ImDC) and 1,2-bi(pyridin-4-yl)ethene (bpe) affords a series of new complexes, namely, [Mn(HImDC)(bpe)(H{sub 2}O)] (1), [M(H{sub 2}ImDC){sub 2}(H{sub 2}O){sub 2}]·(bpe) (M=Fe(2), Co(3), Zn(4), Cd(6)), [Zn{sub 3}(ImDC){sub 2}(bpe)(H{sub 2}O)]·3H{sub 2}O (5) and [Cd(H{sub 2}ImDC)(bpe)] (7), which are characterized by elemental analyses, IR, TG, XRPD and single crystal X-ray diffraction. Complex 1 exhibits a one dimensional (1D) zigzag chain with two types of irregular rings, and the 1D chains are linked to form a three dimensional (3D) supramolecular framework by the hydrogen bonding interactions (O–H∙∙∙O and O–H∙∙∙N). Complexes 2–4 and 6 are isomorphous, andmore » they display the mononuclear structures. In these complexes, the O–H∙∙∙O and O–H∙∙∙N hydrogen bonds play an important role in sustaining the whole 3D supramolecular frameworks. Complex 5 shows a (3,3)-connected 3D framework with (10{sup 3}) topology, and the lattice water molecules as guest molecules exist in the 3D framework. Complex 7 is a wave-like two dimensional (2D) structure, in which the adjacent 1D chains point at the opposite directions. Moreover, the fluorescent properties of complexes 1–7 and the magnetic property of 1 have been investigated. The water vapor adsorption for complex 5 has been researched at 298 K. - Graphical abstract: Seven new complexes based on different structural characteristics have been hydrothermally synthesized by the mixed ligands. The fluorescent properties, the magnetic property and the water vapor adsorption have been investigated. - Highlights: • The semi-rigid ligand with C=C bonds and imidazole dicarboxylates with some advantages have been used. • A series of new complexes with different structural characteristics have been discussed in detail. • The fluorescent properties, the magnetic property and the water vapor adsorption

Anti-Atherosclerotic Actions of Azelaic acid, an End Product of Linoleic Acid Peroxidation, in Mice

PubMed Central

Litvinov, Dmitry; Selvarajan, Krithika; Garelnabi, Mahdi; Brophy, Larissa; Parthasarathy, Sampath

2009-01-01

Background Atherosclerosis is a chronic inflammatory disease associated with the accumulation of oxidized lipids in arterial lesions. Recently we studied the degradation of peroxidized linoleic acid and suggested that oxidation is an essential process that results in the generation of terminal products, namely mono- and dicarboxylic acids that may lack the pro-atherogenic effects of peroxidized lipids. In continuation of that study, we tested the effects of azelaic acid (AzA), one of the end products of linoleic acid peroxidation, on the development of atherosclerosis using low density lipoprotein receptor knockout (LDLr−/−) mice. Methods and results LDLr−/− mice were fed with a high fat and high cholesterol Western diet (WD group). Another group of animals were fed the same diet with AzA supplementation (WD+AzA group). After four months of feeding, mice were sacrificed and atherosclerotic lesions were measured. The results showed that the average lesion area in WD+AzA group was 38% (p<0.001) less as compared to WD group. The athero-protective effect of AzA was not related to changes in plasma lipid content. AzA supplementation decreased the level of CD68 macrophage marker by 34% (p<0.05). Conclusions The finding that AzA exhibits an anti-atherogenic effect suggests that oxidation of lipid peroxidation-derived aldehydes into carboxylic acids could be an important step in the body’s defense against oxidative damage. PMID:19880116

Anti-atherosclerotic actions of azelaic acid, an end product of linoleic acid peroxidation, in mice.

PubMed

Litvinov, Dmitry; Selvarajan, Krithika; Garelnabi, Mahdi; Brophy, Larissa; Parthasarathy, Sampath

2010-04-01

Atherosclerosis is a chronic inflammatory disease associated with the accumulation of oxidized lipids in arterial lesions. Recently we studied the degradation of peroxidized linoleic acid and suggested that oxidation is an essential process that results in the generation of terminal products, namely mono- and dicarboxylic acids that may lack the pro-atherogenic effects of peroxidized lipids. In continuation of that study, we tested the effects of azelaic acid (AzA), one of the end products of linoleic acid peroxidation, on the development of atherosclerosis using low density lipoprotein receptor knockout (LDLr(-/-)) mice. LDLr(-/-) mice were fed with a high fat and high cholesterol Western diet (WD group). Another group of animals were fed the same diet with AzA supplementation (WD+AzA group). After 4 months of feeding, mice were sacrificed and atherosclerotic lesions were measured. The results showed that the average lesion area in WD+AzA group was 38% (p<0.001) less as compared to WD group. The athero-protective effect of AzA was not related to changes in plasma lipid content. AzA supplementation decreased the level of CD68 macrophage marker by 34% (p<0.05). The finding that AzA exhibits an anti-atherogenic effect suggests that oxidation of lipid peroxidation-derived aldehydes into carboxylic acids could be an important step in the body's defense against oxidative damage. Copyright 2009 Elsevier Ireland Ltd. All rights reserved.

Anti-epileptic activity of group II metabotropic glutamate receptor agonists (--)-2-oxa-4-aminobicyclo[3.1.0]hexane-4,6-dicarboxylate (LY379268) and (--)-2-thia-4-aminobicyclo[3.1.0]hexane-4,6-dicarboxylate (LY389795).

PubMed

Moldrich, R X; Jeffrey, M; Talebi, A; Beart, P M; Chapman, A G; Meldrum, B S

2001-07-01

The selective group II metabotropic glutamate receptor (mGlu(2/3)) agonists (-)-2-oxa-4-aminobicyclo[3.1.0]hexane-4,6-dicarboxylate (LY379268) and (-)-2-thia-4-aminobicyclo[3.1.0]hexane-4,6-dicarboxylate (LY389795) have been evaluated as anti-epileptic drugs in dilute brown agouti (DBA/2) mice, lethargic (lh/lh) mice, genetically epilepsy-prone-9 (GEP) rats and amygdala-kindled rats. Sound-induced clonic seizures in DBA/2 mice were transiently inhibited by both agonists intracerebroventricularly (i.c.v.), LY379268 ED(50)=0.08 [0.02-0.33]nmol and LY389795 ED(50)=0.82 [0.27-3.24]nmol or intraperitoneally (i.p.), LY379268 ED(50)=2.9 [0.9-9.6]mg/kg and LY389795 ED(50)=3.4 [1.0-11.7]mg/kg. Both mGlu(2/3) agonists inhibited seizures induced by the group I mGlu receptor agonist (R,S)-3,5-dihydroxyphenylglycine (DHPG), where LY379268, i.c.v. ED(50)=0.3 [0.02-5.0]pmol and LY389795, i.c.v. ED(50)=0.03 [0.05-0.19]nmol. The spike and wave discharge (SWD) duration of absence seizures in lh/lh mice was significantly reduced by both agonists at 1 and 10nmol (i.c.v.) up to 90min following infusion. The electrically induced seizure score and afterdischarge duration of amygdala-kindled rats was partially inhibited by the agonists 30min after i.p. injection of 10mg/kg. The agonists did not inhibit sound-induced seizures in GEP rats (0.1-1mg/kg, 30min 1h, i.p.), but were proconvulsant following sound stimulus (> or =0.1mg/kg). These findings identify a potential role for mGlu(2/3) agonists in the amelioration of generalised and partial epileptic seizures.

Field observation on secondary organic aerosols during Asian dust storm periods: Formation mechanism of oxalic acid and related compounds on dust surface

NASA Astrophysics Data System (ADS)

Wang, Gehui; Cheng, Chunlei; Meng, Jingjing; Huang, Yao; Li, Jianjun; Ren, Yanqin

2015-07-01

Chemical evolution of East Asian dust during transpacific transport has been given much attention for inorganic species such as sulfate, nitrate and ammonium. However, the role of organic species during the transport has almost entirely been ignored. To understand the formation mechanism of secondary organic aerosols (SOA) on dust surfaces, this study investigated the concentrations and compositions of dicarboxylic acids, keto-carboxylic acids, α-dicarbonyls and inorganic ions in size-segregated aerosols (9-stages) collected in Xi'an, central China during the two dust storm episodes in the springs of 2009 and 2011 and compared with those in nondust storm periods. During the events the ambient particulate dicarboxylic acids were 932-2240 ng m-3, which are comparable and even higher than those in nondust periods. Molecular compositions of the above SOA are similar to those in nondust periods with oxalic acid being the leading species. In the presence of the dust storms, all the above mentioned SOA species in Xi'an were predominantly enriched on the coarse particles (>2.1 μm), and oxalic acid well correlated with NO3- (R2 = 0.72, p < 0.001) rather than SO42-. This phenomenon differs greatly from the SOA in any other nondust period that is usually characterized by an enrichment of oxalic acid in fine mode and a strong correlation of oxalic acid with SO42-. We propose a formation pathway to explain these observations, in which nitric acid and/or nitrogen oxides react with dust to produce Ca(NO3)2 and form a liquid phase on the surface of dust aerosols via water vapor-absorption of Ca(NO3)2, followed by a partitioning of the gas-phase water-soluble organic precursors (e.g.,glyoxal and methylglyoxal) into the aqueous-phase and a subsequent oxidation into oxalic acid. To the best of our knowledge, we found for the first time the enrichment of glyoxal and methylglyoxal on dust surface. Our data suggest an important role of nitrate in the heterogeneous formation process of

Degradation of malathion by salt-marsh microorganisms.

PubMed Central

Bourquin, A W

1977-01-01

Numerous bacteria from a salt-marsh environment are capable of degrading malathion, an organophosphate insecticide, when supplied with additional nutrients as energy and carbon sources. Seven isolates exhibited ability (48 to 90%) to degrade malathion as a sole carbon source. Gas and thin-layer chromatography and infrared spectroscopy confirmed malathion to be degraded via malathion-monocarboxylic acid to the dicarboxylic acid and then to various phosphothionates. These techniques also identified desmethyl-malathion, phosphorthionates, and four-carbon dicarboxylic acids as degradation products formed as a result of phosphatase activity. PMID:192147

Catabolism of α-Ketoglutarate by a sucA Mutant of Bradyrhizobium japonicum: Evidence for an Alternative Tricarboxylic Acid Cycle

PubMed Central

Green, Laura S.; Li, Youzhong; Emerich, David W.; Bergersen, Fraser J.; Day, David A.

2000-01-01

A complete tricarboxylic acid (TCA) cycle is generally considered necessary for energy production from the dicarboxylic acid substrates malate, succinate, and fumarate. However, a Bradyrhizobium japonicum sucA mutant that is missing α-ketoglutarate dehydrogenase is able to grow on malate as its sole source of carbon. This mutant also fixes nitrogen in symbiosis with soybean, where dicarboxylic acids are its principal carbon substrate. Using a flow chamber system to make direct measurements of oxygen consumption and ammonium excretion, we confirmed that bacteroids formed by the sucA mutant displayed wild-type rates of respiration and nitrogen fixation. Despite the absence of α-ketoglutarate dehydrogenase activity, whole cells of the mutant were able to decarboxylate α-[U-14C]ketoglutarate and [U-14C]glutamate at rates similar to those of wild-type B. japonicum, indicating that there was an alternative route for α-ketoglutarate catabolism. Because cell extracts from B. japonicum decarboxylated [U-14C]glutamate very slowly, the γ-aminobutyrate shunt is unlikely to be the pathway responsible for α-ketoglutarate catabolism in the mutant. In contrast, cell extracts from both the wild type and mutant showed a coenzyme A (CoA)-independent α-ketoglutarate decarboxylation activity. This activity was independent of pyridine nucleotides and was stimulated by thiamine PPi. Thin-layer chromatography showed that the product of α-ketoglutarate decarboxylation was succinic semialdehyde. The CoA-independent α-ketoglutarate decarboxylase, along with succinate semialdehyde dehydrogenase, may form an alternative pathway for α-ketoglutarate catabolism, and this pathway may enhance TCA cycle function during symbiotic nitrogen fixation. PMID:10781553

Geochemical roots of autotrophic carbon fixation: hydrothermal experiments in the system citric acid, H 2O-(±FeS)-(±NiS)

NASA Astrophysics Data System (ADS)

Cody, G. D.; Boctor, N. Z.; Hazen, R. M.; Brandes, J. A.; Morowitz, Harold J.; Yoder, H. S.

2001-10-01

Recent theories have proposed that life arose from primitive hydrothermal environments employing chemical reactions analogous to the reductive citrate cycle (RCC) as the primary pathway for carbon fixation. This chemistry is presumed to have developed as a natural consequence of the intrinsic geochemistry of the young, prebiotic, Earth. There has been no experimental evidence, however, demonstrating that there exists a natural pathway into such a cycle. Toward this end, the results of hydrothermal experiments involving citric acid are used as a method of deducing such a pathway. Homocatalytic reactions observed in the citric acid-H2O experiments encompass many of the reactions found in modern metabolic systems, i.e., hydration-dehydration, retro-Aldol, decarboxylation, hydrogenation, and isomerization reactions. Three principal decomposition pathways operate to degrade citric acid under thermal and aquathermal conditions. It is concluded that the acid catalyzed βγ decarboxylation pathway, leading ultimately to propene and CO2, may provide the most promise for reaction network reversal under natural hydrothermal conditions. Increased pressure is shown to accelerate the principal decarboxylation reactions under strictly hydrothermal conditions. The effect of forcing the pH via the addition of NaOH reveals that the βγ decarboxylation pathway operates even up to intermediate pH levels. The potential for network reversal (the conversion of propene and CO2 up to a tricarboxylic acid) is demonstrated via the Koch (hydrocarboxylation) reaction promoted heterocatalytically with NiS in the presence of a source of CO. Specifically, an olefin (1-nonene) is converted to a monocarboxylic acid; methacrylic acid is converted to the dicarboxylic acid, methylsuccinic acid; and the dicarboxylic acid, itaconic acid, is converted into the tricarboxylic acid, hydroaconitic acid. A number of interesting sulfur-containing products are also formed that may provide for additional

Gas chromatography/trace analysis of derivatized azelaic acid as a stability marker.

PubMed

Alzweiri, Muhammed; Tarawneh, Ruba; Khanfar, Mohammad A

2013-10-01

Azelaic acid, a naturally occurring saturated dicarboxylic acid, is found in many topical formulations for its various medical benefits or as a byproduct of the oxidative decomposition of unsaturated fatty acids. The poor volatility of azelaic acid hinders its applicability in GC analysis. Therefore, azelaic acid was derivatized by methylation and silylation procedures to enhance its volatility for GC analysis. Accordingly, dimethyl azelate (DMA) and di(trimethylsilyl) azelate were synthesized and characterized by GC-MS. Subsequently, a GC with flame ionization detection method was developed and validated to analyze trace amounts of azelaic acid in some marketed skin creams. Unlike DMA, di(trimethylsilyl) azelate was chemically unstable and degraded within few hours. Nonane was used as a stable internal standard. Variability due to derivatization and extraction was controlled by a standard addition procedure. DMA analysis was linear in a wide concentration range (100 ng/mL to 100 mg/mL). Moreover, the method was accurate (96.4-103.4%) and precise with inter- and intraday variability <2.0% and LOQ and LOD of 100 and 10 ng/mL, respectively. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Seizures induced in immature rats by homocysteic acid and the associated brain damage are prevented by group II metabotropic glutamate receptor agonist (2R,4R)-4-aminopyrrolidine-2,4-dicarboxylate.

PubMed

Folbergrová, Jaroslava; Druga, Rastislav; Otáhal, Jakub; Haugvicová, Renata; Mares, Pavel; Kubová, Hana

2005-04-01

The present study has examined the anticonvulsant and neuroprotective effect of group II metabotropic glutamate receptor (mGluR) agonist (2R,4R)-4-aminopyrrolidine-2,4-dicarboxylate (2R,4R-APDC) in the model of seizures induced in immature 12-day-old rats by bilateral intracerebroventricular infusion of dl-homocysteic acid (DL-HCA, 600 nmol/side). For biochemical analyses, rat pups were sacrificed during generalized clonic-tonic seizures, approximately 45-50 min after infusion. Comparable time intervals were used for sacrificing the pups which had received 2R,4R-APDC. Low doses of 2R,4R-APDC (0.05 nmol/side) provided a pronounced anticonvulsant effect which was abolished by pretreatment with a selective group II mGluR antagonist LY341495. Generalized clonic-tonic seizures were completely suppressed and cortical energy metabolite changes which normally accompany these seizures were either normalized (decrease of glucose and glycogen) or markedly reduced (an accumulation of lactate). EEG recordings support the marked anticonvulsant effect of 2R,4R-APDC, nevertheless, this was only partial. In spite of the absence of obvious motor phenomena, isolated spikes or even short periods of partial ictal activity could be observed. Isolated spikes could also be seen in some animals after application of 2R,4R-APDC alone, reflecting most likely subclinical proconvulsant activity of this agonist. The neuroprotective effect of 2R,4R-APDC was evaluated after 24 h and 6 days of survival following DL-HCA-induced seizures. Massive neuronal degeneration, as revealed by Fluoro-Jade B staining, was observed in a number of brain regions following infusion of DL-HCA alone (seizure group), whereas 2R,4R-APDC pretreatment provided substantial neuroprotection. The present findings support the possibility that group II mGluRs are a promising target for a novel approach to treating epilepsy.

