78 FR 70878 - Octadecanoic Acid, 12-Hydroxy-, Homopolymer, Ester With 2-Methyloxirane Polymer With Oxirane...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-27

... a finite tolerance is not necessary to ensure that there is a reasonable certainty that no harm will... of its composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed in...

Effects of high pressure processing on fatty acid composition and volatile compounds in Korean native black goat meat.

PubMed

Kang, Geunho; Cho, Soohyun; Seong, Pilnam; Park, Beomyoung; Kim, Sangwoo; Kim, Donghun; Kim, Youngjun; Kang, Sunmun; Park, Kyoungmi

2013-08-01

This study investigated the effects of high pressure processing (HPP) on fatty acid composition and volatile compounds in Korean native black goat (KNBG) meat. Fatty acid content in KNBG meat was not significantly (p > 0.05) different among the control goats and those subjected HPP. The 9,12-octadecadienoic acid and octadecanoic acid, well-known causes of off-flavors, were detected from meat of some KNBG. A difference between the control and HPP treatment was observed in the discriminated function analysis using an electronic nose. The results suggest that the volatile compounds in KNBG meat were affected by HPP.

[Characterization of an extracellular glycolipid from Lentinus edodes (Berk.) Sing [Lentinula edodes (Berk.) Pegler

PubMed

Tsivileva, O M; Nikitina, V E; Makarov, O E

2008-01-01

Submerged mycelium of a xylotrophic basidiomycete Lentinus edodes produces an extracellular glycolipid, S3, associated with a lectin. Galactose glycan residue, as well as the lipid pool composition, which includes nonhydroxylated short-chain fatty acids, is uncommon for basidiomycetes. The glycolipid consists of D-galactopyranose (15% of S3 contains galactose sulfate) acylated by octadecanoic and nonadecanoic fatty acid residues (28 and 72%, respectively). The glycolipid structure and composition are confirmed by physicochemical analysis. The glycolipid is assumed to be a regulator of lectin activity.

Volatile components of ethanolic extract from broccolini leaves.

PubMed

Wang, Xiaoqin; Zhang, Bochao; Wang, Bingfang; Zhang, Xuewu

2012-01-01

Broccolini (Brassica oleracea Italica × Alboglabra) is a hybrid of broccoli and kai-lan, Chinese broccoli. To date, no study has been reported on the chemical composition of the volatile fractions of this raw material. In this study, the volatile constituents from the ethanolic extract of broccolini leaves were analysed by gas chromatography-mass spectrometry (GC-MS). Sixteen compounds were identified. The major components include 5-phenyl-undecane (11%), n-hexadecanoic acid (9.34%), octadecanoic acid (6.39%), 1,1,3-trimethyl-3-phenyl-indan (4.0%), 3-(2-phenylethyl)benzonitrile (3.48%) and phytol (3.37%).

Evaluation of degradation of antibiotic tetracycline in pig manure by electron beam irradiation.

PubMed

Cho, Jae-Young

2010-04-01

This study was carried out to evaluate the degradation efficiency and intermediate products of the tetracycline from artificially contaminated pig manure using of electron beam irradiation as a function of the absorbed dose. The degradation efficiency of tetracycline was 42.77% at 1 kGy, 64.20% at 3 kGy, 77.83% at 5 kGy, and 90.50% at 10 kGy. The initial concentration of tetracycline (300 mg kg(-1)) in pig manure decreased significantly to 24.2 +/- 5.3 mg kg(-1) after electron beam irradiation at 10 kGy. The radiolytic degradation products of tetracycline were 1,4-benzenedicarboxylic acid, hexadecanoic acid, 9-octadecenamide, 11-octadecenamide, and octadecanoic acid.

Simple and sensitive analysis of long-chain free fatty acids in milk by fluorogenic derivatization and high-performance liquid chromatography.

PubMed

Lu, Chi-Yu; Wu, Hsin-Lung; Chen, Su-Hwei; Kou, Hwang-Shang; Wu, Shou-Mei

2002-01-02

A highly sensitive high-performance liquid chromatography (HPLC) method is described for the simultaneous determination of some important saturated and unsaturated fatty acids in milk, including lauric (dodecanoic), myristic (tetradecanoic), palmitic (hexadecanoic), stearic (octadecanoic), palmitoleic (hexadecenoic), oleic (octadecenoic), and linoleic acids (octadecadienoic acids). The fatty acids were fluorogenically derivatized with 2-(2-naphthoxy)ethyl 2-(piperidino)ethanesulfonate (NOEPES) as their naphthoxyethyl derivatives. The resulting derivatives were separated by isocratic HPLC and monitored with a fluorometric detector (lambdaex = 235 nm, lambdaem = 350 nm). The fatty acids in milk were extracted with toluene, and the extract with the fatty acids was directly derivatized with NOEPES without solvent replacement. Determination of long-chain free fatty acids in milk is feasible by a standard addition method. A small amount of milk product, 10 microL, is sufficient for the analysis.

Gas Chromatography-Mass Spectrometry Analysis of Constituent Oil from Lingzhi or Reishi Medicinal Mushroom, Ganoderma lucidum (Agaricomycetes), from Nigeria.