Effect of Oral Sebacic Acid on Postprandial Glycemia, Insulinemia, and Glucose Rate of Appearance in Type 2 Diabetes

PubMed Central

Iaconelli, Amerigo; Gastaldelli, Amalia; Chiellini, Chiara; Gniuli, Donatella; Favuzzi, Angela; Binnert, Christophe; Macé, Katherine; Mingrone, Geltrude

2010-01-01

OBJECTIVE Dicarboxylic acids are natural products with the potential of being an alternate dietary source of energy. We aimed to evaluate the effect of sebacic acid (a 10-carbon dicarboxylic acid; C10) ingestion on postprandial glycemia and glucose rate of appearance (Ra) in healthy and type 2 diabetic subjects. Furthermore, the effect of C10 on insulin-mediated glucose uptake and on GLUT4 expression was assessed in L6 muscle cells in vitro. RESEARCH DESIGN AND METHODS Subjects ingested a mixed meal (50% carbohydrates, 15% proteins, and 35% lipids) containing 0 g (control) or 10 g C10 in addition to the meal or 23 g C10 as a substitute of fats. RESULTS In type 2 diabetic subjects, the incremental glucose area under the curve (AUC) decreased by 42% (P < 0.05) and 70% (P < 0.05) in the 10 g C10 and 23 g C10 groups, respectively. At the largest amounts used, C10 reduced the glucose AUC in healthy volunteers also. When fats were substituted with 23 g C10, AUC of Ra was significantly reduced on the order of 18% (P < 0.05) in both healthy and diabetic subjects. The insulin-dependent glucose uptake by L6 cells was increased in the presence of C10 (38.7 ± 10.3 vs. 11.4 ± 5.4%; P = 0.026). This increase was associated with a 1.7-fold raise of GLUT4. CONCLUSIONS Sebacic acid significantly reduced hyperglycemia after a meal in type 2 diabetic subjects. This beneficial effect was associated with a reduction in glucose Ra, probably due to lowered hepatic glucose output and increased peripheral glucose disposal. PMID:20724647

Size distributions of low molecular weight dicarboxylic acids, ketocarboxylic acids, glyoxal and methylglyoxal in the marine aerosols from Okinawa Island, Japan

NASA Astrophysics Data System (ADS)

Kawamura, K.; Lazaar, M.

2008-12-01

Size-segregated marine aerosol samples (5 sets) were collected in 2008 spring at Cape Hedo Station of National Institute of Environmental Studies, Okinawa (128.25° E, 26.87° N), an outflow region of Chinese aerosols and their precursors, using an Andersen middle volume impactor at a flow rate of 100 lpm and pre-combusted quartz fiber filters. The samples were analyzed for low molecular weight diacids and related compounds, using a capillary gas chromatography and GC/MS after BF3/n-butanol derivatization. Particle size cuts (8 stages + BUF) are 0.43, 0.65, 1.1, 2.1, 3.3, 4.7, 7 and 11.3 µm in diameter. Homologous series of aliphatic (C2-C12) and aromatic (phthalic, iso- and tere-phthalic) diacids were detected as well as w-oxoacids (C2-C9), glyoxal and methylglyoxal. Oxalic acid (C2) was found as the dominant diacid in all the size ranges, followed by malonic (C3) and succinic (C4) acids. Glyoxylic (wC2) acid was the most abundant ketoacid followed by wC4 acid. Most of the organic species maximized in fine mode of 0.65-1.1 or 1.1-2.1µm. Oxalic acid (C2, 4.4-70.6 ngm-3, av. 23.9 ngm-3) comprised 54-80% (av. 67%) of total diacid concentrations. The small diacids showed concentration peaks on fine mode, suggesting that they are produced by photochemical oxidation of volatile organic precursors during long-range atmospheric transport from Asian Continent. They may also be produced by heterogeneous reactions in the atmospheric particles (dusts and cloud droplets).

Comparison of the relative stability of pharmaceutical cocrystals consisting of paracetamol and dicarboxylic acids.

PubMed

Suzuki, Naoto; Kawahata, Masatoshi; Yamaguchi, Kentaro; Suzuki, Toyofumi; Tomono, Kazuo; Fukami, Toshiro

2018-04-01

The aim of this study is to evaluate the relative stability of pharmaceutical cocrystals consisting of paracetamol (APAP) and oxalic acid (OXA) or maleic acid (MLA). These observations of cocrystal stability under various conditions are useful coformer criteria when cocrystals are selected as the active pharmaceutical ingredient in drug development. The relative stability was determined from the preferentially formed cocrystals under various conditions. Cocrystal of APAP-OXA was more stable than that of APAP-MLA in a ternary cogrinding system and possessed thermodynamical stability. On the other hand, when grinding with moisture or maintaining at high temperatures and relative humidity conditions, APAP-MLA was more stable, and OXA converted to OXA dihydrate. In the slurry method, APAP-OXA was more stable in aprotic solvents because the APAP-OXA with low-solubility product precipitated. The relative stability order was affected by preparing conditions of presence of moisture. This order might attribute to the small difference of crystal structure in the extension of the hydrogen bond network.

Wind tunnel investigations on the retention of carboxylic acids during riming

NASA Astrophysics Data System (ADS)

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

2015-04-01

In mid-latitudes, precipitation is mainly initiated via the ice phase in mixed phase clouds. In such clouds the ice particles grow to precipitation sizes at the expense of liquid drops through riming which means that supercooled droplets collide with ice particles and subsequently freeze. Water-soluble trace substances present in the liquid phase might remain only fractionally in the ice phase after freezing. This fractionation is called retention and is an important ratio which quantifies the partitioning of atmospheric trace substances between the phases. Laboratory experiments were carried out at the Mainz vertical wind tunnel to determine the retention of lower mono- and di-carboxylic acids during riming. Due to their low molecular weight and their polarity these acids are water-soluble. In the atmosphere formic acid and acetic acid are the most abundant mono-carboxylic acids in the gas and aqueous phase, thus, they represent the major fraction of carboxylic acids in cloud water. Oxalic and malonic acid are common coatings on aerosol particles because of their relatively low saturation vapor pressure. These di-carboxylic acids might therefore promote the aerosol particles to act as cloud condensation nuclei and additionally contribute to the aqueous phase chemistry in cloud droplets. The conditions during the riming experiments in the wind tunnel were similar to those in atmospheric mixed phase clouds, i.e. temperatures from -18°C to -6 °C, liquid water contents between 0.5 and 1.5 g/m3, and liquid drop radii between 10 and 20 μm. The liquid phase concentrations ranged from 3 to 5 mg/l (4.1 < pH < 4.5). As rime collectors captively floating ice particles and quasi-floating snowflakes with diameters between 0.6 and 1.5 cm were used. The wind speed in the vertical wind tunnel was very close to the terminal velocities of the rime collectors, thus, the ventilation during riming was in the same order of magnitude as under atmospheric riming conditions. After

Capillary electrophoretic study of dibasic acids of different structures: Relation to separation of oxidative intermediates in remediation

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

Yu, Z.; Cocke, D.L.

Dicarboxylic acids are important in environmental chemistry because they are intermediates in oxidative processes involved in natural remediation and waste management processes such as oxidative detoxification and advanced oxidation. Capillary electrophoresis (CE), a promising technique for separating and analyzing these intermediates, has been used to examine a series of dibasic acids of different structures and conformations. This series includes malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, phthalic acid, and trans, trans-muconic acid. The CE parameters as well as structural variations (molecular structure and molecular isomers, buffer composition, pH, applied voltage, injection mode, current,more » temperature, and detection wavelength) that affect the separations and analytical results have been examined in this study. Those factors that affect the separation have been delineated. Among these parameters, the pH has been found to be the most important, which affects the double-layer of the capillary wall, the electro-osmotic flow and analyte mobility. The optimum pH for separating these dibasic acids, as well as the other parameters are discussed in detail and related to the development of methods for analyzing oxidation intermediates in oxidative waste management procedures.« less

Metal cleaner poisoning

MedlinePlus

Metal cleaners contain organic compounds called hydrocarbons, including: 1,2-butylene oxide Boric acid Cocoyl sarcosine Dicarboxylic fatty acid Dimethoxymethane Dodecanedioic acid N-propyl bromide Sodium hydroxide T-butanol

Volatility of organic aerosol: evaporation of ammonium sulfate/succinic acid aqueous solution droplets.

PubMed

Yli-Juuti, Taina; Zardini, Alessandro A; Eriksson, Axel C; Hansen, Anne Maria K; Pagels, Joakim H; Swietlicki, Erik; Svenningsson, Birgitta; Glasius, Marianne; Worsnop, Douglas R; Riipinen, Ilona; Bilde, Merete

2013-01-01

Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol.

Volatility of Organic Aerosol: Evaporation of Ammonium Sulfate/Succinic Acid Aqueous Solution Droplets

PubMed Central

2013-01-01

Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol. PMID:24107221

Succinic acid functionalized silver nanoparticles (Suc-Ag NPs) for colorimetric sensing of melamine

NASA Astrophysics Data System (ADS)

Rajar, Kausar; Sirajuddin; Balouch, Aamna; Bhanger, M. I.; Shah, Muhammad Tariq; Shaikh, Tayyaba; Siddiqui, Samia

2018-03-01

In this study, a quantitative colorimetric sensing strategy is developed for the rapid, sensitive and selective determination of melamine. The sensing system relies on the application of succinic acid as a selective recognition probe functionalized over Ag NPs. The synthesized Ag NPs were modified with cysteamine to induce positively charged atmosphere which allowed easy and favorable functionalization of succinic acid. The di-carboxyl nature of succinic acid enabled its binding to both cysteamine and melamine. The strong and favorable linkage between succinic acids carbonyl and amine moieties of melamine triggered aggregation of silver NPs producing a significant shift in the measured absorption excitation. This change in the excitation along with the colorimetric response was found linearly proportional to the melamine concentration in the range of 0.1-1.2 μM. The developed sensor system is simple and unlike electrostatic attraction based sensor system utilize selective linkage for the recognition of melamine. In addition to this, the developed optical probe can efficiently be used for the determination of melamine in milk samples.

Anthracycline antibiotics derivate mitoxantrone-Destructive sorption and photocatalytic degradation.

PubMed

Štenglová-Netíková, Irena R; Petruželka, Luboš; Šťastný, Martin; Štengl, Václav

2018-01-01

Nanostructured titanium(IV) oxide was used for the destructive adsorption and photocatalytic degradation of mitoxantrone (MTX), a cytostatic drug from the group of anthracycline antibiotics. During adsorption on a titania dioxide surface, four degradation products of MTX, mitoxantrone dicarboxylic acid, 1,4-dihydroxy-5-((2-((2-hydroxyethyl)amino)ethyl)amino)-8-((2-(methylamino)ethyl)amino)anthracene-9,10-dione, 1,4-dihydroxy-5,8-diiminoanthracene-9,10(5H,8H)-dione and 1,4-dihydroxy-5-imino-8-(methyleneamino)anthracene-9,10(5H,8H)-dione, were identified. In the case of photocatalytic degradation, only one degradation product after 15 min at m/z 472 was identified. This degradation product corresponded to mitoxantrone dicarboxylic acid, and complete mineralization was attained in one hour. Destructive adsorbent manganese(IV) oxide, MnO2, was used only for the destructive adsorption of MTX. Destructive adsorption occurred only for one degradation product, mitoxantrone dicarboxylic acid, against anatase TiO2.

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

PubMed

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

2009-10-01

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 investigated. Good agreement has been obtained between the value calculated by Langmuir-Freundlich-Hinshelwood (L-F-H) model and experimental data, with coefficient of multiple determination (R2) varying from 0.880 to 0.999. The L-F-H model has been proven to be feasible in describing the kinetic characteristic of the photocatalytic degradation of aliphatic carboxylic acids. Moreover, the apparent reaction rate constant (k) of the photocatalytic degradation of dicarboxylic acids is higher than that of monocarboxylic acids with the same carbon atoms. This shows that the photocatalytic degradation rate is favoured by different chemical structure.

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Three cocrystals and a cocrystal salt of pyrimidin-2-amine and glutaric acid.

PubMed

Odiase, Isaac; Nicholson, Catherine E; Ahmad, Ruksanna; Cooper, Jerry; Yufit, Dmitry S; Cooper, Sharon J

2015-04-01

Four new cocrystals of pyrimidin-2-amine and propane-1,3-dicarboxylic (glutaric) acid were crystallized from three different solvents (acetonitrile, methanol and a 50:50 wt% mixture of methanol and chloroform) and their crystal structures determined. Two of the cocrystals, namely pyrimidin-2-amine-glutaric acid (1/1), C4H5N3·C6H8O4, (I) and (II), are polymorphs. The glutaric acid molecule in (I) has a linear conformation, whereas it is twisted in (II). The pyrimidin-2-amine-glutaric acid (2/1) cocrystal, 2C4H5N3·C6H8O4, (III), contains glutaric acid in its linear form. Cocrystal-salt bis(2-aminopyrimidinium) glutarate-glutaric acid (1/2), 2C4H6N3(+)·C6H6O4(2-)·2C6H8O4, (IV), was crystallized from the same solvent as cocrystal (II), supporting the idea of a cocrystal-salt continuum when both the neutral and ionic forms are present in appreciable concentrations in solution. The diversity of the packing motifs in (I)-(IV) is mainly caused by the conformational flexibility of glutaric acid, while the hydrogen-bond patterns show certain similarities in all four structures.

A Comparison of the Essential Amino Acid Content and the Retention Rate by Chicken Part according to Different Cooking Methods.

PubMed

Kim, Honggyun; Do, Hyun Wook; Chung, Heajung

2017-01-01

This study set out to identify the changes in the nutrient contents during the chicken cooking process as basic data for the establishment of a national health nutrition policy. Samples were produced using 3 chicken parts (wing, breast, and leg) and 7 cooking methods (boiling, pancooking, pan-frying, deep-frying, steaming, roasting, and microwaving), and the essential amino acid contents, principal components, and retention rates were analyzed. Weight loss was observed in all chicken parts with all cooking methods. The protein and essential amino acid contents of the chicken samples differed significantly according to the part and the cooking method ( p <0.01). The protein and essential amino acid contents (g/100 g) of raw and cooked chicken parts showed ranges of 16.81-32.36 and 0.44-2.45, respectively. The principal component analysis (PCA) clearly demonstrated that the cooking methods and chicken parts produced similar trends for the essential amino acid contents. The retention rates of the chicken parts varied with the cooking methods, yielding a minimum value of 83% for isoleucine in a roasted wing, 91% for protein in a steamed breast, and 77% for isoleucine and lysine in a roasted leg. Therefore, the protein and amino acid contents of the roasted breast were higher than those of the other cooked chicken parts.

A Comparison of the Essential Amino Acid Content and the Retention Rate by Chicken Part according to Different Cooking Methods

PubMed Central

Kim, Honggyun

2017-01-01

This study set out to identify the changes in the nutrient contents during the chicken cooking process as basic data for the establishment of a national health nutrition policy. Samples were produced using 3 chicken parts (wing, breast, and leg) and 7 cooking methods (boiling, pancooking, pan-frying, deep-frying, steaming, roasting, and microwaving), and the essential amino acid contents, principal components, and retention rates were analyzed. Weight loss was observed in all chicken parts with all cooking methods. The protein and essential amino acid contents of the chicken samples differed significantly according to the part and the cooking method (p<0.01). The protein and essential amino acid contents (g/100 g) of raw and cooked chicken parts showed ranges of 16.81-32.36 and 0.44-2.45, respectively. The principal component analysis (PCA) clearly demonstrated that the cooking methods and chicken parts produced similar trends for the essential amino acid contents. The retention rates of the chicken parts varied with the cooking methods, yielding a minimum value of 83% for isoleucine in a roasted wing, 91% for protein in a steamed breast, and 77% for isoleucine and lysine in a roasted leg. Therefore, the protein and amino acid contents of the roasted breast were higher than those of the other cooked chicken parts. PMID:29147085

Azelaic acid 15% gel: in the treatment of papulopustular rosacea.

PubMed

Frampton, James E; Wagstaff, Antona J

2004-01-01

Azelaic acid is a naturally occurring, straight-chain dicarboxylic acid which is effective in the treatment of rosacea, presumably on account of its anti-inflammatory properties. In randomized, double-blind, multicenter studies involving patients with moderate papulopustular facial rosacea, twice-daily topical application of azelaic acid 15% gel to the face was significantly more effective than twice-daily administration of either its vehicle (two studies) or metronidazole 0.75% gel (one study) in reducing inflammatory lesion counts and erythema severity. However, neither active treatment had a clinically discernable effect on telangiectasia. In all three studies, azelaic acid 15% gel recipients experienced continuous decreases in lesion counts and erythema throughout the 12- to 15-week treatment periods. However, the effects of metronidazole 0.75% gel plateauxed after 8 weeks. In other efficacy assessments in these studies, azelaic acid 15% gel was superior to its vehicle and metronidazole 0.75% gel in both the investigators' global assessment of rosacea and the investigators' end-of-study evaluation of overall improvement, and superior to its vehicle in the patients' end-of-study evaluation of overall improvement. The most frequent treatment-related cutaneous adverse events during administration of azelaic acid 15% gel include burning/stinging/tingling and pruritus (itching); however, these events are predominantly transient in nature and mild-to-moderate in intensity.

Amino acid neurotransmitters and new approaches to anticonvulsant drug action.

PubMed

Meldrum, B

1984-01-01

Amino acids provide the most universal and important inhibitory (gamma-aminobutyric acid (GABA), glycine) and excitatory (glutamate, aspartate, cysteic acid, cysteine sulphinic acid) neurotransmitters in the brain. An anticonvulsant action may be produced (1) by enhancing inhibitory (GABAergic) processes, and (2) by diminishing excitatory transmission. Possible pharmacological mechanisms for enhancing GABA-mediated inhibition include (1) GABA agonist action, (2) GABA prodrugs, (3) drugs facilitating GABA release from terminals, (4) inhibition of GABA-transaminase, (5) allosteric enhancement of the efficacy of GABA at the receptor complex, (6) direction action on the chloride ionophore, and (7) inhibition of GABA reuptake. Examples of these approaches include the use of irreversible GABA-transaminase inhibitors, such as gamma-vinyl GABA, and the development of anticonvulsant beta-carbolines that interact with the "benzodiazepine receptor." Pharmacological mechanisms for diminishing excitatory transmission include (1) enzyme inhibitors that decrease the maximal rate of synthesis of glutamate or aspartate, (2) drugs that decrease the synaptic release of glutamate or aspartate, and (3) drugs that block the post-synaptic action of excitatory amino acids. Compounds that selectively antagonise excitation due to dicarboxylic amino acids have recently been developed. Those that selectively block excitation produced by N-methyl-D-aspartate (and aspartate) have proved to be potent anticonvulsants in many animal models of epilepsy. This provides a novel approach to the design of anticonvulsant drugs.

40 CFR Appendix A to Part 434 - Alternate Storm Limitations for Acid or Ferruginous Mine Drainage

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Alternate Storm Limitations for Acid or Ferruginous Mine Drainage A Appendix A to Part 434 Protection of Environment ENVIRONMENTAL... Storm Limitations for Acid or Ferruginous Mine Drainage EC01MY92.113 ...

40 CFR Appendix A to Part 434 - Alternate Storm Limitations for Acid or Ferruginous Mine Drainage

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Alternate Storm Limitations for Acid or Ferruginous Mine Drainage A Appendix A to Part 434 Protection of Environment ENVIRONMENTAL... Storm Limitations for Acid or Ferruginous Mine Drainage EC01MY92.113 ...

Renewable unsaturated polyesters from muconic acid

DOE PAGES

Rorrer, Nicholas A.; Dorgan, John R.; Vardon, Derek R.; ...

2016-09-27

cis,cis-Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis-muconate is synthesized and subsequently incorporated intomore » poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the case of poly(butylene succinate), utilization of neat muconic acid yields substoichiometric incorporation consistent with a tapered copolymer structure, whereas the muconate diester exhibits stoichiometric incorporation and a random copolymer structure based on thermal and mechanical properties. Prototypical fiberglass panels were produced by infusing a mixture of low molecular weight poly(butylene succinate-co-muconate) and styrene into a woven glass mat and thermally initiating polymerization resulting in thermoset composites with shear moduli in excess of 30 GPa, a value typical of commercial composites. The increased glass transition temperatures with increasing mucconic incorporation leads to improved composites properties. We find that the molecular tunability of poly(butylene succinate-co-muconate) as a tapered or random copolymer enables the tunability of composite properties. Altogether, this study demonstrates the utility of muconic acid as a

Renewable unsaturated polyesters from muconic acid

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

Rorrer, Nicholas A.; Dorgan, John R.; Vardon, Derek R.

cis,cis-Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis-muconate is synthesized and subsequently incorporated intomore » poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the case of poly(butylene succinate), utilization of neat muconic acid yields substoichiometric incorporation consistent with a tapered copolymer structure, whereas the muconate diester exhibits stoichiometric incorporation and a random copolymer structure based on thermal and mechanical properties. Prototypical fiberglass panels were produced by infusing a mixture of low molecular weight poly(butylene succinate-co-muconate) and styrene into a woven glass mat and thermally initiating polymerization resulting in thermoset composites with shear moduli in excess of 30 GPa, a value typical of commercial composites. The increased glass transition temperatures with increasing mucconic incorporation leads to improved composites properties. We find that the molecular tunability of poly(butylene succinate-co-muconate) as a tapered or random copolymer enables the tunability of composite properties. Altogether, this study demonstrates the utility of muconic acid as a

Role of 3-Hydroxy Fatty Acid-Induced Hepatic Lipotoxicity in Acute Fatty Liver of Pregnancy

PubMed Central

Ibdah, Jamal A.

2018-01-01

Acute fatty liver of pregnancy (AFLP), a catastrophic illness for both the mother and the unborn offspring, develops in the last trimester of pregnancy with significant maternal and perinatal mortality. AFLP is also recognized as an obstetric and medical emergency. Maternal AFLP is highly associated with a fetal homozygous mutation (1528G>C) in the gene that encodes for mitochondrial long-chain hydroxy acyl-CoA dehydrogenase (LCHAD). The mutation in LCHAD results in the accumulation of 3-hydroxy fatty acids, such as 3-hydroxy myristic acid, 3-hydroxy palmitic acid and 3-hydroxy dicarboxylic acid in the placenta, which are then shunted to the maternal circulation leading to the development of acute liver injury observed in patients with AFLP. In this review, we will discuss the mechanistic role of increased 3-hydroxy fatty acid in causing lipotoxicity to the liver and in inducing oxidative stress, mitochondrial dysfunction and hepatocyte lipoapoptosis. Further, we also review the role of 3-hydroxy fatty acids in causing placental damage, pancreatic islet β-cell glucolipotoxicity, brain damage, and retinal epithelial cells lipoapoptosis in patients with LCHAD deficiency. PMID:29361796

Biochemistry of Suberization

PubMed Central

Agrawal, Vishwanath P.; Kolattukudy, P. E.

1977-01-01

A cell-free extract obtained from suberizing potato (Solanum tuberosum L.) tuber disks catalyzed the conversion of 16-hydroxy[G-3H]hexadecanoic acid to the corresponding dicarboxylic acid with NADP or NAD as the cofactor, with a slight preference for the former. This ω-hydroxyacid dehydrogenase activity, located largely in the 100,000g supernatant fraction, has a pH optimum of 9.5. It showed an apparent Km of 50 μM for 16-hydroxyhexadecanoic acid. The dehydrogenase activity was inhibited by thiol reagents, such as p-chloromercuribenzoate, N-ethylmaleimide, and iodoacetamide, and this dehydrogenase is shown to be different from alcohol dehydrogenase. That 16-oxohexadecanoic acid was an intermediate in the conversion of 16-hydroxyhexadecanoic acid to the corresponding dicarboxylic acid was suggested by the observation that the cell-free extract also catalyzed the conversion of 16-oxohexadecanoic acid to the dicarboxylic acid, with NADP as the preferred cofactor. The time course of development of the ω-hydroxyacid dehydrogenase activity in the suberizing potato disks correlated with the rate of deposition of suberin. Experiments with actinomycin D and cycloheximide suggested that the transcriptional processes, which are directly related to suberin biosynthesis and ω-hydroxyacid dehydrogenase biosynthesis, occurred between 72 and 96 hours after wounding. These results strongly suggest that a wound-induced ω-hydroxyacid dehydrogenase is involved in suberin biosynthesis in potato disks. PMID:16659915

Chemical evolution of multicomponent aerosol particles during evaporation

NASA Astrophysics Data System (ADS)

Zardini, Alessandro; Riipinen, Ilona; Pagels, Joakim; Eriksson, Axel; Worsnop, Douglas; Switieckli, Erik; Kulmala, Markku; Bilde, Merete

2010-05-01

Atmospheric aerosol particles have an important but not well quantified effect on climate and human health. Despite the efforts made in the last decades, the formation and evolution of aerosol particles in the atmosphere is still not fully understood. The uncertainty is partly due to the complex chemical composition of the particles which comprise inorganic and organic compounds. Many organics (like dicarboxylic acids) can be present both in the gas and in the condensed phase due to their low vapor pressure. Clearly, an understanding of this partition is crucial to address any other issue in atmospheric physics and chemistry. Moreover, many organics are water soluble, and their influence on the properties of aqueous solution droplets is still poorly characterized. The solid and sub-cooled liquid state vapor pressures of some organic compounds have been previously determined by measuring the evaporation rate of single-compound crystals [1-3] or binary aqueous droplets [4-6]. In this work, we deploy the HTDMA technique (Hygroscopicity Tandem Differential Mobility Analyzer) coupled with a 3.5m laminar flow-tube and an Aerosol Mass Spectrometer (AMS) for determining the chemical evolution during evaporation of ternary droplets made of one dicarboxylic acid (succinic acid, commonly found in atmospheric samples) and one inorganic compound (sodium chloride or ammonium sulfate) in different mixing ratios, in equilibrium with water vapor at a fixed relative humidity. In addition, we investigate the evaporation of multicomponent droplets and crystals made of three organic species (dicarboxylic acids and sugars), of which one or two are semi-volatile. 1. Bilde M. and Pandis, S.N.: Evaporation Rates and Vapor Pressures of Individual Aerosol Species Formed in the Atmospheric Oxidation of alpha- and beta-Pinene. Environmental Science and Technology, 35, 2001. 2. Bilde M., et al.: Even-Odd Alternation of Evaporation Rates and Vapor Pressures of C3-C9 Dicarboxylic Acid Aerosols

40 CFR Appendix A to Part 434 - Alternate Storm Limitations for Acid or Ferruginous Mine Drainage

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 30 2014-07-01 2014-07-01 false Alternate Storm Limitations for Acid or Ferruginous Mine Drainage A Appendix A to Part 434 Protection of Environment ENVIRONMENTAL...—Alternate Storm Limitations for Acid or Ferruginous Mine Drainage EC01MY92.113 ...

40 CFR Appendix A to Part 434 - Alternate Storm Limitations for Acid or Ferruginous Mine Drainage

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 31 2013-07-01 2013-07-01 false Alternate Storm Limitations for Acid or Ferruginous Mine Drainage A Appendix A to Part 434 Protection of Environment ENVIRONMENTAL...—Alternate Storm Limitations for Acid or Ferruginous Mine Drainage EC01MY92.113 ...

40 CFR Appendix A to Part 434 - Alternate Storm Limitations for Acid or Ferruginous Mine Drainage

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 31 2012-07-01 2012-07-01 false Alternate Storm Limitations for Acid or Ferruginous Mine Drainage A Appendix A to Part 434 Protection of Environment ENVIRONMENTAL...—Alternate Storm Limitations for Acid or Ferruginous Mine Drainage EC01MY92.113 ...

Atmospheric production of oxalic acid/oxalate and nitric acid/nitrate in the Tampa Bay airshed: Parallel pathways

NASA Astrophysics Data System (ADS)

Martinelango, P. Kalyani; Dasgupta, Purnendu K.; Al-Horr, Rida S.

Oxalic acid is the dominant dicarboxylic acid (DCA), and it constitutes up to 50% of total atmospheric DCAs, especially in non-urban and marine atmospheres. A significant amount of particulate H 2Ox/oxalate (Ox) occurred in the coarse particle fraction of a dichotomous sampler, the ratio of oxalate concentrations in the PM 10 to PM 2.5 fractions ranged from 1 to 2, with mean±sd being 1.4±0.2. These results suggest that oxalate does not solely originate in the gas phase and condense into particles. Gaseous H 2Ox concentrations are much lower than particulate Ox concentrations and are well correlated with HNO 3, HCHO, and O 3, supporting a photochemical origin. Of special relevance to the Bay Region Atmospheric Chemistry Experiment (BRACE) is the extent of nitrogen deposition in the Tampa Bay estuary. Hydroxyl radical is primarily responsible for the conversion of NO 2 to HNO 3, the latter being much more easily deposited. Hydroxyl radical is also responsible for the aqueous phase formation of oxalic acid from alkenes. Hence, we propose that an estimate of rad OH can be obtained from H 2Ox/Ox production rate and we accordingly show that the product of total oxalate concentration and NO 2 concentration approximately predicts the total nitrate concentration during the same period.

Air pollution, acid rain and the future of forests. Part 5

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

Postel, S.

1984-11-01

Part 5 of a 6-part series by Worldwatch Institute examines the need for international cooperation in dealing with transboundary air pollution. Comparisons of annual sulfur emissions and acid depositions on the European countries show that there is often a large discrepancy between a country's contribution of air pollutants and the amount it receives. Efforts to acknowledge the common interest and to develop multilateral agreements have found the European Economic Community to be the best forum, although political and economic goals tend to dilute long-term solutions. Copies of the complete report can be obtained by sending $2 to Worldwatch Institute, 1776more » Massachusetts Ave., N.W., Washington, DC. 1 table.« less

One-dimensional Cu(II) coordination polymers containing C2h-symmetric 1,1':4',1''-terphenyl-3,3'-dicarboxylate linkers.

PubMed

Kim, Hyun Chul; Gu, Ja Min; Huh, Seong; Yo, Chul Hyun; Kim, Youngmee

2015-10-01

Two new one-dimensional Cu(II) coordination polymers (CPs) containing the C2h-symmetric terphenyl-based dicarboxylate linker 1,1':4',1''-terphenyl-3,3'-dicarboxylate (3,3'-TPDC), namely catena-poly[[bis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(4)O,O':O'':O'''] monohydrate], {[Cu(C20H12O4)(C2H7N)2]·H2O}n, (I), and catena-poly[[aquabis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(2)O(3):O(3')] monohydrate], {[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O}n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X-ray crystallography. The 3,3'-TPDC bridging ligands coordinate the Cu(II) ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one-dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one-dimensional coordination polymer chains, forming a two-dimensional network in (I) and a three-dimensional network in (II).

Activation of cryptic metabolite production through gene disruption: Dimethyl furan-2,4-dicarboxylate produced by Streptomyces sahachiroi.

PubMed

Simkhada, Dinesh; Zhang, Huitu; Mori, Shogo; Williams, Howard; Watanabe, Coran M H

2013-01-01

At least 65% of all small molecule drugs on the market today are natural products, however, re-isolation of previously identified and characterized compounds has become a serious impediment to the discovery of new bioactive natural products. Here, genetic knockout of an unusual non-ribosomal peptide synthetase (NRPS) C-PCP-C module, aziA2, is performed resulting in the accumulation of the secondary metabolite, dimethyl furan-2,4-dicarboxylate. The cryptic metabolite represents the first non-azinomycin related compound to be isolated and characterized from the soil bacterium, S. sahachiroi. The results from this study suggest that abolishing production of otherwise predominant natural products through genetic knockout may constitute a means to "activate" the production of novel secondary metabolites that would otherwise lay dormant within microbial genome sequences.

Photodetachment of Zwitterions: Probing Intramolecular Coulomb Repulsion and Attraction in the Gas Phase Using Pyridinium Dicarboxylate Anions

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

Wang, Xue B.; Dacres, J E.; Yang, Xin

2003-10-23

Zwitterions are critically important in many biological transformations and are used in numerous chemical processes. The consequences of electrostatic effects on reactivity and physical properties, however, are largely unknown. In this work, we report the results of negative ion photoelectron spectra of nine isomeric pyridinium dicarboxylate zwitterions and three nonzwitterionic methoxycarbonylpyridine carboxylate isomers (-O(2)CPyrCO(2)CH(3)). Information about the intramolecular electrostatic interactions was directly obtained from the photoelectron spectra. The adiabatic and vertical detachment energies were measured and understood in terms of intramolecular Coulombic forces. Calculations at the B3LYP and CCSD(T) level were performed and compared to the experimental electron binding energies.more » Structures, relative stabilities, and the electron detachment sites also were obtained from the calculations.« less

Using a fully recyclable dicarboxylic acid for producing dispersible and thermally stable cellulose nanomaterials from different cellulosic sources

Treesearch

Chao Jia; Liheng Chen; Ziqiang Shao; Umesh P. Agarwal; Liangbing Hu; J. Y. Zhu

2017-01-01

We fabricated cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) from different cellulose materials (bleached eucalyptus pulp (BEP), spruce dissolving pulp (SDP) and cotton based qualitative filter paper (QFP) using concentrated oxalic acid hydrolysis and subsequent mechanical fibrillation (for CNFs). The process was green as acid can easily be recovered,...