PubMed

Ohiri, Reginald Chibueze; Bassey, Essien Eka

2016-01-01

Gas chromatography-mass spectrometry analysis of constituent oil from dried Ganoderma lucidum was carried out. Fresh G. lucidum obtained from its natural environment was thoroughly washed with distilled water and air-dried for 2 weeks and the component oils were extracted and analyzed. Four predominant components identified were pentadecanoic acid, 14-methyl-ester (retention time [RT] = 19.752 minutes; percentage total = 25.489), 9,12-octadecadienoic acid (Z,Z)- (RT = 21.629 minutes and 21.663 minutes; percentage total = 25.054), n-hexadecanoic acid (RT = 20.153 minutes; percentage total = 24.275), and 9-octadecenoic acid (Z)-, methyl ester (RT = 21.297 minutes; percentage total = 13.027). The two minor oils identified were 9,12-octadecadienoic acid, methyl ester, (E,E)- and octadecanoic acid, methyl ester (RT = 21.246 minutes and 21.503 minutes; percentage total = 7.057 and 5.097, respectively).

Chemometric profile, antioxidant and tyrosinase inhibitory activity of Camel's foot creeper leaves (Bauhinia vahlii).

PubMed

Panda, Pritipadma; Dash, Priyanka; Ghosh, Goutam

2018-03-01

The present study is the first effort to a comprehensive evaluation of antityrosinase activity and chemometric analysis of Bauhinia vahlii. The experimental results revealed that the methanol extract of Bauhinia vahlii (BVM) possesses higher polyphenolic compounds and total antioxidant activity than those reported elsewhere for other more conventionally and geographically different varieties. The BVM contain saturated fatty acids such as hexadecanoic acid (10.15%), octadecanoic acid (1.97%), oleic acid (0.61%) and cis-vaccenic acid (2.43%) along with vitamin E (12.71%), α-amyrin (9.84%), methyl salicylate (2.39%) and β-sitosterol (17.35%), which were mainly responsible for antioxidant as well as tyrosinase inhibitory activity. Tyrosinase inhibitory activity of this extract was comparable to that of Kojic acid. These findings suggested that the B. vahlii leaves could be exploited as potential source of natural antioxidant and tyrosinase inhibitory agent, as well.

[Fatty acids composition of cellular lipids of the collected and newly isolated Pseudomonas lupini strains].

PubMed

Hvozdiak, R I; Dankevych, L A; Votselko, S K; Holubets', O V

2005-01-01

Fatty acid composition of cellular lipids of 23 Pseudomonas lupini strains (Beltjukova et Koroljova 1968) has been investigated. Cellular fatty acids which contained from C10 to C19 carbon atoms have been identified. Basic fatty acid of those Pseudomonas cells are hexadecanoic, hexadecenoic and octadecanoic acids. The 3-hydroxydecanoic (C10:0 3OH), 3-hydroxydodecanoic (C12:0 3OH), 2-hydroxydodecanoic (C12:0 2OH) and cyclopropane fatty acids which contain 17 and 19 carbon atoms have been detected in cellular lipids. The cellular fatty acids spectra of 22 P. lupini strains are similar to cellular fatty acids spectrum of the type strain Pseudomonas syringae pv. syringae 8511. Pathogenic isolate 2, which fatty acid content of cell lipids significantly differ from lipids of cell fatty acids from P. lupini strains and cell lipids of fatty acids of typical strains Pseudomonas syringae pv. syringae 8511 and Pseudomonas savastanoi pv. phaseolicola 9066 is the exception.

Study on vacuum pyrolysis of coffee industrial residue for bio-oil production

NASA Astrophysics Data System (ADS)

Chen, Nanwei; Ren, Jie; Ye, Ziwei; Xu, Qizhi; Liu, Jingyong; Sun, Shuiyu

2017-03-01

Coffee industrial residue (CIR) is a biomass with high volatile content (64.94 wt.%) and heating value (21.3 MJ·kg-1). This study was carried out to investigate the pyrolysis condition and products of CIR using thermogravimetric analyser (TGA) and vacuum tube furnace. The influence of pyrolysis temperature, time, pressure and heating rate on the yield of pyrolysis products were discussed. There was an optimal pyrolysis condition: CIR was heated from normal temperature to 400 °C for 60 min, with 10 °C·min-1 heating rate and a pressure of 30 kPaabs. In this condition, the yields of bio-oil, char and non-condensable gas were 42.29, 33.14 and 24.57 wt.%, respectively. The bio-oil contained palmitic acid (47.48 wt.%), oleic acid (17.45 wt.%), linoleic acid (11.34 wt.%), octadecanoic acid (7.62 wt.%) and caffeine (5.18 wt.%).

Exogenous Indole Regulates Lipopeptide Biosynthesis in Antarctic Bacillus amyloliquefaciens Pc3.