Fabrication of zinc-dicarboxylate- and zinc-pyrazolate-carboxylate-framework thin films through vapour-solid deposition.

PubMed

Medishetty, Raghavender; Zhang, Zongji; Sadlo, Alexander; Cwik, Stefan; Peeters, Daniel; Henke, Sebastian; Mangayarkarasi, Nagarathinam; Devi, Anjana

2018-05-17

Fabrication of three-dimensional metal-organic framework (MOF) thin films has been investigated for the first time through the conversion of a ZnO layer via a pure vapour-solid deposition reaction at ambient pressure. The fabrication of MOF thin films with a dicarboxylate linker, (DMA)2[Zn3(bdc)4] (1) (bdc = 1,4-benzenedicarboxylate), and a carboxy-pyrazolate linker, [Zn4O(dmcapz)6] (2) (dmcapz = 3,5-dimethyl-4-carboxypyrazole), involves the deposition of the linker and/or the preparation of a composite film preliminarily and its subsequent conversion into a MOF film using closed cell thermal treatment. Furthermore, it was possible to isolate thin films with a MOF-5 isotype structure grown along the [110] direction, using a carboxy-pyrazolate linker. This was achieved just by the direct reaction of the ZnO film and the organic linker vapors, employing a simple route that demonstrates the feasibility of MOF thin film fabrication using inexpensive routes at ambient pressure.

Antioxidant capacity and fatty acid composition of different parts of Adenocarpus complicatus (Fabaceae) from Turkey.

PubMed

Berber, Adnan; Zengin, Gokhan; Aktumsek, Abdurrahman; Sanda, Murad Aydin; Uysal, Tuna

2014-03-01

Adenocarpus complicatus is distributed throughout the Anatolian peninsula and is widely used for human and animal nutrition. The purpose of this work was to study the antioxidant properties and fatty acid composition of different parts of this plant (fruits and mixed materials). The species was collected from Golyuzu village of the Seydisehir district near Konya province, Turkey. Fruit and mixed parts obtained from this species were ground and a 15g sample was used to prepare methanolic extracts. Powdered plant samples were extracted with 100mL methanol in a mechanical shaker. The obtained extracts were filtered and concentrated to dryness under reduced pressure and were subsequently stored at -20 degrees C. Antioxidant components, namely total phenolic and flavonoid content, were detected for each extract using spectrophotometric methods. Antioxidant capacity was evaluated by various assays including phosphomolybdenum, DPPH free radical scavenging capacity, metal chelating activity, and ferric and cupric ion reducing power. The fatty acid profiles of plant parts were also determined by using gas chromatography. The total phenolic content of fruit (36.21mgGAE/g) was higher than that of mixed materials (13.79mgGAE/g). The methanolic extract of mixed material had higher amounts of flavonoid than fruit extract. The free radical scavenging activity of extracts was expressed as IC50 value (microg/mL) (amount required to inhibit DPPH radical formation by 50%). The lower IC50 value reflects better free radical scavenging action. The radical scavenging activity of the samples was compared with BHT, it showed the mixed material to be almost two times more potent than the fruit extract. However, BHT is an excellent free radical scavenger with an IC50 of 34.061 microg/mL. The ferric and cupric reducing power potentials of the extracts were expressed as EC50 value (the effective concentration at which the absorbance was 0.5). Fruit extract exhibited strong ferric reducing

Implication of azelaic acid in a Greenland Ice Core for oceanic and atmospheric changes in high latitudes

NASA Astrophysics Data System (ADS)

Kawamura, K.; Yokoyama, K.; Fujii, Y.; Watanabe, O.

A Greenland ice core (450 years) has been studied for low molecular weight dicarboxylic acids (C2-C10) using a capillary gas chromatography and mass spectrometer. Their molecular distribution generally showed a predominance of succinic acid (C4) followed by oxalic (C2), malonic (C3), glutaric (C5), adipic (C6), and azelaic (C9) acids. Azelaic acid, that is a specific photochemical reaction product of biogenic unsaturated fatty acids, gave a characteristic historical trend in the ice core; i.e., the concentrations are relatively low during late 16th to 19th century (Little Ice Age) but become very high in late 19th to 20th century (warmer periods) with a large peak in 1940s AD. Lower concentrations of azelaic acid may have been caused by a depressed emission of unsaturated fatty acids from seawater microlayers due to enhanced sea ice coverage during Little Ice Age. Inversely, increased concentrations of azelaic acid in late 19th to 20th century are likely interpreted by an enhanced sea-to-air emission of the precursor unsaturated fatty acids due to a retreat of sea ice and/or by the enhanced production due to a potentially increased oxidizing capability of the atmosphere.

Possible carcinogenic potential of dimethyl dimethoxy biphenyl dicarboxylate in experimental animals

PubMed Central

Botros, Sanaa Sabet; El-Lakkany, Naglaa Mohamed; Hammam, Olfat Ali; Sabra, Abdel-Naser Abdel-Aal; Taha, Alaa Awad

2016-01-01

Dimethyl dimethoxy biphenyl dicarboxylate (DDB) has been extensively used in the treatment of liver diseases accounting for 1–6% of the global disease burden. Cell replication, DNA synthesis, and proliferation, providing significant information about behavior of cells were examined in mice exposed to subchronic administration with DDB. Conventional liver functions specifically gamma-glutamyltransferase (γ-GT), a marker expressing liver canceration was also investigated. Normal mice were allocated into two groups each of 10 mice. The 1st and 2nd groups were treated with DDB in a dose of 50 mg/kg/day, 5 days/week for 1 month and 3 months, respectively. Comparable groups of normal mice were left without treatment as controls. Compared to normal control group, animals receiving DDB for 3 months showed marked elevations of both alanine aminotransferase and γ-GT, significant inhibition in cytochrome P450, a significant increase in the mean ploidy and 4C with moderate to marked increase in S-phase populations and the number of proliferating cell nuclear antigen-positive cells. In conclusion, this is the first report on the potential relationship between the subchronic administration of DDB and the increase in the hepatocyte proliferation, cell replication and DNA synthesis that may raise an alarm regarding possible DDB insult on the biological behavior of cells. PMID:27144153

Biosynthesis of Cutin

PubMed Central

Kolattukudy, P.E.; Croteau, Rodney; Walton, T.J.

1975-01-01

Long chain dicarboxylic acids are constituents of the protective biopolymers cutin and suberin of plants. Cell-free extracts from the excised epidermis of Vicia faba leaves catalyzed conversion of 16-hydroxy[G-3H]hexadecanoic acid to the corresponding dicarboxylic acid with nicotinamide-adenine dinucleotide phosphate as the preferred cofactor. This enzymatic activity, located largely in the 100,000g supernatant fraction, had a pH optimum near 8. This dehydrogenase showed an apparent Km of 1.25 × 10−5m and 3.6 × 10−4m for 16-hydroxyhexadecanoic acid and NADP, respectively. Modification of the substrate, either by esterification of the carboxyl group or by introduction of another hydroxyl group at C-10, resulted in a substantial (two-thirds) decrease in the rate of reaction, and hexadecanol was not a good substrate. The enzyme was inhibited by thiol reagents such as N-ethylmaleimide and p-chloromercuribenzoate. The aldehyde intermediate was trapped by the inclusion of dinitrophenyl hydrazine in the reaction mixture, and the 16-oxo compound was regenerated and identified. Furthermore, synthetic 16-oxo-[G-3H] hexadecanoic acid was readily converted to the dicarboxylic acid by the cell-free preparation. These results demonstrate that epidermis of Vicia faba contains an ω-hydroxyacid dehydrogenase and an ω-oxoacid dehydrogenase. PMID:16659184

Syntheses, structures and magnetic properties of four coordination polymers based on nitrobenzene dicarboxylate and various N-donor coligands

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

Li, Gui-Lian; Yin, Wei-Dong; Liu, Guang-Zhen

Four new coordination polymers ([Ni(4-Nbdc)(bpa)(H{sub 2}O)]){sub n} (1), ([Co(4-Nbdc)(bpp) (H{sub 2}O)]){sub n} (2), ([Ni(4-Nbdc)(bpp)(H{sub 2}O)]·H{sub 2}O){sub n} (3), and ([Mn{sub 2}(3-Nbdc){sub 2}(bib){sub 3}]·2H{sub 2}O){sub n} (4) (4-Nbdc=4-nitrobenzene-1,2-dicarboxylate, 3-Nbdc=3-nitrobenzene-1,2-dicarboxylate, bpa=1,2-bi(4-pyridyl)ethane, bpp=1,3-bis(4-pyridyl)propane, and bib=1,4-bis(1-imidazoly)benzene), were synthesized by hydrothermal reactions, and characterized by single-crystal X-ray diffractions, elemental analysis, FT-IR, PXRD, TGA and magnetic analysis. Complexes 1 and 2 display quasi-trapezoidal chain and brick-wall layer, and both of them contain metal–carboxylate binuclear units. Complexes 3 and 4 exhibit three-dimensional frameworks with the (6{sup 6}) dia topology and (4{sup 4}.6{sup 10}.8)(4{sup 4}.6{sup 2}) fsc topology, and both of them contain metal–carboxylate chains. The carboxyl groupsmore » with syn-anti coordination mode mediate effectively the weak ferromagnetic coupling interaction within Ni(II)–carboxylate binuclear in 1 (J=1.27 cm{sup −1}) and Ni(II)–carboxylate chain in 3 (J=1.44 cm{sup −1}), respectively, and the carboxyl groups with anti-anti coordination mode leads to the classic antiferromagnetic coupling interaction within Mn(II)–carboxylate chain in 4 (J=−0.77 cm{sup −1}). - Highlights: • Four novel coordination polymers were hydrothermally synthesized. • 1 is 1D quasi-trapezoidal chain and 2 is brick-wall layer both with dinuclear units. • 3 and 4 show 3D frameworks both with 1D metal–carboxylate chains. • 1 and 3 exhibit ferromagnetic coupling, while 4 shows antiferromagnetic coupling.« less

Historic records of organic compounds from a high Alpine glacier: influences of biomass burning, anthropogenic emissions, and dust transport

NASA Astrophysics Data System (ADS)

Müller-Tautges, C.; Eichler, A.; Schwikowski, M.; Pezzatti, G. B.; Conedera, M.; Hoffmann, T.

2016-01-01

Historic records of α-dicarbonyls (glyoxal, methylglyoxal), carboxylic acids (C6-C12 dicarboxylic acids, pinic acid, p-hydroxybenzoic acid, phthalic acid, 4-methylphthalic acid), and ions (oxalate, formate, calcium) were determined with annual resolution in an ice core from Grenzgletscher in the southern Swiss Alps, covering the time period from 1942 to 1993. Chemical analysis of the organic compounds was conducted using ultra-high-performance liquid chromatography (UHPLC) coupled to electrospray ionization high-resolution mass spectrometry (ESI-HRMS) for dicarbonyls and long-chain carboxylic acids and ion chromatography for short-chain carboxylates. Long-term records of the carboxylic acids and dicarbonyls, as well as their source apportionment, are reported for western Europe. This is the first study comprising long-term trends of dicarbonyls and long-chain dicarboxylic acids (C6-C12) in Alpine precipitation. Source assignment of the organic species present in the ice core was performed using principal component analysis. Our results suggest biomass burning, anthropogenic emissions, and transport of mineral dust to be the main parameters influencing the concentration of organic compounds. Ice core records of several highly correlated compounds (e.g., p-hydroxybenzoic acid, pinic acid, pimelic, and suberic acids) can be related to the forest fire history in southern Switzerland. P-hydroxybenzoic acid was found to be the best organic fire tracer in the study area, revealing the highest correlation with the burned area from fires. Historical records of methylglyoxal, phthalic acid, and dicarboxylic acids adipic acid, sebacic acid, and dodecanedioic acid are comparable with that of anthropogenic emissions of volatile organic compounds (VOCs). The small organic acids, oxalic acid and formic acid, are both highly correlated with calcium, suggesting their records to be affected by changing mineral dust transport to the drilling site.

Tunable Keplerate Type-Cluster "Mo132 " Cavity with Dicarboxylate Anions.

PubMed

Lai, Thanh-Loan; Awada, Mouhamad; Floquet, Sébastien; Roch-Marchal, Catherine; Watfa, Nancy; Marrot, Jérôme; Haouas, Mohamed; Taulelle, Francis; Cadot, Emmanuel

2015-09-14

The internal functionalization of the Keplerate-type capsule Mo132 has been carried out by ligand exchange leading to the formation of glutarate and succinate containing species isolated as ammonium or dimethylammonium salts. Solution NMR analysis is consistent with asymmetric inner dicarboxylate ions containing one carboxylato group grafted onto the inner side of the spheroidal inorganic shell while the second hangs toward the center of the cavity. Such a disposition has been confirmed by the single-crystal X-ray diffraction analysis of the glutarate containing {Mo132 } species. A detailed NMR solution study of the ligand-exchange process allowed determining the binding constant KL of acetate (AcO(-) ), succinate (HSucc(-) ) or glutarate (HGlu(-) ) ligands at the 30 inner coordinating sites, which vary such as K AcO -

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Tris(5,6-dimethyl-1H-benzimidazole-κN 3)(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)nickel(II)

PubMed Central

Li, Yue-Hua; Li, Feng-Feng; Liu, Xin-Hua; Zhao, Ling-Yan

2012-01-01

The title mononuclear complex, [Ni(C7H3NO4)(C9H10N2)3], shows a central NiII atom which is coordinated by two carboxyl­ate O atoms and the N atom from a pyridine-2,6-dicarboxyl­ate ligand and by three N atoms from different 5,6-dimethyl-1H-­benzimidazole ligands in a distorted octa­hedral geometry. The crystal structure shows intermolecular N—H⋯O hydrogen bonds. PMID:22719301

Formation of itraconazole-succinic acid cocrystals by gas antisolvent cocrystallization.

PubMed

Ober, Courtney A; Gupta, Ram B

2012-12-01

Cocrystals of itraconazole, an antifungal drug with poor bioavailability, and succinic acid, a water-soluble dicarboxylic acid, were formed by gas antisolvent (GAS) cocrystallization using pressurized CO(2) to improve itraconazole dissolution. In this study, itraconazole and succinic acid were simultaneously dissolved in a liquid solvent, tetrahydrofuran, at ambient conditions. The solution was then pressurized with CO(2), which decreased the solvating power of tetrahydrofuran and caused crystallization of itraconazole-succinic acid cocrystals. The cocrystals prepared by GAS cocrystallization were compared to those produced using a traditional liquid antisolvent, n-heptane, for crystallinity, chemical structure, thermal behavior, size and surface morphology, potential clinical relevance, and stability. Powder X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy analyses showed that itraconazole-succinic acid cocrystals with physical and chemical properties similar to cocrystals produced using a traditional liquid antisolvent technique can be prepared by CO(2) antisolvent cocrystallization. The dissolution profile of itraconazole was significantly enhanced through GAS cocrystallization with succinic acid, achieving over 90% dissolution in less than 2 h. The cocrystals appeared stable against thermal stress for up to 4 weeks under accelerated stability conditions, showing only moderate decreases in their degree of crystallinity but no change in their crystalline structure. This study shows the utility of an itraconazole-succinic acid cocrystal for improving itraconazole bioavailability while also demonstrating the potential for CO(2) to replace traditional liquid antisolvents in cocrystal preparation, thus making cocrystal production more environmentally benign and scale-up more feasible.

Recovery of succinic acid produced by fermentation of a metabolically engineered Mannheimia succiniciproducens strain.

PubMed

Song, Hyohak; Huh, Yun Suk; Lee, Sang Yup; Hong, Won Hi; Hong, Yeon Ki

2007-12-01

There have recently been much advances in the production of succinic acid, an important four-carbon dicarboxylic acid for many industrial applications, by fermentation of several natural and engineered bacterial strains. Mannheimia succiniciproducens MBEL55E isolated from bovine rumen is able to produce succinic acid with high efficiency, but also produces acetic, formic and lactic acids just like other anaerobic succinic acid producers. We recently reported the development of an engineered M. succiniciproducens LPK7 strain which produces succinic acid as a major fermentation product while producing much reduced by-products. Having an improved succinic acid producer developed, it is equally important to develop a cost-effective downstream process for the recovery of succinic acid. In this paper, we report the development of a simpler and more efficient method for the recovery of succinic acid. For the recovery of succinic acid from the fermentation broth of LPK7 strain, a simple process composed of a single reactive extraction, vacuum distillation, and crystallization yielded highly purified succinic acid (greater than 99.5% purity, wt%) with a high yield of 67.05wt%. When the same recovery process or even multiple reactive extraction steps were applied to the fermentation broth of MBEL55E, lower purity and yield of succinic acid were obtained. These results suggest that succinic acid can be purified in a cost-effective manner by using the fermentation broth of engineered LPK7 strain, showing the importance of integrating the strain development, fermentation and downstream process for optimizing the whole processes for succinic acid production.

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

Yi, Xiu-Chun; Xi, Fu-Gui; Wang, Kun

From a new dicarboxylate ligand, 9H-carbazole-2,7-dicarboxylic acid (2,7-H{sub 2}CDC), three Zn(II) metal-organic frameworks were synthesized in the absence or presence of ditopic N-donor ligands. They are formulated as [Zn{sub 5}(μ{sub 3}-OH){sub 2}(2,7-CDC){sub 4}(DEF){sub 2}] (1) (DEF=N,N-diethylformamide), [Zn{sub 2}(2,7-CDC){sub 2}(DABCO)(H{sub 2}O)]·5DMF·H{sub 2}O (2) (DABCO=1-diaza-bicyclo[2.2.2]octane, DMF=N,N-dimethylformamide), and [Zn{sub 2}(2,7-CDC){sub 2}(bpea)]·3DMA·2 H{sub 2}O (3) (bpea=1,2-bis(4-pyridyl)ethylane, DMA=N,N-dimethylacetamide). Compounds 1 and 3 display the 3D pcu frameworks. In 1 the unusual pentanuclear [Zn{sub 5}(μ{sub 3}-OH){sub 2}(COO){sub 8}] secondary building units (SBUs) are linked by dicarboxylate ligands. Differently, in 3 the well-known paddle–wheel [Zn{sub 2}(COO){sub 4}] SBUs are linked by dicarboxylate and dipyridyl ligands. Compound 2more » shows the rare self-catenated 3D alb-3,6-C2/c net topology based on the dinuclear paddle–wheel SBU and a mononuclear unit. The stability and fluorescent properties of the compounds have been studied. - Graphical abstract: A new dicarboxylate ligand, 9H-carbazole-2,7-dicarboxylic acid, was used to construct Zn(II) metal-organic frameworks, including a novel self-catenated network with the rare 3D alb-3,6-C2/c net and two pcu-type networks based on an unprecedented pentanuclear clusters and the common paddle–wheel units. The compounds show blue fluorescent properties. Display Omitted - Highlights: • MOFs with a new carbazole-based dicarboxylate ligand. • New pentanuclear [Zn{sub 5}(μ{sub 3}-OH){sub 2}(COO){sub 8}] secondary building unit. • The rare self-catenated 3D alb-3,6-C2/c net.« less

Ni(ClO4)(2)-catalysed regio- and diastereoselective [3+2] cycloaddition of indoles and aryl oxiranyl-dicarboxylates/diketones: a facile access to furo[3,4-b]indoles.

PubMed

Zhang, Jieming; Chen, Zuliang; Wu, Hai-Hong; Zhang, Junliang

2012-02-07

Ni(ClO(4))(2)·6H(2)O-catalysed regioselective and diastereoselective [3+2]-annulations of aryl oxiranyl-dicarboxylates and indoles via selective C-C bond cleavage of oxirane were revealed. The cycloadditions proceed smoothly with high regio- and diastereoselectivity under mild conditions leading to 1H-furo[3,4-b]indoles in good to excellent yields. This journal is © The Royal Society of Chemistry 2012

The main chemical composition and in vitro antifungal activity of the essential oils of Ocimum basilicum Linn. var. pilosum (Willd.) Benth.

PubMed

Zhang, Ji-Wen; Li, Sheng-Kun; Wu, Wen-Jun

2009-01-08

The essential oils of the aerial parts of Ocimum basilicum Linn.var. pilosum (Willd.) Benth., an endemic medicinal plant growing in China, was obtained by hydrodistillation and analysed by GC-MS. Fifteen compounds, representing 74.19% of the total oil were identified. The main components were as follows: linalool (29.68%), (Z)-cinnamic acid methyl ester (21.49%), cyclohexene (4.41%), alpha- cadinol (3.99%), 2,4-diisopropenyl-1-methyl-1-vinylcyclohexane (2.27%), 3,5-pyridine-dicarboxylic acid, 2,6-dimethyl-diethyl ester (2.01%), beta-cubebene (1.97%), guaia-1(10),11-diene (1.58%), cadinene (1.41%) (E)-cinnamic acid methyl ester (1.36%) and beta-guaiene (1.30%). The essential oils showed significant antifungal activity against some plant pathogenic fungi.

Flotation selectivity of novel alkyl dicarboxylate reagents for apatite-calcite separation.

PubMed

Karlkvist, Tommy; Patra, Anuttam; Rao, Kota Hanumantha; Bordes, Romain; Holmberg, Krister

2015-05-01

The investigation aims to demonstrate the conceptual thoughts behind developing mineral specific reagents for use in flotation of calcium containing ores. For this purpose, a series of dicarboxylate-based surfactants with varying distance between the carboxylate groups (one, two or three methylene groups) was synthesized. A surfactant with the same alkyl chain length but with only one carboxylate group was also synthesized and evaluated. The adsorption behavior of these new reagents on pure apatite and pure calcite surfaces was studied using Hallimond tube flotation, FTIR and ζ potential measurements. The relation between the adsorption behavior of a given surfactant at a specific mineral surface and its molecular structure over a range of concentrations and pH values, as well as the region of maximum recovery, was established. It was found that one of the reagents, with a specific distance between the carboxylate groups, was much more selective for a particular mineral surface than the other homologues. For example, out of the four compounds synthesized, only the one where the carboxylate groups were separated by a single methylene group floated apatite but not calcite, whereas calcite was efficiently floated with the monocarboxylic reagent, but not with the other reagents synthesized. This selective adsorption of a given surfactant to a particular mineral surface relative to other mineral surfaces as evidenced in the flotation studies was substantiated by ζ potential and infra-red spectroscopy data. Copyright © 2014 Elsevier Inc. All rights reserved.

New fatty acid and acyl glycoside from the aerial parts of Phyllanthus fraternus Webster.

PubMed

Ali, Abuzer; Jameel, Mohammad; Ali, Mohammed

2016-01-01

Phyllanthus fraternus Webster (Euphorbiaceae) is used to treat dyspepsia, indigestion, jaundice, dysentery, diabetes, influenza, kidney stones, urinary tract diseases, vaginitis, and skin eruptions in traditional systems of medicine. The methanol extract of aerial parts of P. fraternus was obtained by soxhlation method. Isolation of compounds was done by silica gel column chromatography. Analytical thin layer chromatography was used to check the homogeneity of eluted fractions. The structures of isolated compounds were established on the basis of spectral studies and chemical reactions. Phytochemical investigation of a methanolic extract of the aerial parts yielded a new fatty acid characterized as cis-n-octacos-17-enoic acid (5) and a new acyl tetraglycoside formulated as n-dodecanoyl-O-β-D-glucopyranosyl-(2'→1'')-O-β-D-glucopyranosyl-(2''→1''')-O-β-D-glucopyranosyl-(2'''→1'''')-O-β-D-glucopyranoside (7) along with known compounds 1-pentacosanol (1), β-sitosteryl oleate (2), β-sitosteryl linoleate (3), stigmasterol (4) and palmityl glucuronoside (6).

Enantioselective Metabolism of Chiral 3-Phenylbutyric Acid, an Intermediate of Linear Alkylbenzene Degradation, by Rhodococcus rhodochrous PB1

PubMed Central

Simoni, S.; Klinke, S.; Zipper, C.; Angst, W.; Kohler, H. E.

1996-01-01

Rhodococcus rhodochrous PB1 was isolated from compost soil by selective culture with racemic 3-phenylbutyric acid as the sole carbon and energy source. Growth experiments with the single pure enantiomers as well as with the racemate showed that only one of the two enantiomers, (R)-3-phenylbutyric acid, supported growth of strain PB1. Nevertheless, (S)-3-phenylbutyric acid was cometabolically transformed to, presumably, (S)-3-(2,3-dihydroxyphenyl)butyric acid (the absolute configuration at the C-3 atom is not known yet) by (R)-3-phenylbutyric acid-grown cells of strain PB1, as shown by (sup1)H nuclear magnetic resonance spectroscopy of the partially purified compound and gas chromatography-mass spectrometry analysis of the trimethylsilyl derivative. Oxygen uptake rates suggest that either 3-phenylpropionic acid or cinnamic acid (trans-3-phenyl-2-propenoic acid) is the substrate for aromatic ring hydroxylation. This view is substantiated by the fact that 3-(2,3-dihydroxyphenyl)propionic acid was a substrate for meta cleavage in cell extracts of (R)-3-phenylbutyric acid-grown cells of strain PB1. Gas chromatography-mass spectrometry analysis of trimethylsilane-treated ethyl acetate extracts of incubation mixtures showed that both the meta-cleavage product, 2-hydroxy-6-oxo-2,4-nonadiene-1,9-dicarboxylic acid, and succinate, a hydrolysis product thereof, were formed during such incubations. PMID:16535265

Natural abiotic formation of oxalic acid in soils: results from aromatic model compounds and soil samples.

PubMed

Studenroth, Sabine; Huber, Stefan G; Kotte, Karsten; Schöler, Heinz F

2013-02-05

Oxalic acid is the smallest dicarboxylic acid and plays an important role in soil processes (e.g., mineral weathering and metal detoxification in plants). We have first proven its abiotic formation in soils and investigated natural abiotic degradation processes based on the oxidation of soil organic matter, enhanced by Fe(3+) and H(2)O(2) as hydroxyl radical suppliers. Experiments with the model compound catechol and further hydroxylated benzenes were performed to examine a common degradation pathway and to presume a general formation mechanism of oxalic acid. Two soil samples were tested for the release of oxalic acid and the potential effects of various soil parameters on oxalic acid formation. Additionally, the soil samples were treated with different soil sterilization methods to prove the oxalic acid formation under abiotic soil conditions. Different series of model experiments were conducted to determine a range of factors including Fe(3+), H(2)O(2), reaction time, pH, and chloride concentration on oxalic acid formation. Under certain conditions, catechol is degraded up to 65.6% to oxalic acid referring to carbon. In serial experiments with two soil samples, oxalic acid was produced, and the obtained results are suggestive of an abiotic degradation process. In conclusion, Fenton-like conditions with low Fe(3+) concentrations and an excess of H(2)O(2) as well as acidic conditions were required for an optimal oxalic acid formation. The presence of chloride reduced oxalic acid formation.

pH-Dependent Uptake of Fumaric Acid in Saccharomyces cerevisiae under Anaerobic Conditions

PubMed Central

Jamalzadeh, Elaheh; Verheijen, Peter J. T.; Heijnen, Joseph J.

2012-01-01

Microbial production of C4 dicarboxylic acids from renewable resources has gained renewed interest. The yeast Saccharomyces cerevisiae is known as a robust microorganism and is able to grow at low pH, which makes it a suitable candidate for biological production of organic acids. However, a successful metabolic engineering approach for overproduction of organic acids requires an incorporation of a proper exporter to increase the productivity. Moreover, low-pH fermentations, which are desirable for facilitating the downstream processing, may cause back diffusion of the undissociated acid into the cells with simultaneous active export, thereby creating an ATP-dissipating futile cycle. In this work, we have studied the uptake of fumaric acid in S. cerevisiae in carbon-limited chemostat cultures under anaerobic conditions. The effect of the presence of fumaric acid at different pH values (3 to 5) has been investigated in order to obtain more knowledge about possible uptake mechanisms. The experimental results showed that at a cultivation pH of 5.0 and an external fumaric acid concentration of approximately 0.8 mmol · liter−1, the fumaric acid uptake rate was unexpectedly high and could not be explained by diffusion of the undissociated form across the plasma membrane alone. This could indicate the presence of protein-mediated import. At decreasing pH levels, the fumaric acid uptake rate was found to increase asymptotically to a maximum level. Although this observation is in accordance with protein-mediated import, the presence of a metabolic bottleneck for fumaric acid conversion under anaerobic conditions could not be excluded. PMID:22113915

Olfactory receptor Olfr544 responding to azelaic acid regulates glucagon secretion in α-cells of mouse pancreatic islets.

PubMed

Kang, NaNa; Bahk, Young Yil; Lee, NaHye; Jae, YoonGyu; Cho, Yoon Hee; Ku, Cheol Ryong; Byun, Youngjoo; Lee, Eun Jig; Kim, Min-Soo; Koo, JaeHyung

2015-05-08

Olfactory receptors (ORs) are extensively expressed in olfactory as well as non-olfactory tissues. Although many OR transcripts are expressed in non-olfactory tissues, only a few studies demonstrate the functional role of ORs. Here, we verified that mouse pancreatic α-cells express potential OR-mediated downstream effectors. Moreover, high levels of mRNA for the olfactory receptors Olfr543, Olfr544, Olfr545, and Olfr1349 were expressed in α-cells as assessed using RNA-sequencing, microarray, and quantitative real-time RT-PCR analyses. Treatment with dicarboxylic acids (azelaic acid and sebacic acid) increased intracellular Ca(2+) mobilization in pancreatic α-cells. The azelaic acid-induced Ca(2+) response as well as glucagon secretion was concentration- and time-dependent manner. Olfr544 was expressed in α-cells, and the EC50 value of azelaic acid to Olfr544 was 19.97 μM, whereas Olfr545 did not respond to azelaic acid. Our findings demonstrate that Olfr544 responds to azelaic acid to regulate glucagon secretion through Ca(2+) mobilization in α-cells of the mouse pancreatic islets, suggesting that Olfr544 may be an important therapeutic target for metabolic diseases. Copyright © 2015 Elsevier Inc. All rights reserved.

Observing HNO3 release dependent upon metal complexes in malonic acid/nitrate droplets.

PubMed

Shao, Xu; Wu, Feng-Min; Yang, Hui; Pang, Shu-Feng; Zhang, Yun-Hong

2018-05-09

Although the dicarboxylic acid has been reported to react with nitrate for aged internally mixed aerosols in atmosphere, the quantitative nitrate depletion dependent upon composition in particles is still not well constrained. The chemical composition evolutions for malonic acid/sodium nitrate (MA/SN), malonic acid/magnesium nitrate (MA/MN) and malonic acid/calcium nitrate (MA/CN) particles with the organic to inorganic molar ratio (OIR) of 1:1 are investigated by vacuum Fourier transform infrared spectroscopy (FTIR). Upon dehydration, the intensity of the asymmetric stretching mode of COO - group (ν as -COO - ) increases, accompanying the decrease in OH feather band and COOH band and NO 3 - band. These band changes suggest malonate salts formation and HNO 3 release. The quantitative NO 3 - depletion data shows that the reactivity of MA-MN is most and that of MA-SN is least. Analysis of the stretching mode of COO - indicates the different bond type between metal cation and carboxylate anion. In addition, water content in particles decreases at the constant RH, implying water loss with the chemical reaction. When the RH changes very quickly, water uptake delay during the humidification process reveals that water mass transport is limited below 37% RH. Copyright © 2018 Elsevier B.V. All rights reserved.

3-Nitropropionic Acid is a Suicide Inhibitor of MitochondrialRespiration that, Upon Oxidation by Complex II, Forms a Covalent AdductWith a Catalytic Base Arginine in the Active Site of the Enzyme

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

Huang, Li-shar; Sun, Gang; Cobessi, David

We report three new structures of mitochondrial respiratory Complex II (succinate ubiquinone oxidoreductase, E.C. 1.3.5.1) at up to 2.1 {angstrom} resolution, with various inhibitors. The structures define the conformation of the bound inhibitors and suggest the residues involved in substrate binding and catalysis at the dicarboxylate site. In particular they support the role of Arg297 as a general base catalyst accepting a proton in the dehydrogenation of succinate. The dicarboxylate ligand in oxaloacetate-containing crystals appears to be the same as that reported for Shewanella flavocytochrome c treated with fumarate. The plant and fungal toxin 3-nitropropionic acid, an irreversible inactivator ofmore » succinate dehydrogenase, forms a covalent adduct with the side chain of Arg297. The modification eliminates a trypsin cleavage site in the flavoprotein, and tandem mass spectroscopic analysis of the new fragment shows the mass of Arg 297 to be increased by 83 Da and to have potential of losing 44 Da, consistent with decarboxylation, during fragmentation.« less

40 CFR 721.3000 - Dicarboxylic acid monoester.

Code of Federal Regulations, 2011 CFR

2011-07-01

... smoking. —Keep container closed. FIRST AID: In case of contact. EYES: Immediately flush with water for at... prevent dermal contact for any person involved in any processing or use operation where dermal contact may... CAUSE REPRODUCTIVE EFFECTS. —Do not get in eye, on skin, or clothing. —Do not breathe (vapor, mist...