PubMed

Ding, Lianshuai; Zhang, Song; Guo, Wenbin; Chen, Xinhua

2018-05-28

Bacillus amyloliquefaciens Pc3 was isolated from Antarctic seawater with antifungal activity. In order to investigate the metabolic regulation mechanism in the biosynthesis of lipopeptides in B. amyloliquefaciens Pc3, GC/MS-based metabolomics was used when exogenous indole was added. The intracellular metabolite profiles showed decreased asparagine, aspartic acid, glutamine, glutamic acid, threonine, valine, isoleucine, hexadecanoic acid, and octadecanoic acid in the indole-treated groups, which were involved in the biosynthesis of lipopeptides. B. amyloliquefaciens Pc3 exhibited a growth promotion, bacterial total protein increase, and lipopeptide biosynthesis inhibition upon the addition of indole. Besides this, real-time PCR analysis further revealed that the transcription of lipopeptide biosynthesis genes ituD, fenA , and srfA-A were downregulated by indole with 22.4-, 21.98-, and 26.0-fold, respectively. It therefore was speculated that as the metabolic flux of most of the amino acids and fatty acids were transferred to the synthesis of proteins and biomass, lipopeptide biosynthesis was weakened owing to the lack of precursor amino acids and fatty acids.

Effect of growth temperature on outer membrane components and virulence of Aeromonas hydrophila strains of serotype O:34.

PubMed Central

Merino, S; Camprubí, S; Tomás, J M

1992-01-01

Growth of Aeromonas hydrophila strains from serotype O:34 at 20 and 37 degrees C in tryptic soy broth resulted in changes in the lipids, lipopolysaccharide (LPS), and virulence of the strains tested. Cells grown at 20 degrees C contained, relative to those cultured at 37 degrees C, increased levels of the phospholipid fatty acids hexadecanoate and octadecanoate and reduced levels of the corresponding saturated fatty acids. Furthermore, the lipid A fatty acids also showed thermoadaptation. In addition, LPS extracted from cells cultivated at 20 degrees C was smooth, while the LPS extracted from the same cells cultivated at 37 degrees C was rough. Finally, the strains were more virulent for fish and mice when they were grown at 20 degrees C than when they were grown at 37 degrees C and also showed increased different extracellular activities when they were grown at 20 degrees C. Images PMID:1398945

Metabolomics and Trace Element Analysis of Camel Tear by GC-MS and ICP-MS.

PubMed

Ahamad, Syed Rizwan; Raish, Mohammad; Yaqoob, Syed Hilal; Khan, Altaf; Shakeel, Faiyaz

2017-06-01

Camel tear metabolomics and elemental analysis are useful in getting the information regarding the components responsible for maintaining the protective system that allows living in the desert and dry regions. The aim of this study was to correlate that the camel tears can be used as artificial tears for the evaluation of dryness in the eye. Eye biomarkers of camel tears were analyzed by gas chromatography-mass spectroscopy (GC-MS) and inductively coupled plasma mass spectroscopy (ICP-MS). The major compounds detected in camel tears by GC-MS were alanine, valine, leucine, norvaline, glycine, cadaverine, urea, ribitol, sugars, and higher fatty acids like octadecanoic acid and hexadecanoic acid. GC-MS analysis of camel tears also finds several products of metabolites and its associated metabolic participants. ICP-MS analysis showed the presence of different concentration of elemental composition in the camel tears.

Chemical constituents of the femoral gland secretions of male tegu lizards (Tupinambis merianae) (Family teiidae).

PubMed

Martín, José; Chamut, Silvia; Manes, Mario E; López, Pilar

2011-01-01

In spite of the importance of chemical signals (pheromones) in the reproductive behaviour of lizards, the chemical compounds secreted by their femoral glands, which may be used as sexual signals, are only known for a few lizard species. Based on mass spectra, obtained by GC-MS, we found 49 lipophilic compounds in femoral gland secretions of male tegu lizards (Tupinambis merianae) (fam. Teiidae), including a very high proportion of carboxylic acids and their esters ranging between n-C8 and n-C20 (mainly octadecanoic and 9,12-octadecadienoic acids), with much less proportions of steroids, tocopherol, aldehydes, and squalene. We discuss the potential function of these compounds in secretions, and compare the compounds found here with those documented for other lizard species.

Phospholipid and fatty acid compositions of Rhizobium leguminosarum biovar trifolii ANU843 in relation to flavone-activated pSym nod gene expression.

PubMed

Orgambide, G G; Huang, Z H; Gage, D A; Dazzo, F B

1993-11-01

The phospholipid and associated fatty acid compositions of the bacterial symbiont of clover, Rhizobium leguminosarum biovar trifolii wild-type ANU843, was analyzed by two-dimensional silica thin-layer chromatography, fast atom bombardment-mass spectrometry, flame-ionization detection gas-liquid chromatography and combined gas-liquid chromatography/mass spectrometry. The phospholipid composition included phosphatidylethanolamine (15%), N-methylphosphatidylethanolamine (47%), N,N-dimethylphosphatidylethanolamine (9%), phosphatidylglycerol (19%), cardiolipin (5%) and phosphatidylcholine (2%). Fatty acid composition included predominantly cis-11-octadecenoic acid, lower levels of cis-9-hexadecenoic acid, hexadecanoic acid, 11-methyl-11-octadecenoic acid, octadecanoic acid, 11,12-methyleneoctadecanoic acid, eicosanoic acid and traces of branched, and di- and triunsaturated fatty acids. The influence of expression of the "nodulation" genes encoding symbiotic functions on the composition of these membrane lipids was examined in wild-type cells grown with or without the flavone inducer, 4',7-dihydroxyflavone and in mutated cells lacking the entire symbiotic plasmid where these genes reside, or containing single transposon insertions in selected nodulation genes. No significant changes in phospholipid or associated fatty acid compositions were detected by the above methods of analysis.