40 CFR 721.3000 - Dicarboxylic acid monoester.

Code of Federal Regulations, 2010 CFR

2010-07-01

... prevent dermal contact for any person involved in any processing or use operation where dermal contact may... prevent contact or exposure. —Promptly remove contaminated non-imprevious clothing, wash before reuse... smoking. —Keep container closed. FIRST AID: In case of contact. EYES: Immediately flush with water for at...

Production of Plant Phthalate and its Hydrogenated Derivative from Bio-Based Platform Chemicals.

PubMed

Lu, Rui; Lu, Fang; Si, Xiaoqin; Jiang, Huifang; Huang, Qianqian; Yu, Weiqiang; Kong, Xiangtao; Xu, Jie

2018-04-06

Direct transformation of bio-based platform chemicals into aromatic dicarboxylic acids and their derivatives, which are widely used for the manufacture of polymers, is of significant importance for the sustainable development of the plastics industry. However, limited successful chemical processes have been reported. This study concerns a sustainable route for the production of phthalate and its hydrogenated derivative from bio-based malic acid and erythritol. The key Diels-Alder reaction is applied to build a substituted cyclohexene structure. The dehydration reaction of malic acid affords fumaric acid with 96.6 % yield, which could be used as the dienophile, and 1,3-butadiene generated in situ through erythritol deoxydehydration serves as the diene. Starting from erythritol and dibutyl fumarate, a 74.3 % yield of dibutyl trans-4-cyclohexene-1,2-dicarboxylate is obtained. The palladium-catalyzed dehydrogenation of the cycloadduct gives a 77.8 % yield of dibutyl phthalate. Dibutyl trans-cyclohexane-1,2-dicarboxylate could be formed in nearly 100 % yield under mild conditions by hydrogenation of the cycloadduct. Furthermore, fumaric acid and fumarate, with trans configurations, were found to be better dienophiles for this Diels-Alder reaction than maleic acid and maleate, with cis configuration, based on the experimental and computational results. This new route will pave the way for the production of environmental friendly plastic materials from plants. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Generation and exploitation of acyclic azomethine imines in chiral Brønsted acid catalysis

NASA Astrophysics Data System (ADS)

Hashimoto, Takuya; Kimura, Hidenori; Kawamata, Yu; Maruoka, Keiji

2011-08-01

Successful implementation of a catalytic asymmetric synthesis strategy to produce enantiomerically enriched compounds requires the adoption of suitable prochiral substrates. The combination of an azomethine imine electrophile with various nucleophiles could give straightforward access to a number of synthetically useful chiral hydrazines, but is used rarely. Here we report the exploitation of acyclic azomethine imines as a new type of prochiral electrophile. They can be generated in situ by the condensation of N‧-benzylbenzoylhydrazide with a variety of aldehydes in the presence of a catalytic amount of an axially chiral dicarboxylic acid. By trapping these electrophiles with alkyl diazoacetate or (diazomethyl)phosphonate nucleophiles, we produced a diverse array of chiral α-diazo-β-hydrazino esters and phosphonates with excellent enantioselectivities.

High abundances of oxalic, azelaic, and glyoxylic acids and methylglyoxal in the open ocean with high biological activity: Implication for secondary OA formation from isoprene

NASA Astrophysics Data System (ADS)

Bikkina, Srinivas; Kawamura, Kimitaka; Miyazaki, Yuzo; Fu, Pingqing

2014-05-01

Atmospheric dicarboxylic acids (DCA) are a ubiquitous water-soluble component of secondary organic aerosols (SOA), which can act as cloud condensation nuclei (CCN), affecting the Earth's climate. Despite the high abundances of oxalic acid and related compounds in the marine aerosols, there is no consensus on what controls their distributions over the open ocean. Marine biological productivity could play a role in the production of DCA, but there is no substantial evidence to support this hypothesis. Here we present latitudinal distributions of DCA, oxoacids and α-dicarbonyls in the marine aerosols from the remote Pacific. Their concentrations were found several times higher in more biologically influenced aerosols (MBA) than less biologically influenced aerosols. We propose isoprene and unsaturated fatty acids as sources of DCA as inferred from significantly higher abundances of isoprene-SOA tracers and azelaic acid in MBA. These results have implications toward the reassessment of climate forcing feedbacks of marine-derived SOA.

The tip and hidden part of the iceberg: Proteinogenic and non-proteinogenic aliphatic amino acids.

PubMed

Fichtner, Maximilian; Voigt, Kerstin; Schuster, Stefan

2017-01-01

Amino acids are the essential building blocks of proteins and, therefore, living organisms. While the focus often lies on the canonical or proteinogenic amino acids, there is also a large number of non-canonical amino acids to explore. Some of them are part of toxins or antibiotics in fungi, bacteria or animals (e.g. sponges). Some others operate at the translational level like an "undercover agent". Here we give an overview of natural aliphatic amino acids, up to a side chain length of five carbons, without rings and with an unmodified backbone, and have a closer look on each of them. Some of them are dehydro amino acids with double or even triple bonds. Moreover, we outline mathematical methods for enumerating the complete list of all potential aliphatic amino acids of a given chain length. This should be of interest for synthetic biology. Most non-proteinogenic amino acids are found within fungi, with particularly many produced by Amanita species as defence chemicals. Several are incorporated into peptide antibiotics. Some of the amino acids occur due to broad substrate specificity of the branched-chain amino acid synthesis pathways. A large variety of amino acids were also found in the Murchison meteorite. Non-proteinogenic amino acids are of interest for numerous medical applications: discovery of new antibiotics, support in designing synthetic antibiotics, improvement of protein and peptide pharmaceuticals by avoiding incorporation of non-canonical amino acids, study of toxic cyanobacteria and other applications. Copyright © 2016 Elsevier B.V. All rights reserved.

[Synthesis and biological activity of 2,3-secotriterpene acid mono- and diamides].

PubMed

Tolmacheva, I A; Igosheva, E V; Vikharev, Iu B; Grishko, V V; Savinova, O V; Boreko, E I; Eremin, V F

2013-01-01

Four types of amide (C3; C28; C3-C28) conjugates based on 2,3-seco-18alphaH-oleanane and 2,3-secolupane mono- and dicarboxylic acids were synthesized. The range of diamide derivatives was supplemented with C3-C3' and C28-C28' dicondensed amides with two A-secotriterpene backbones educed by reacting monocarboxylic A-secoacids with biogenic amino acid lysine. Compounds with inhibitory action against herpes virus reproduction (EC50 8.7 and 4.1 McM) were found among the synthesized mono- and diamide derivatives containing an ethyl-beta-alaninate fragment. It has been ascertained that diamide with ethyl-beta-alaninate fragment combines anti-herpes virus properties and anti-HIV activity (EC50 5.1 McM). For active compounds, the maximum non-toxic concentration (MNTC)/EC50 ratios ranges from 9.7 to 40.8. The synthesized amide conjugates do not exhibit any marked cytotoxic effects against human tumor cell lines rabdomiosarcoma RD TE32, A549 lung carcinoma and melanoma MS.

Study of structural, surface and hydrogen storage properties of boric acid mediated metal (sodium)-organic frameworks

NASA Astrophysics Data System (ADS)

Ozer, Demet; Köse, Dursun A.; Sahin, Onur; Oztas, Nursen A.

2018-04-01

Three boric acid mediated metal organic frameworks were synthesized by solution method with using succinic acid, fumaric acid and acetylene dicarboxylic acid as a ligand source and sodium as a metal source. The complexes were characterized by FT-IR, powder XRD, elemental analyses and single crystal measurements. The complexes with the formula, C4H18B2Na2O14, C4H16B2Na2O14 and C4H14B2Na2O14 were successfully obtained. BET surface area of complexes were calculated and found as 13.474 m2/g for catena-(tetrakis(μ2-hydroxo)-(μ2-trihydrogen borate)-(μ2-succinato)-di-sodium boric acid solvate), 1.692 m2/g for catena-(tetrakis(μ2-hydroxo)-(μ2-trihydrogen borate)-(μ2-fumarato)-di-sodium boric acid solvate) and 5.600 m2/g for catena-(tetrakis(μ2-hydroxo)-(μ2-trihydrogen borate)-(μ2-acetylenedicarboxylato)-di-sodium boric acid solvate). Hydrogen storage capacities of the complexes were also studied at 77 K 1 bar pressure and found as 0.108%, 0.033%, 0.021% by mass. When different ligands were used, the pore volume, pore width and surface area of the obtained complexes were changed. As a consequence, hydrogen storage capacities also changed.

pKa prediction from an ab initio bond length: part 3--benzoic acids and anilines.

PubMed

Harding, A P; Popelier, P L A

2011-06-21

The prediction of pK(a) from a single ab initio bond length has been extended to provide equations for benzoic acids and anilines. The HF/6-31G(d) level of theory is used for all geometry optimisations. Similarly to phenols (Part 2 of this series of publications), the meta-/para-substituted benzoic acids can be predicted from a single model constructed from one bond length. This model had an impressive RMSEP of 0.13 pK(a) units. The prediction of ortho-substituted benzoic acids required the identification of high-correlation subsets, where the compounds in the same subset have at least one of the same (e.g. halogens, hydroxy) ortho substituent. Two pK(a) equations are provided for o-halogen benzoic acids and o-hydroxybenzoic acids, where the RMSEP values are 0.19 and 0.15 pK(a) units, respectively. Interestingly, the bond length that provided the best model differed between these two high-correlation subsets. This demonstrates the importance of investigating the most predictive bond length, which is not necessarily the bond involving the acid hydrogen. Three high-correlation subsets were identified for the ortho-substituted anilines. These were o-halogen, o-nitro and o-alkyl-substituted aniline high-correlation subsets, where the RMSEP ranged from 0.23 to 0.44 pK(a) units. The RMSEP for the meta-/para-substituted aniline model was 0.54 pK(a) units. This value exceeded our threshold of 0.50 pK(a) units and was higher than both the m-/p-benzoic acids in this work and the m-/p-phenols (RMSEP = 0.43) of Part 2. Constructing two separate models for the meta- and para- substituted anilines, where RMSEP values of 0.63 and 0.33 pK(a) units were obtained respectively, revealed it was the meta-substituted anilines that caused the large RMSEP value. For unknown reasons the RMSEP value increased with the addition of a further twenty meta-substituted anilines to this model. The C-N bond always produced the best correlations with pK(a) for all the high-correlation subsets. A

Studies on antioxidant activity, volatile compound and fatty acid composition of different parts of Glycyrrhiza echinata L.

PubMed Central

Çakmak, Yavuz Selim; Aktumsek, Abdurrahman; Duran, Ahmet

2012-01-01

The essential oil compound, fatty acid composition and the in vitro antioxidant activity of the root and aerial of Glycyrrhiza echinata L., a medicinal plant growing in Turkey, have been studied. The antioxidant capacity tests were designed to evaluate the antioxidant activities of methanol extracts. Total phenolic and flavonoid concentrations of each extract were also determined by using both Folin-Ciocalteu reagent and aluminum chloride. The aerial part was found to possess the highest total phenolic content (146.30 ± 4.58 mg GAE/g) and total antioxidant capacity (175.33 ± 3.98 mg AE/g). The essential oil from root and aerial parts was analyzed by gas chromatography mass spectroscopy (GC-MS) systems. The major components identified were n-hexadecanoic acid, hexahydro farnesyl acetone, α-caryophyllen, hexanal and phytol. In fatty acid profiles of plant, palmitic, stearic, oleic and linoleic acid were detected as the main components. The results of this study have shown that the extracts G. echinata are suitable as a natural antioxidant and food supplement source for pharmacological and food industries due to their beneficial chemical composition and antioxidant capacity. PMID:27418901

Ceriporic acid B, an extracellular metabolite of Ceriporiopsis subvermispora, suppresses the depolymerization of cellulose by the Fenton reaction.

PubMed

Rahmawati, Noor; Ohashi, Yasunori; Watanabe, Takahito; Honda, Yoichi; Watanabe, Takashi

2005-01-01

The white rot fungus, Ceriporiopsis subvermispora, is able to degrade lignin in wood without intensive damage to cellulose. Since lignin biodegradation by white rot fungi proceeds by radical reactions, accompanied by the production of a large amount of Fe3+-reductant phenols and reductive radical species in the presence of iron ions, molecular oxygen, and H2O2, C. subvermispora has been proposed to possess a biological system which suppresses the production of a cellulolytic active oxygen species, *OH, by the Fenton reaction. In the present paper, we demonstrate that 1-nonadecene-2,3-dicarboxylic acid (ceriporic acid B), an extracellular metabolite of C. subvermispora, strongly inhibited *OH production and the depolymerization of cellulose by the Fenton reaction in the presence of iron ions, cellulose, H2O2, and a reductant for Fe3+, hydroquinone (HQ), at the physiological pH of the fungus.

Drugs acting on amino acid neurotransmitters.

PubMed

Meldrum, B S

1986-01-01

The most potent agents currently available for suppressing myoclonic activity in animals and humans act to enhance GABA-mediated inhibition and/or to diminish amino acid-induced excitation. Postsynaptic GABA-mediated inhibition plays an important role at the cortical level, diminishing the effect of augmented afferent activity and preventing pathologically enhanced output. Enhancement of GABAergic inhibition, principally at the cortical level but also at lower levels, by clonazepam and by valproate appears to be a predominant element in their antimyoclonic action. Studies in various animal models, including photically induced myoclonus in the baboon, P papio, indicate the value of other approaches to enhancing GABA-mediated inhibition. Among such approaches meriting evaluation in humans are inhibition of GABA-transaminase activity by gamma-vinyl GABA and action at some of the benzodiazepine receptors to enhance the action of GABA, as by the novel anticonvulsant beta-carbolines. Excitatory transmission mediated by dicarboxylic amino acids appears to play a role in myoclonus, especially at the spinal level, but also in the brainstem, cerebellum, basal ganglia, and cortex. Among various novel agents that act at the postsynaptic receptor site to antagonize such excitation, those specifically blocking excitation induced by aspartate and/or NMDA prevent myoclonic activity in a wide range of animal models. Further research is required before such agents can be evaluated in humans.

Zn(II) coordination polymers with flexible V-shaped dicarboxylate ligand: Syntheses, helical structures and properties

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

Li, Lin; Liu, Chong-Bo, E-mail: cbliu@nchu.edu.cn; Yang, Gao-Shan

2015-11-15

Hydrothermal reactions of 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H{sub 2}L) and zinc ions in the presence of N-donor ancillary ligands afford four novel coordination polymers, namely, [Zn{sub 2}(μ{sub 2}-OH)(μ{sub 4}-O){sub 0.5}(L)]·0.5H{sub 2}O (1), [Zn(L)(2,2′-bipy)(H{sub 2}O)] (2), [Zn{sub 3}(L){sub 3}(phen){sub 2}]·H{sub 2}O (3) and [Zn{sub 2}(L){sub 2}(4,4′-bipy)] (4) (2,2′-bipy=2,2′-bipyridine; 4,4′-bipy=4,4′-bipyridine; phen=1,10-phenanthroline). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complex 1 shows a 3-D clover framework consisting of [Zn{sub 4}(µ{sub 4}-O)(µ{sub 2}-OH){sub 2}]{sup 4+} clusters, and exhibits a novel (3,8)-connected topological net with the Schläfli symbol of {3·4·5}{sub 2}{3"4·4"4·5"2·6"6·7"1"0·8"2}, andmore » contains double-stranded and two kinds of meso-helices. 2 displays a helical chain structure, which is further extended via hydrogen bonds into a 3-D supramolecular structure with meso-helix chains. 3 displays a 2-D {4"4·6"2} parallelogram structure, which is further extended via hydrogen bonds into a 3-D supramolecular structure with single-stranded helical chains. 4 shows a 2-D {4"4·6"2} square structure with left- and right-handed helical chains. Moreover, the luminescent properties of 1–4 have been investigated. - Graphical abstract: Four new Zn(II) coordination polymers with helical structures based on flexible V-shaped dicarboxylate ligand have been synthesized and structurally characterized. Photoluminescent properties have been investigated. - Highlights: • Four novel Zn(II) coordination polymers with V-shaped ligand were characterized. • Complexes 1–4 show diverse intriguing helical characters. • Fluorescence properties of complexes 1–4 were investigated.« less

[Pollution characteristics of organic acids in atmospheric particles during haze periods in autumn in Guangzhou].