Lipids of parasitic and saprophytic leptospires.

PubMed

Johnson, R C; Livermore, B P; Walby, J K; Jenkin, H M

1970-09-01

The lipid composition of five parasitic and six saprophytic leptospires was compared. Lipids comprise 18 to 26% of the dry weight of the cells after chloroform-methanol extraction. No residual (bound) lipid was found after acid or alkaline hydrolysis of the extracted residue. The total lipid was composed of 60 to 70% phospholipid, and the remaining lipid was free fatty acids. The phospholipid fraction contained phosphatidylethanolamine as the major component, and phosphatidylglycerol and diphosphatidylglycerol were minor components with traces of lysophatidylethanolamine sometimes found. The major fatty acids of leptospires were hexadecanoic, hexadecenoic, and octadecenoic acids. Both the unusual cis-11-hexadecenoic acid and the more common cis-9-hexadecenoic acid were synthesized by the leptospires. Neither the parasitic nor the saprophytic leptospires can chain elongate fatty acids. However, they were capable of beta-oxidation of fatty acids. Both groups of leptospires desaturate fatty acids by an aerobic pathway. When the parasite canicola was cultivated on octadecanoic acid, 87% of the hexadecenoic acid was the 11 isomer, whereas the saprophyte semeranga consisted of 10% of this isomer. In addition, the saprophytic leptospires contained more tetradecanoic acid than the parasites. No differences were observed in the lipid composition of virulent and avirulent strains of canicola.

Lipids of Parasitic and Saprophytic Leptospires

PubMed Central

Johnson, R. C.; Livermore, B. P.; Walby, Judith K.; Jenkin, H. M.

1970-01-01

The lipid composition of five parasitic and six saprophytic leptospires was compared. Lipids comprise 18 to 26% of the dry weight of the cells after chloroform-methanol extraction. No residual (bound) lipid was found after acid or alkaline hydrolysis of the extracted residue. The total lipid was composed of 60 to 70% phospholipid, and the remaining lipid was free fatty acids. The phospholipid fraction contained phosphatidylethanolamine as the major component, and phosphatidylglycerol and diphosphatidylglycerol were minor components with traces of lysophatidylethanolamine sometimes found. The major fatty acids of leptospires were hexadecanoic, hexadecenoic, and octadecenoic acids. Both the unusual cis-11-hexadecenoic acid and the more common cis-9-hexadecenoic acid were synthesized by the leptospires. Neither the parasitic nor the saprophytic leptospires can chain elongate fatty acids. However, they were capable of β-oxidation of fatty acids. Both groups of leptospires desaturate fatty acids by an aerobic pathway. When the parasite canicola was cultivated on octadecanoic acid, 87% of the hexadecenoic acid was the 11 isomer, whereas the saprophyte semeranga consisted of 10% of this isomer. In addition, the saprophytic leptospires contained more tetradecanoic acid than the parasites. No differences were observed in the lipid composition of virulent and avirulent strains of canicola. PMID:16557833

Effects of complexation between organic matter (OM) and clay mineral on OM pyrolysis

NASA Astrophysics Data System (ADS)

Bu, Hongling; Yuan, Peng; Liu, Hongmei; Liu, Dong; Liu, Jinzhong; He, Hongping; Zhou, Junming; Song, Hongzhe; Li, Zhaohui

2017-09-01

The stability and persistence of organic matter (OM) in source rocks are of great significance for hydrocarbon generation and the global carbon cycle. Clay-OM associations commonly occur in sedimentation and diagenesis processes and can influence the pyrolytic behaviors of OM. In this study, clay-OM complexes, i.e., interlayer clay-OM complexes and clay-OM mixture, were prepared and exposed to high-pressure pyrolysis conditions in confined gold capsule reactors to assess variations in OM pyrolysis products in the presence of clay minerals. Three model organic compounds, octadecanoic acid (OA), octadecy trimethyl ammonium bromide (OTAB), and octadecylamine (ODA), were employed and montmorillonite (Mt) was selected as the representative clay mineral. The solid acidity of Mt plays a key role in affecting the amount and composition of the pyrolysis gases generated by the clay-OM complexes. The Brønsted acid sites significantly promote the cracking of hydrocarbons through a carbocation mechanism and the isomerization of normal hydrocarbons. The Lewis acid sites are primarily involved in the decarboxylation reaction during pyrolysis and are responsible for CO2 generation. Mt exhibits either a catalysis effect or pyrolysis-inhibiting during pyrolysis of a given OM depending on the nature of the model organic compound and the nature of the clay-OM complexation. The amounts of C1-5 hydrocarbons and CO2 that are released from the Mt-OA and Mt-ODA complexes were higher than those of the parent OA and ODA, respectively, indicating a catalysis effect of Mt. In contrast, the amount of C1-5 hydrocarbons produced from the pyrolysis of Mt-OTAB complexes was lower than that of OTAB, which we attribute to an inhibiting effect of Mt. This pyrolysis-inhibiting effect works through the Hoffmann elimination that is promoted by the catalysis of the Brønsted acid sites of Mt, therefore releasing smaller amounts of gas hydrocarbons than the nucleophilic reaction that is induced by the halide ions in OTAB. In particular, the interlayer space of Mt acts as an 'amplifier' that magnifies the above-mentioned catalysis or pyrolysis-inhibiting effect, due to the greater number of Brønsted acid sites with high acidity in the interlayer space. These findings are potentially important for understanding the storage and transfer mechanisms of natural OM in sedimentation and diagenesis processes.

Triterpene Esters and Biological Activities from Edible Fruits of Manilkara subsericea (Mart.) Dubard, Sapotaceae

PubMed Central

Fernandes, Caio P.; Corrêa, Arthur L.; Lobo, Jonathas F. R.; Caramel, Otávio P.; de Almeida, Fernanda B.; Castro, Elaine S.; Souza, Kauê F. C. S.; Burth, Patrícia; Amorim, Lidia M. F.; Santos, Marcelo G.; Ferreira, José Luiz P.; Falcão, Deborah Q.; Carvalho, José C. T.; Rocha, Leandro

2013-01-01

Manilkara subsericea (Mart.) Dubard (Sapotaceae) is popularly known in Brazil as “guracica.” Studies with Manilkara spp indicated the presence of triterpenes, saponins, and flavonoids. Several activities have been attributed to Manilkara spp such as antimicrobial, antiparasitic and antitumoral, which indicates the great biological potential of this genus. In all, 87.19% of the hexanic extract from fruits relative composition were evaluated, in which 72.81% were beta- and alpha-amyrin esters, suggesting that they may be chemical markers for M. subsericea. Hexadecanoic acid, hexadecanoic acid ethyl ester, (E)-9-octadecenoic acid ethyl ester, and octadecanoic acid ethyl ester were also identified. Ethanolic crude extracts from leaves, stems, and hexanic extract from fruits exhibited antimicrobial activity against Staphylococcus aureus ATCC25923. These extracts had high IC50 values against Vero cells, demonstrating weak cytotoxicity. This is the first time, to our knowledge, that beta- and alpha-amyrin caproates and caprylates are described for Manilkara subsericea. PMID:23509702

HEPATIC FATTY ACID PROFILE OF RATS FED A TRIHEPTANOIN-BASED KETOGENIC DIET.

PubMed

Vieira de Melo, Ingrid Sofia; Da Rocha Ataide, Terezinha; Lima de Oliveira, Suzana; Bezerra Bueno, Nassib; Duarte de Freitas, Johnnatan; Goulart Sant'Ana, Antônio Euzébio

2015-07-01

the aim of this study was to evaluate the influence of consumption of a ketogenic diet supplemented with triheptanoin, a medium-chain anaplerotic triacylglycerol, on the liver fatty acid profile of Wistar rats. three groups of male Wistar rats (n = 10) were submitted to an AIN-93 control diet, a triheptanoin- based ketogenic diet, or a soybean oil-based ketogenic diet for 60 days. Excised livers were subjected to lipid extraction and methylation to obtain fatty acids methyl esters, which were subjected to gas chromatography- mass spectrometry. compared to the rats fed the control diet, those fed ketogenic diets showed a significant reduction in the concentrations of 9-hexadecenoic and 9-octadecenoic acids, whereas those fed triheptanoin showed increased levels of octadecanoic acid. changes in the liver fatty acid profiles of the rats fed a triheptanoin-based or a soybean oil-based ketogenic diet did not seem to be related to the dietary fat source, but rather to the characteristics of the ketogenic diets themselves. Copyright AULA MEDICA EDICIONES 2014. Published by AULA MEDICA. All rights reserved.

Description of strain 3CB-1, a genomovar of Thauera aromatica, capable of degrading 3-chlorobenzoate coupled to nitrate reduction.

PubMed

Song, B; Palleroni, N J; Häggblom, M M

2000-03-01

A Gram-negative bacterium, strain 3CB-1, isolated from a 3-chlorobenzoate enrichment culture inoculated with a sediment sample is capable of degrading various aromatic compounds and halogenated derivatives with nitrate as electron acceptor. Compounds capable of serving as carbon and energy sources include 3-chlorobenzoate, 3-bromobenzoate, 2-fluorobenzoate, 4-fluorobenzoate, benzoate, 3-hydroxybenzoate, 4-hydroxybenzoate, 3-aminobenzoate, protocatechuate, m-cresol and p-cresol. Oxygen, nitrate and nitrite were used as electron acceptors for growth. Cells are Gram-negative short rods with peritrichous flagellation. The predominant fatty acids are cis-9-hexadecenoic acid (16:1 omega 7c), hexadecanoic acid (16:0), octadecanoic acid (18:0), octadecenoic acid (18:1), 3-hydroxydecanoic acid (10:0 3OH) and dodecanoic acid (12:0). The sequence of the 16S rRNA gene, as well as the fatty acid composition, indicate that the strain is a member of the genus Thauera in the beta-subclass of the Proteobacteria and very close to Thauera aromatica. DNA-DNA hybridization and nutrient screening indicate that strain 3CB-1 is a genomovar of Thauera aromatica with the proposed name Thauera aromatica genomovar chlorobenzoica.