PubMed

Tan, Ji-hua; Zhao, Jing-ping; Duan, Jing-chun; Ma, Yong-liang; He, Ke-bin; Yang, Fu-mo

2013-05-01

Total suspended particles (TSP), collected during a typical haze period in Guangzhou, were analyzed for the fatty acids (C12-C30) and low molecular weight dicarboxylic acids (C3-C9) using gas chromatography/mass spectrometry (GC/MS). The results showed that the concentration of total fatty and carboxylic acids was pretty high during the haze episode. The ratios of fatty acids and carboxylic acids in haze to those in normal days were 1.9 and 2.5, respectively. During the episode of the increasing pollution, the fatty acids and carboxylic acids at night (653 ng x m(-3)) was higher than that (487 ng x m(-3)) in days. After that, the level of fatty acids and carboxylic acids in days (412 ng x m(-3)) was higher than that (336 ng x m(-3)) at night. In general, the time-series of fatty acids and carboxylic acids was similar to that of the air particle and carbonaceous species, however, the trend of the ratio of fatty acids and carboxylic acids to organic carbon was opposite to that of air particle and carbonaceous species. This ratio decreased with the increase of the concentration of air particle and after the night of 27th, the ratio increased with the decrease in the concentration of air particle. The results showed that haze pollution had a significant inhibitory effect on the enrichment of fatty and carboxylic acids. Based on the ratio of malonate to succinate (C3/C4), it could be found that primary sources contribute more to the atmospheric fatty and carboxylic acids during the autumn haze pollution periods in Guangzhou.

pH-independent immediate release polymethacrylate formulations--an observational study.

PubMed

Claeys, Bart; Vandeputte, Reinout; De Geest, Bruno G; Remon, Jean Paul; Vervaet, Chris

2016-01-01

Using Eudragit® E PO (EudrE) as a polymethacrylate carrier, the aim of the study was to develop a pH-independent dosage form containing ibuprofen (IBP) as an active compound via chemical modification of the polymer (i.e. quaternization of amine function) or via the addition of dicarboxylic acids (succinic, glutaric and adipic acid) to create a pH micro-environment during dissolution. Biconvex tablets (diameter: 10 mm; height: 5 mm) were produced via hot melt extrusion and injection molding. In vitro dissolution experiments revealed that a minimum of 25% of quaternization was sufficient to partially (up to pH 5) eliminate the pH-dependent effect of the EudrE/IBP formulation. The addition of dicarboxylic acids did not alter IBP release in a pH 1 and 3 medium as the dimethyl amino groups of EudrE are already fully protonated, while in a pH 5 solvent IBP release was significantly improved (cf. from 0% to 92% release after 1 h dissolution experiments upon the addition of 20 wt.% succinic acid). Hence, both approaches resulted in a pH-independent (up to pH 5) immediate release formulation. However, the presence of a positively charged polymer induced stability issues (recrystallization of API) and the formulations containing dicarboxylic acids were classified as mechanically unstable. Hence, further research is needed to obtain a pH-independent immediate release formulation while using EudrE as a polmethacrylate carrier.

Size distributions of dicarboxylic acids, ketoacids, α-dicarbonyls, sugars, WSOC, OC, EC and inorganic ions in atmospheric particles over Northern Japan: implication for long-range transport of Siberian biomass burning and East Asian polluted aerosols

NASA Astrophysics Data System (ADS)

Agarwal, S.; Aggarwal, S. G.; Okuzawa, K.; Kawamura, K.

2010-03-01

To better understand the size-segregated chemical composition of aged organic aerosols in the western Pacific rim, day- and night-time aerosol samples were collected in Sapporo, Japan during summer 2005 using Andersen impactor sampler with 5 size bins: <1.1, 1.1-2.0, 2.0-3.3, 3.3-7.0, >7.0 μm. Samples were analyzed for the molecular compositions of dicarboxylic acids, ketoacids, α-dicarbonyls, and sugars, together with water-soluble organic carbon (WSOC), organic carbon (OC), elemental carbon (EC) and inorganic ions. Based on the analyses of backward trajectory and chemical tracers, we found that during campaign, the air masses were arrived from Siberia (biomass burning source region) on 8-9 August, China (anthropogenic source region) on 9-10 August and from the East China Sea/Sea of Japan (a mixed source receptor region) on 10-11 August. Most of the diacids, ketoacids, dicarbonyls, levoglucosan, WSOC, and inorganic ions, i.e., SO42-, NH42+ and K+ were enriched in fine particles (PM1.1) whereas Ca2+, Mg2+ and Cl- peaked in coarse sizes (>1.1 μm). Interestingly, OC, most sugar compounds and NO4

[The content of phenolic acids in the edible parts of selected varieties of apples].

PubMed

Malik, Agnieszka; Kiczorowska, Bozena; Zdyb, Justyna

2009-01-01

Fruits and vegetables are essential sources of many nutritive substances which are necessary for normal function of the organism. One of the mostly consumed fruits in many European countries, including Poland is apples. The prohealthy properties of apples are associated with the contents of polyphenolic compounds, thus including in parts phenolic acids which have antioxidant properties. The concentration of these compounds depends on many factors such as variety climate and soil conditions, maturity as well as agro technical operations. The aim of this investigation was to compare the concentrations of phenolic acids and epicatechin in the varieties of apple Champion and Jonica, which were collected from different orchards around Lublin. The phenolic compounds were assayed using a Symmetry column carrier RP-C18 (Waters) integrated with a high pressure liquid chromatography apparatus. The dominant phenolic acids found in the Champion variety was chlorogenic acid, whereas in the Jonica variety, chlorogenic and homovanilic acids were the dominate once. The highest concentrations of chlorogenic acid was detected in the pulp of an apple (Jonica variety) collected from the orchards around the cities of Puławy and Lublin, whereas homovanilic acid was the highest in the other samples collected from the orchards in the vicinity of Stryjno and Góry Markuszowskie. Among the Jonica and Champion varieties of apples collected from various orchards in the vicinity of Lublin, the highest content of epicatechin (13,12 mg/kg) was found in the pulps of Champions variety collected in Puławy. In general, the Champion variety was the best source of phenolic acids and epicatechin compared to the Jonica variety independent of the harvest zone.

New effective azelaic acid liposomal gel formulation of enhanced pharmaceutical bioavailability.

PubMed

Burchacka, E; Potaczek, P; Paduszyński, P; Karłowicz-Bodalska, K; Han, T; Han, S

2016-10-01

Azelaic acid is a naturally occurring saturated C9-dicarboxylic acid which has been shown to be effective in the treatment of comedonal acne and inflammatory acne, as well as hiperpigmentary skin disorders. The aim of the present study is to compare new developed liposomal hydrogel (lipogel) and commercially available product in terms of the active substance-azelaic acid bioavailability. Topical formulations were evaluated for physical parameters, such as pH measurement, organoleptic evaluation and liposome size analysis in lipogel formulation. In addition, studies were performed on in vitro antimicrobial preservation, stability and accumulation in the stratum corneum according to guidelines established by European Pharmacopoeia and International Conferences on Harmonisation. The new formula for liposomal gel with azelaic acid has the stability required for pharmaceutical preparations. Moreover, presented formulation F2 reveals a very high accumulation (187.5μg/cm 2 ) of an active substance in the stratum corneum, which results in opportunity to decrease of the API content to 10% in comparison to a reference formula: commercially available cream with 20% of azelaic acid. The study reveals that the final formula of lipogel F2 with azelaic acid had acceptable physical parameters that showed that they were compatible with the skin and in addition this formulation passed stability studies. In vitro antimicrobial preservation studies showed that the formulated lipogel F2 showed strong antibacterial activity; thus, no preservatives were added to the final composition of the preparation. The present study concludes that the formulated lipogel F2 with azelaic acid is stable, efficient in antimicrobial preservation and reveals improved active substance bioavailability. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Chemical composition and antibacterial properties of essential oil and fatty acids of different parts of Ligularia persica Boiss

PubMed Central

Mohadjerani, Maryam; Hosseinzadeh, Rahman; Hosseini, Maryam

2016-01-01

Objective: The objective of this research was to investigate the chemical composition and antibacterial activities of the fatty acids and essential oil from various parts of Ligularia persica Boiss (L. persica) growing wild in north of Iran. Materials and Methods: Essential oils were extracted by using Clevenger-type apparatus. Antibacterial activity was tested on two Gram-positive and two Gram-negative bacteria by using micro dilution method. Results: GC and GC∕MS analysis of the oils resulted in detection of 94%, 96%, 93%, 99% of the total essential oil of flowers, stems, roots and leaves, respectively. The main components of flowers oil were cis-ocimene (15.4%), β-myrcene (4.4%), β-ocimene (3.9%), and γ-terpinene (5.0%). The major constituents of stems oil were β-phellandrene (5.4%), β-cymene (7.0%), valencene (3.9%). The main compounds of root oil were fukinanolid (17.0%), α-phellandrene (11.5%) and Β-selinene (5.0%) and in the case of leaves oil were cis-ocimene (4.8%), β-ocimene (4.9%), and linolenic acid methyl ester (4.7%). An analysis by GC-FID and GC-MS on the fatty-acid composition of the different parts of L. persica showed that major components were linoleic acid (11.3-31.6%), linolenic acid (4.7-21.8%) and palmitic acid (7.2-23.2%). Saturated fatty acids were found in lower amounts than unsaturated ones. The least minimum inhibition concentration (MIC) of the L. persica was 7.16 μg/ml against Pseudomonas aeruginosa. Conclusion: Our study indicated that the essential oil from L. persica stems and flowers showed high inhibitory effect on the Gram negative bacteria. The results also showed that fatty acids from the stems and leaves contained a high amount of poly-unsaturated fatty acids (PUFAs). PMID:27462560

Azelaic acid modulates the inflammatory response in normal human keratinocytes through PPARgamma activation.

PubMed

Mastrofrancesco, Arianna; Ottaviani, Monica; Aspite, Nicaela; Cardinali, Giorgia; Izzo, Enzo; Graupe, Klaus; Zouboulis, Christos C; Camera, Emanuela; Picardo, Mauro

2010-09-01

Azelaic acid (AzA), a nine-carbon dicarboxylic acid, is an agent for the topical treatment of acne. It has also been shown to be effective in rosacea; however, the mechanism of action has not been clarified. Because inflammation is a common feature of both conditions, we investigated the effects of azelaic acid on the inflammatory response of normal human keratinocytes to ultraviolet B light, which is a photosensitizer agent in rosacea. AzA, at 20 mM, a concentration achievable following topical application of a 15% gel, suppresses ultraviolet B light-induced interleukins-1beta, -6 and tumor necrosis factor-alpha mRNA expression and protein secretion. Mechanistically, azelaic acid significantly reduced the ultraviolet B light-induced nuclear translocation of nuclear factor kB p65 subunit and the phosphorylation of the p38 mitogen and stress-activated protein kinase. Moreover, as peroxisome proliferators-activated receptor gamma, (PPARgamma) which has a crucial role in the control of inflammation, is activated by fatty acids and products of lipid peroxidation, we further investigated the effect of azelaic acid on the expression of this nuclear receptor. AzA induced peroxisome proliferators-activated receptor-gamma mRNA and its transcriptional activity. The PPARgamma antagonist GW9662 abrogated the inhibitory effects of AzA on the UVB-induced pro-inflammatory cytokines release and on the cell proliferation. Our study provides new insights into the molecular mechanisms of the activity of azelaic acid and lands additional evidences for its therapeutic effects on inflammatory skin diseases, such as rosacea.

Study on HCl Driving Force for the Reaction of NaCl-Maleic Acid Mixing Single Droplet Using Micro-FTIR Spectroscopy

NASA Astrophysics Data System (ADS)

He, Xiang; Zhang, Yunhong

2016-04-01

Chemical aging is the one of the most important physicochemical process in atmospheric aerosols. Mixing of sea salt and water-soluble organic components has profound effects on the volatile characteristic and evolving chemical composition of the anthropogenic origin aerosols, which are poorly understood. In this study, the chemical reaction behavior of the mixture of NaCl and maleic acid (H2MA) micron-level single droplet was investigated using a gas-flow system combined with microscopic Fourier transform infrared (micro-FTIR) spectrometer over the range of relative humidity (63˜95% RH) for the first time. The results showed that the mixture of NaCl and H2MA single droplet could react to form monosodium maleate salt (NaHMA) at the constant RH from the characterization of the FTIR. The reaction is a result of an acid displacement reaction R1, which is driven by high volatility of the HCl product. NaCl(aq)+H2MA(aq)=NaHMA(aq)+HCl(aq,g) (R1) According to the change tendency of the absorbance values of 1579 cm-1 COO- stretching band of the NaHMA dependent upon reaction times at different RHs, the growth range of the trend which could lead to the faster reaction rate was obvious at lower RH. The water content of the droplet was also more likely to reduce rapidly with the loss of the RH from the absorbance changes of 3400 cm-1H2O stretching band dependent upon reaction times. These may be due to irreversible evaporation of HCl gas which is the main driving force for this type of reaction and the NaHMA is a less hygroscopic component compared to H2MA. And the HCl gas is more likely to evaporate faster from the single droplet and promote the reaction rate and the consumption of water content at lower RH. These results could help in understanding the chemical conversion processes of water-soluble dicarboxylic acids to dicarboxylate salts, as well as the consumption of Cl in sea salt aerosols by organic acids in the atmosphere.

Three new 5-fold interpenetrating diamondoid frameworks constructed by rigid diimidazole and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Huo, Jianqiang; Yan, Shuai; Li, Haiqiang; Yu, Donghui; Arulsamy, Navamoney

2018-03-01

A series of three-dimensional coordination polymers, namely, [Cd(BIMB)(SCA)]n (1), [M(BIMB)(trans-CHDC)]n (2, M = Cd2+; 3, M = Co2+), where BIMB = 1,4-di(1H-imidazol-1-yl)benzene, SCA2- = succinate dianion, CHDC2- = cyclohexane-1,4-dicarboxylate dianion) are synthesized hydro/solvatothermal methods. The products are characterized by elemental analysis and single-crystal X-ray diffraction data. Both the dianion and BIMB bridge different pairs of the metal ions, the three complexes are polymeric and their three-dimensional topology feature a diamond-like metal-organic framework (MOF). Owing to the length of the two bridging ligands, moderate size voids are formed in the diamondoid networks. However, the voids are filled by mutual interpenetration of four independent equivalent frameworks in a 5-fold interpenetrating architecture, and there is no sufficient void volume available for any guest molecules. The phase purity and thermal stability of the compounds are verified by powder X-ray diffraction (PXRD) and thermogravimetric (TG) data. The solid-state fluorescence spectra for the 3d10 Cd2+ MOF's 1 and 2 reveal significant enhancement in their emission intensities in comparison to the non-metallated BIMB. The enhanced emission is attributed to perturbation of intra-ligand emission states due to Cd2+ coordination.

Dicarboxylic acids, oxoacids, benzoic acid, α-dicarbonyls, WSOC, OC, and ions in spring aerosols from Okinawa Island in the western North Pacific Rim: size distributions and formation processes

NASA Astrophysics Data System (ADS)

Deshmukh, D. K.; Kawamura, K.; Lazaar, M.; Kunwar, B.; Boreddy, S. K. R.

2015-09-01

Size-segregated aerosols (9-stages from < 0.43 to > 11.3 μm in diameter) were collected at Cape Hedo, Okinawa in spring 2008 and analyzed for water-soluble diacids (C2-C12), ω-oxoacids (ωC2-ωC9), pyruvic acid, benzoic acid and α-dicarbonyls (C2-C3) as well as water-soluble organic carbon (WSOC), organic carbon (OC) and major ions. In all the size-segregated aerosols, oxalic acid (C2) was found as the most abundant species followed by malonic and succinic acids whereas glyoxylic acid (ωC2) was the dominant oxoacid and glyoxal (Gly) was more abundant than methylglyoxal. Diacids (C2-C5), ωC2 and Gly as well as WSOC and OC peaked at 0.65-1.1 μm in fine mode whereas azelaic (C9) and 9-oxononanoic (ωC9) acids peaked at 3.3-4.7 μm in coarse mode. Sulfate and ammonium are enriched in fine mode whereas sodium and chloride are in coarse mode. These results imply that water-soluble species in the marine aerosols could act as cloud condensation nuclei (CCN) to develop the cloud cover over the western North Pacific Rim. The organic species are likely produced by a combination of gas-phase photooxidation, and aerosol-phase or in-cloud processing during long-range transport. The coarse mode peaks of malonic and succinic acids were obtained in the samples with marine air masses, suggesting that they may be associated with the reaction on sea salt particles. Bimodal size distributions of longer-chain diacid (C9) and oxoacid (ωC9) with a major peak in the coarse mode suggest their production by photooxidation of biogenic unsaturated fatty acids via heterogeneous reactions on sea salt particles.

Two-dimensional Zn(II) and one-dimensional Co(II) coordination polymers based on benzene-1,4-dicarboxylate and pyridine ligands.