Responses of microalgae Coelastrella sp. to stress of cupric ions in treatment of anaerobically digested swine wastewater.

PubMed

Li, Xiang; Yang, William L; He, Huijun; Wu, Shaohua; Zhou, Qi; Yang, Chunping; Zeng, Guangming; Luo, Le; Lou, Wei

2018-03-01

Microalgae Coelastrella sp. could remove nutrients from anaerobically digested swine wastewater (ADSW) effectively, while its responses to the stress of Cu(II) were not well understood. In this paper, nutrients removal and growth of Coelastrella sp. were investigated at the presence of Cu(II) in ADSW. Results showed ammonium nitrogen concentration in ADSW decreased with culturing duration, while increased with an increased Cu(II) concentration. Total phosphorous concentration decreased with time, while did not drop in 4 days at Cu(II) concentration ≥1.0 mg/L. Microalgal growth was inhibited at all the Cu(II) concentrations, and ceased in about 6-8 days at Cu(II) concentration ≥1.0 mg/L. With an increased Cu(II) concentration, the contents of chlorophyll a and proteins decreased, those of malondialdehyde and superoxide dismutase, and ratios of octadecanoic acid (C18:0), hexadecanoic acid (C16:0) and octadecenoic acid (C18:1) to fatty acids in Coelastrella sp. increased, while octadecatrienoic acid (C18:3) gradually disappeared. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fatty Acid Profile, Phenolics and Flavonoids Contents in Olea europaea L. Callus Culture cv. cornicabra.

PubMed

Rodríguez-Hernandez, Ludwi; Nájera-Gomez, Humberto; Luján-Hidalgo, Maria Celína; Ruiz-Lau, Nancy; Lecona-Guzmán, Carlos Alberto; Abud-Archila, Miguel; Ruíz-Valdiviezo, Víctor Manuel; Gutiérrez-Miceli, Federico Antonio

2018-05-01

Olive trees are one of the most important oil crops in the world due to the sensorial and nutritional characteristics of olive oil, such as lipid composition and antioxidant content, and the medicinal properties of its leaves. In this paper, callus formation was induced using nodal segments of olive tree (Olea europaea cv. cornicabra) as explants. Fatty acid profile, total phenolic compounds and total flavonoid compounds were determined in callus culture after 15 weeks and compared with leaf and nodal segments tissues. There was no statistical difference in phenolic compounds among leaf, nodal segments and callus culture, whereas flavonoid compounds were higher in leaf. Fatty acid profile was similar in leaf, nodal segments and callus culture and was constituted by hexadecanoic acid, octadecanoic acid, cis-9-octadecenoic acid, cis-9,12-octadecadienoic acid, cis-9,12,15-octadecatrienoic acid. Hexadecanoic acid was the main fatty acid in callus, leaf and nodal segments with 35.0, 39.0 and 40.0% (w/w), of the lipid composition, respectively. With this paper, it is being reported for the first time the capacity of callus culture to accumulate fatty acids. Our results could serve to continue studying the production of fatty acids in callus cultivation as a biotechnological tool to improve different olive cultivars.

EFFECT OF TEMPERATURE ON THE COMPOSITION OF FATTY ACIDS IN ESCHERICHIA COLI

PubMed Central

Marr, Allen G.; Ingraham, John L.

1962-01-01

Marr, Allen G. (University of California, Davis) and John L. Ingraham. Effect of temperature on composition of fatty acids in Escherichia coli. J. Bacteriol. 84:1260–1267. 1962.—Variations in the temperature of growth and in the composition of the medium alter the proportions of individual fatty acids in the lipids of Escherichia coli. As the temperature of growth is lowered, the proportion of unsaturated fatty acids (hexadecenoic and octadecenoic acids) increases. The increase in content of unsaturated acids with a decrease in temperature of growth occurs in both minimal and complex media. Cells harvested in the stationary phase contained large amounts of cyclopropane fatty acids (methylenehexadecanoic and methylene octadecanoic acids) in comparison with cells harvested during exponential growth. Cells grown in a chemostat, limited by the concentration of ammonium salts, show a much higher content of saturated fatty acids (principally palmitic acid) than do cells harvested from an exponentially-growing batch culture in the same medium. Cells grown in a chemostat, limited by the concentration of glucose, show a slightly higher content of unsaturated fatty acids than cells from the corresponding batch culture. The results do not indicate a direct relation between fatty acid composition and minimal growth temperature. PMID:16561982

Fatty Acid and Proximate Composition of Bee Bread.

PubMed

Kaplan, Muammer; Karaoglu, Öznur; Eroglu, Nazife; Silici, Sibel

2016-12-01

Palynological spectrum, proximate and fatty acid (FA) composition of eight bee bread samples of different botanical origins were examined and significant variations were observed. The samples were all identified as monofloral, namely Castanea sativa (94.4%), Trifolium spp. (85.6%), Gossypium hirsutum (66.2%), Citrus spp. (61.4%) and Helianthus annuus (45.4%). Each had moisture content between 11.4 and 15.9%, ash between 1.9 and 2.54%, fat between 5.9 and 11.5%, and protein between 14.8 and 24.3%. A total of 37 FAs were determined with most abundant being (9Z,12Z,15Z)-octadeca-9,12,15-trienoic, (9Z,12Z)- -octadeca-9,12-dienoic, hexadecanoic, (Z)-octadec-9-enoic, (Z)-icos-11-enoic and octadecanoic acids. Among all, cotton bee bread contained the highest level of ω-3 FAs, i.e. 41.3%. Unsaturated to saturated FA ratio ranged between 1.38 and 2.39, indicating that the bee bread can be a good source of unsaturated FAs.

Fatty Acid and Proximate Composition of Bee Bread

PubMed Central

Kaplan, Muammer; Karaoglu, Öznur; Eroglu, Nazife

2016-01-01

Summary Palynological spectrum, proximate and fatty acid (FA) composition of eight bee bread samples of different botanical origins were examined and significant variations were observed. The samples were all identified as monofloral, namely Castanea sativa (94.4%), Trifolium spp. (85.6%), Gossypium hirsutum (66.2%), Citrus spp. (61.4%) and Helianthus annuus (45.4%). Each had moisture content between 11.4 and 15.9%, ash between 1.9 and 2.54%, fat between 5.9 and 11.5%, and protein between 14.8 and 24.3%. A total of 37 FAs were determined with most abundant being (9Z,12Z,15Z)-octadeca-9,12,15-trienoic, (9Z,12Z)- -octadeca-9,12-dienoic, hexadecanoic, (Z)-octadec-9-enoic, (Z)-icos-11-enoic and octadecanoic acids. Among all, cotton bee bread contained the highest level of ω-3 FAs, i.e. 41.3%. Unsaturated to saturated FA ratio ranged between 1.38 and 2.39, indicating that the bee bread can be a good source of unsaturated FAs. PMID:28115909

Identification of Scirpus triqueter root exudates and the effects of organic acids on desorption and bioavailability of pyrene and lead in co-contaminated wetland soils.

PubMed

Hou, Yunyun; Liu, Xiaoyan; Zhang, Xinying; Chen, Xiao; Tao, Kaiyun; Chen, Xueping; Liang, Xia; He, Chiquan

2015-11-01

Root exudates (REs) of Scirpus triqueter were extracted from the rhizosphere soil in this study. The components in the REs were identified by GC-MS. Many organic acids, such as hexadecanoic acid, pentadecanoic acid, vanillic acid, octadecanoic acid, citric acid, succinic acid, glutaric acid, and so on, were found. Batch simulated experiments were conducted to evaluate the impacts of different organic acids, such as citric acid, artificial root exudates (ARE), succinic acid, and glutaric acid in REs of S. triqueter on desorption of pyrene (PYR) and lead (Pb) in co-contaminated wetland soils. The desorption amount of PYR and Pb increased with the rise in concentrations of organic acids in the range of 0-50 g·L(-1), within shaking time of 2-24 h. The desorption effects of PYR and Pb in soils with various organic acids treatments decreased in the following order: citric acid > ARE > succinic acid > glutaric acid. The desorption rate of PYR and Pb was higher in co-contaminated soil than in single pollution soil. The impacts of organic acids in REs of S. triqueter on bioavailability of PYR and Pb suggested that organic acids enhanced the bioavailability of PYR and Pb in wetland soil, and the bioavailability effects of organic acids generally followed the same order as that of desorption effects.

Kinetics of coffee industrial residue pyrolysis using distributed activation energy model and components separation of bio-oil by sequencing temperature-raising pyrolysis.

PubMed

Chen, Nanwei; Ren, Jie; Ye, Ziwei; Xu, Qizhi; Liu, Jingyong; Sun, Shuiyu

2016-12-01

This study was carried out to investigate the kinetics of coffee industrial residue (CIR) pyrolysis, the effect of pyrolysis factors on yield of bio-oil component and components separation of bio-oil. The kinetics of CIR pyrolysis was analyzed using distributed activation energy model (DAEM), based on the experiments in thermogravimetric analyzer (TGA), and it indicated that the average of activation energy (E) is 187.86kJ·mol -1 . The bio-oils were prepared from CIR pyrolysis in vacuum tube furnace, and its components were determined by gas chromatography/mass spectrometry (GC-MS). Among pyrolysis factors, pyrolysis temperature is the most influential factor on components yield of bio-oil, directly concerned with the volatilization and yield of components (palmitic acid, linoleic acid, oleic acid, octadecanoic acid and caffeine). Furthermore, a new method (sequencing temperature-raising pyrolysis) was put forward and applied to the components separation of bio-oil. Based on experiments, a solution of components separation of bio-oil was come out. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metabolic changes in rat serum after administration of suberoylanilide hydroxamic acid and discriminated by SVM.