PubMed

Zhou, Li-Juan; Han, Chang-Bao; Wang, Yu-Ling

2016-02-01

Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene-1,4-dicarboxylic acid (H2BDC) and pyridine (py) with Zn(II) or Co(II) yielded two new coordination polymers, namely, poly[(μ4-benzene-1,4-dicarboxylato-κ(4)O:O':O'':O''')(pyridine-κN)zinc(II)], [Zn(C8H4O2)(C5H5N)]n, (I), and catena-poly[aqua(μ3-benzene-1,4-dicarboxylato-κ(3)O:O':O'')bis(pyridine-κN)cobalt(II)], [Co(C8H4O2)(C5H5N)2(H2O)]n, (II). In compound (I), the Zn(II) cation is five-coordinated by four carboxylate O atoms from four BDC(2-) ligands and one pyridine N atom in a distorted square-pyramidal coordination geometry. Four carboxylate groups bridge two Zn(II) ions to form centrosymmetric paddle-wheel-like Zn2(μ2-COO)4 units, which are linked by the benzene rings of the BDC(2-) ligands to generate a two-dimensional layered structure. The two-dimensional layer is extended into a three-dimensional supramolecular structure with the help of π-π stacking interactions between the aromatic rings. Compound (II) has a one-dimensional double-chain structure based on Co2(μ2-COO)2 units. The Co(II) cations are bridged by BDC(2-) ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC(2-) ligands, one water O atom and two pyridine N atoms. Interchain O-H...O hydrogen-bonding interactions link these chains to form a three-dimensional supramolecular architecture.

Facile and Promising Method for Michael Addition of Indole and Pyrrole to Electron-Deficient trans-β-Nitroolefins Catalyzed by a Hydrogen Bond Donor Catalyst Feist's Acid and Preliminary Study of Antimicrobial Activity

PubMed Central

Al Majid, Abdullah M. A.; Islam, Mohammad Shahidul; Barakat, Assem; Al-Agamy, Mohamed H. M.; Naushad, Mu.

2014-01-01

The importance of cooperative hydrogen-bonding effects has been demonstrated using novel 3-methylenecyclopropane-1,2-dicarboxylic acid (Feist's acid (FA)) as hydrogen bond donor catalysts for the addition of indole and pyrrole to trans-β-nitrostyrene derivatives. Because of the hydrogen bond donor (HBD) ability, Feist's acid (FA) has been introduced as a new class of hydrogen bond donor catalysts for the activation of nitroolefin towards nucleophilic substitution reaction. It has effectively catalyzed the Michael addition of indoles and pyrrole to β-nitroolefins under optimum reaction condition to furnish the corresponding Michael adducts in good to excellent yields (up to 98%). The method is general, atom-economical, convenient, and eco-friendly and could provide excellent yields and regioselectivities. Some newly synthesized compounds were for examined in vitro antimicrobial activity and their preliminary results are reported. PMID:24574906

Characterization of oryza sativa acyl activating enzyme3 (OsAAE3)

USDA-ARS?s Scientific Manuscript database

Oxalate, the smallest of the dicarboxylic acids, is produced in many plants. This acid has been shown to play an important role in both plant physiology and defense, specifically in regards to metal detoxification, calcium regulation, sucking and chewing insect deterrence, and the production of calc...

Products of Dark CO2 Fixation in Pea Root Nodules Support Bacteroid Metabolism 1

PubMed Central

Rosendahl, Lis; Vance, Carroll P.; Pedersen, Walther B.

1990-01-01

Products of the nodule cytosol in vivo dark [14C]CO2 fixation were detected in the plant cytosol as well as in the bacteroids of pea (Pisum sativum L. cv “Bodil”) nodules. The distribution of the metabolites of the dark CO2 fixation products was compared in effective (fix+) nodules infected by a wild-type Rhizobium leguminosarum (MNF 300), and ineffective (fix−) nodules of the R. leguminosarum mutant MNF 3080. The latter has a defect in the dicarboxylic acid transport system of the bacterial membrane. The 14C incorporation from [14C]CO2 was about threefold greater in the wild-type nodules than in the mutant nodules. Similarly, in wild-type nodules the in vitro phosphoenolpyruvate carboxylase activity was substantially greater than that of the mutant. Almost 90% of the 14C label in the cytosol was found in organic acids in both symbioses. Malate comprised about half of the total cytosol organic acid content on a molar basis, and more than 70% of the cytosol radioactivity in the organic acid fraction was detected in malate in both symbioses. Most of the remaining 14C was contained in the amino acid fraction of the cytosol in both symbioses. More than 70% of the 14C label found in the amino acids of the cytosol was incorporated in aspartate, which on a molar basis comprised only about 1% of the total amino acid pool in the cytosol. The extensive 14C labeling of malate and aspartate from nodule dark [14C]CO2 fixation is consistent with the role of phosphoenolpyruvate carboxlase in nodule dark CO2 fixation. Bacteroids from the effective wild-type symbiosis accumulated sevenfold more 14C than did the dicarboxylic acid transport defective bacteroids. The bacteroids of the effective MNF 300 symbiosis contained the largest proportion of the incorporated 14C in the organic acids, whereas ineffective MNF 3080 bacteroids mainly contained 14C in the amino acid fraction. In both symbioses a larger proportion of the bacteroid 14C label was detected in malate and aspartate

Seasonal and spatial variability of the organic matter-to-organic carbon mass ratios in Chinese urban organic aerosols and a first report of high correlations between aerosol oxalic acid and zinc

NASA Astrophysics Data System (ADS)

Xing, L.; Fu, T.-M.; Cao, J. J.; Lee, S. C.; Wang, G. H.; Ho, K. F.; Cheng, M.-C.; You, C.-F.; Wang, T. J.

2013-01-01

We calculated the organic matter to organic carbon mass ratios (OM/OC mass ratios) in PM2.5 collected from 14 Chinese cities during summer and winter of 2003 and analyzed the causes for their seasonal and spatial variability. The OM/OC mass ratios were calculated two ways. Using a mass balance method, the calculated OM/OC mass ratios averaged 1.92 ± 0.39 yr-round, with no significant seasonal or spatial variation. The second calculation was based on chemical species analyses of the organic compounds extracted from the PM2.5 samples using dichloromethane/methanol and water. The calculated OM/OC mass ratio in summer was relatively high (1.75 ± 0.13) and spatially-invariant, due to vigorous photochemistry and secondary OA production throughout the country. The calculated OM/OC mass ratio in winter (1.59 ± 0.18) was significantly lower than that in summer, with lower values in northern cities (1.51 ± 0.07) than in southern cities (1.65 ± 0.15). This likely reflects the wider usage of coal for heating purposes in northern China in winter, in contrast to the larger contributions from biofuel and biomass burning in southern China in winter. On average, organic matters constituted 36% and 34% of Chinese urban PM2.5 mass in summer and winter, respectively. We reported, for the first time, high correlations between Zn and oxalic acid in Chinese urban aerosols in summer. This is consistent with the formation of stable Zn oxalate complex in the aerosol phase previously proposed by Furukawa and Takahashi (2011). We found that many other dicarboxylic acids were also highly correlated with Zn in the summer Chinese urban aerosol samples, suggesting that they may also form stable organic complexes with Zn. Such formation may have profound implications for the atmospheric abundance and hygroscopic property of aerosol dicarboxylic acids.

Vibrational studies in aqueous solutions. Part II. The acid oxalate ion and oxalic acid

NASA Astrophysics Data System (ADS)

Shippey, T. A.

1980-08-01

Assignments for oxalic acid in solution are re-examined. A detailed assignment of the IR and Raman spectra of the acid oxalate ion is presented for the first time. Raman spectroscopy is used to study the first ionization of oxalic acid.

Isotherm-Based Thermodynamic Models for Solute Activities of Organic Acids with Consideration of Partial Dissociation.

PubMed

Nandy, Lucy; Ohm, Peter B; Dutcher, Cari S

2016-06-23

Organic acids make up a significant fraction of the organic mass in atmospheric aerosol particles. The calculation of gas-liquid-solid equilibrium partitioning of the organic acid is therefore critical for accurate determination of atmospheric aerosol physicochemical properties and processes such as new particle formation and activation to cloud condensation nuclei. Previously, an adsorption isotherm-based statistical thermodynamic model was developed for capturing solute concentration-activity relationships for multicomponent aqueous solutions over the entire concentration range (Dutcher et al. J. Phys. Chem. C/A 2011, 2012, 2013), with model parameters for energies of adsorption successfully related to dipole-dipole electrostatic forces in solute-solvent and solvent-solvent interactions for both electrolytes and organics (Ohm et al. J. Phys. Chem. A 2015). However, careful attention is needed for weakly dissociating semivolatile organic acids. Dicarboxylic acids, such as malonic acid and glutaric acid are treated here as a mixture of nondissociated organic solute (HA) and dissociated solute (H(+) + A(-)). It was found that the apparent dissociation was greater than that predicted by known dissociation constants alone, emphasizing the effect of dissociation on osmotic and activity coefficient predictions. To avoid additional parametrization from the mixture approach, an expression was used to relate the Debye-Hückel hard-core collision diameter to the adjustable solute-solvent intermolecular distance. An improved reference state treatment for electrolyte-organic aqueous mixtures, such as that observed here with partial dissociation, has also been proposed. This work results in predictive correlations for estimation of organic acid and water activities for which there is little or no activity data.

Positional isomeric tunable two Co(II) 6-connected 3-D frameworks with pentanuclear to binuclear units: structures, ion-exchange and magnetic properties.

PubMed

Han, Min-Le; Duan, Ya-Ping; Li, Dong-Sheng; Wang, Hai-Bin; Zhao, Jun; Wang, Yao-Yu

2014-11-07

Two new Co(II) based metal-organic frameworks, namely {[Co5(μ3-OH)2(m-pda)3(bix)4]·2ClO4}n (1) and {[Co2(p-pda)2(bix)2(H2O)]·H2O}n (2), were prepared by hydrothermal reactions of Co(II) salt with two isomeric dicarboxyl tectons 1,3-phenylenediacetic acid (m-pda) and 1,4-phenylenediacetic acid (p-pda), along with 1,3-bis(imidazol-L-ylmethyl)benzene (bix). Both complexes 1 and 2 have been characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). 1 shows a 6-connected 3-D pcu cationic framework with pentanuclear [Co5(μ3-OH)2(COO)6(bix)2](2+) units, while 2 exhibits a 6-connected 3-D msw net based on [Co2(μ2-H2O)(COO)2](2+) clusters. The results indicate that the different dispositions of the carboxylic groups of dicarboxylates have an important effect on the overall coordination frameworks. Perchlorate anions in 1 can be partly exchanged by thiocyanate and azide anions, however they are unavailable to nitrate anions. Magnetic susceptibility measurements indicate that both 1 and 2 show weak antiferromagnetic interactions between the adjacent Co(II) ions.

Dicarboxylic acids, oxoacids, benzoic acid, α-dicarbonyls, WSOC, OC, and ions in spring aerosols from Okinawa Island in the western North Pacific Rim: size distributions and formation processes

NASA Astrophysics Data System (ADS)

Deshmukh, Dhananjay K.; Kawamura, Kimitaka; Lazaar, Manuel; Kunwar, Bhagawati; Boreddy, Suresh K. R.

2016-04-01

Size-segregated aerosols (nine stages from < 0.43 to > 11.3 µm in diameter) were collected at Cape Hedo, Okinawa, in spring 2008 and analyzed for water-soluble diacids (C2-C12), ω-oxoacids (ωC2-ωC9), pyruvic acid, benzoic acid, and α-dicarbonyls (C2-C3) as well as water-soluble organic carbon (WSOC), organic carbon (OC), and major ions (Na+, NH4+, K+, Mg2+, Ca2+, Cl-, NO3-, SO42-, and MSA-). In all the size-segregated aerosols, oxalic acid (C2) was found to be the most abundant species, followed by malonic and succinic acids, whereas glyoxylic acid (ωC2) was the dominant oxoacid and glyoxal (Gly) was more abundant than methylglyoxal. Diacids (C2-C5), ωC2, and Gly as well as WSOC and OC peaked at fine mode (0.65-1.1 µm) whereas azelaic (C9) and 9-oxononanoic (ωC9) acids peaked at coarse mode (3.3-4.7 µm). Sulfate and ammonium were enriched in fine mode, whereas sodium and chloride were in coarse mode. Strong correlations of C2-C5 diacids, ωC2 and Gly with sulfate were observed in fine mode (r = 0.86-0.99), indicating a commonality in their secondary formation. Their significant correlations with liquid water content in fine mode (r = 0.82-0.95) further suggest an importance of the aqueous-phase production in Okinawa aerosols. They may also have been directly emitted from biomass burning in fine mode as supported by strong correlations with potassium (r = 0.85-0.96), which is a tracer of biomass burning. Bimodal size distributions of longer-chain diacid (C9) and oxoacid (ωC9) with a major peak in the coarse mode suggest that they were emitted from the sea surface microlayers and/or produced by heterogeneous oxidation of biogenic unsaturated fatty acids on sea salt particles.

Keloids in rural black South Africans. Part 2: dietary fatty acid intake and total phospholipid fatty acid profile in the blood of keloid patients.

PubMed

Louw, L; Dannhauser, A

2000-11-01

In the second part of this study, emphasis is placed on nutritional intakes (fatty acids and micronutrients) and fatty acid intake and metabolism in the blood, respectively, according to a combined 24 h recall and standardized food frequency questionnaire analyses of keloid prone patients (n=10), compared with normal black South Africans (n=80), and total phospholipid blood (plasma and red blood cell ) analyses of keloid patients (n=20), compared with normal individuals (n=20). Lipid extraction and fractionation by standard procedures, total phospholipid (TPL) separation with thin layer chromatography, and fatty acid methyl ester analyses with gas liquid chromatography techniques were used. Since nutrition may play a role in several disease disorders, the purpose of this study was to confirm or refute a role for essential fatty acids (EFAs) in the hypothesis of keloid formations stated in part 1 of this study. (1)According to the Canadian recommendation (1991), we observed that in keloid patients linoleic acid (LA) and arachidonic acid (AA) dietary intakes, as EFAs of the omega-6-series, are higher than the recommended 7-11 g/d. However, the a-linolenic acid (ALA), eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) dietary intakes, as EFAs of the omega-3 series, are lower than the recommendation of 1.1-1.5 g/d. This was also the case in the control group, where a higher dietary intake of the omega-6 fatty acids and a slightly lower dietary intake of the omega-3 fatty acids occurred. Thus, we confirm a high dietary intake of LA (as a product of organ meats, diary products and many vegetable oils) and AA (as a product of meats and egg yolks), as well as lower dietary intakes of ALA (as a product of grains, green leafy vegetables, soy oil, rapeseed oil and linseed), and EPA and DHA (as products of marine oils). Lower micronutrient intakes than the recommended dietary allowances were observed in the keloid group that may influence EFA metabolism and/or collagen

Seasonal and spatial variability of the OM/OC mass ratios and high regional correlation between oxalic acid and zinc in Chinese urban organic aerosols

NASA Astrophysics Data System (ADS)

Xing, L.; Fu, T.-M.; Cao, J. J.; Lee, S. C.; Wang, G. H.; Ho, K. F.; Cheng, M.-C.; You, C.-F.; Wang, T. J.

2013-04-01

We calculated the organic matter to organic carbon mass ratios (OM/OC mass ratios) in PM2.5 collected from 14 Chinese cities during summer and winter of 2003 and analyzed the causes for their seasonal and spatial variability. The OM/OC mass ratios were calculated two ways. Using a mass balance method, the calculated OM/OC mass ratios averaged 1.92 ± 0.39 year-round, with no significant seasonal or spatial variation. The second calculation was based on chemical species analyses of the organic compounds extracted from the PM2.5 samples using dichloromethane/methanol and water. The calculated OM/OC mass ratio in summer was relatively high (1.75 ± 0.13) and spatially-invariant due to vigorous photochemistry and secondary organic aerosol (OA) production throughout the country. The calculated OM/OC mass ratio in winter (1.59 ± 0.18) was significantly lower than that in summer, with lower values in northern cities (1.51 ± 0.07) than in southern cities (1.65 ± 0.15). This likely reflects the wider usage of coal for heating purposes in northern China in winter, in contrast to the larger contributions from biofuel and biomass burning in southern China in winter. On average, organic matter constituted 36% and 34% of Chinese urban PM2.5 mass in summer and winter, respectively. We report, for the first time, a high regional correlation between Zn and oxalic acid in Chinese urban aerosols in summer. This is consistent with the formation of stable Zn oxalate complex in the aerosol phase previously proposed by Furukawa and Takahashi (2011). We found that many other dicarboxylic acids were also highly correlated with Zn in the summer Chinese urban aerosol samples, suggesting that they may also form stable organic complexes with Zn. Such formation may have profound implications for the atmospheric abundance and hygroscopic properties of aerosol dicarboxylic acids.

Assembly and property research on seven 0D-3D complexes derived from imidazole dicarboxylate and 1,2-bi(pyridin-4-yl)ethene

NASA Astrophysics Data System (ADS)