PubMed

Yu, J; Wu, H; Lin, Z; Su, K; Zhang, J; Sun, F; Wang, X; Wen, C; Cao, H; Hu, L

2017-12-01

Suberoylanilide hydroxamic acid (SAHA) exerts marked anticancer effects via promotion of apoptosis, cell cycle arrest, and prevention of oncogene expression. In this study, serum metabolomics and artificial intelligence recognition were used to investigate SAHA toxicity. Forty rats (220 ± 20 g) were randomly divided into control and three SAHA groups (low, medium, and high); the experimental groups were treated with 12.3, 24.5, or 49.0 mg kg -1 SAHA once a day via intragastric administration. After 7 days, blood samples from the four groups were collected and analyzed by gas chromatography-mass spectrometry, and pathological changes in the liver were examined using microscopy. The results showed that increased levels of urea, oleic acid, and glutaconic acid were the most significant indicators of toxicity. Octadecanoic acid, pentadecanoic acid, glycerol, propanoic acid, and uric acid levels were lower in the high SAHA group. Microscopic observation revealed no obvious damage to the liver. Based on these data, a support vector machine (SVM) discrimination model was established that recognized the metabolic changes in the three SAHA groups and the control group with 100% accuracy. In conclusion, the main toxicity caused by SAHA was due to excessive metabolism of saturated fatty acids, which could be recognized by an SVM model.

Carbon nanodots as a matrix for the analysis of low-molecular-weight molecules in both positive- and negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and quantification of glucose and uric acid in real samples.

PubMed

Chen, Suming; Zheng, Huzhi; Wang, Jianing; Hou, Jian; He, Qing; Liu, Huihui; Xiong, Caiqiao; Kong, Xianglei; Nie, Zongxiu

2013-07-16

Carbon nanodots were applied for the first time as a new matrix for the analysis of low-molecular-weight compounds by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) in both positive- and negative-ion modes. A wide range of small molecules including amino acids, peptides, fatty acids, as well as β-agonists and neutral oligosaccharides were analyzed by MALDI MS with carbon nanodots as the matrix, and the lowest 0.2 fmol limits-of-detection were obtained for octadecanoic acid. Clear sodium and potassium adducts and deprotonated signals were produced in positive- and negative-ion modes. Furthermore, the glucose and uric acid in real samples were quantitatively determined by the internal standard method with the linear range of 0.5-9 mM and 0.1-1.8 mM (R(2) > 0.999), respectively. This work gives new insight into the application of carbon nanodots and provides a general approach for rapid analysis of low-molecular-weight compounds.

Discovery and characterizaton of a novel lipase with transesterification activity from hot spring metagenomic library.

PubMed

Yan, Wei; Li, Furong; Wang, Li; Zhu, Yaxin; Dong, Zhiyang; Bai, Linhan

2017-03-01

A new gene encoding a lipase (designated as Lip-1 ) was identified from a metagenomic bacterial artificial chromosome(BAC) library prepared from a concentrated water sample collected from a hot spring field in Niujie, Eryuan of Yunnan province in China. The open reading frame of this gene encoded 622 amino acid residues. It was cloned, fused with the oleosin gene and over expressed in Escherichia coli to prepare immobilized lipase artificial oil body AOB-sole-lip-1. The monomeric Sole-lip-1 fusion protein presented a molecular mass of 102.4 kDa. Enzyme assays using olive oil and methanol as the substrates in petroleum ether confirmed its transesterification activity. Hexadecanoic acid methyl ester, 8,11-Octadecadienoic acid methyl ester, 8-Octadecenoic acid methyl ester, and Octadecanoic acid methyl ester were detected. It showed favorable transesterification activity with optimal temperature 45 °C. Besides, the maximal biodiesel yield was obtained when the petroleum ether system as the organic solvent and the substrate methanol in 350 mmol/L (at a molar ratio of methanol of 10.5:1) and the water content was 1%. In light of these advantages, this lipase presents a promising resource for biodiesel production.

Characterization and chemical composition of fatty acids content of watermelon and muskmelon cultivars in Saudi Arabia using gas chromatography/mass spectroscopy.

PubMed

Albishri, Hassan M; Almaghrabi, Omar A; Moussa, Tarek A A

2013-01-01

The growth in the production of biodiesel, which is principally fatty acid methyl esters (FAME), has been phenomenal in the last ten years because of the general desire to cut down on the release of greenhouse gases into the atmosphere, and also as a result of the increasing cost of fossil fuels. Establish whether there is any relationship between two different species (watermelon and muskmelon) within the same family (Cucurbitaceae) on fatty acid compositions and enumerate the different fatty acids in the two species. Extraction of fatty acids from the two species and preparation the extract to gas chromatography/mass spectroscopy analysis to determine the fatty acids compositions qualitatively and quantitatively. The analyzed plants (watermelon and muskmelon) contain five saturated fatty acids; tetrdecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid with different concentrations, while muskmelon contains an extra saturated fatty acid named eicosanoic acid. The watermelon plant contains five unsaturated fatty acids while muskmelon contains three only, the two plants share in two unsaturated fatty acids named 9-hexadecenoic acid and 9-octadecenoic acid, the muskmelon plant contains higher amounts of these two acids (2.04% and 10.12%, respectively) over watermelon plant (0.88% and 0.25%, respectively). The chemical analysis of watermelon and muskmelon revealed that they are similar in saturated fatty acids but differ in unsaturated fatty acids which may be a criterion of differentiation between the two plants.

Plasmodium falciparum: differing effects of non-esterified fatty acids and phospholipids on intraerythrocytic growth in serum-free medium.

PubMed

Asahi, Hiroko; Izumiyama, Shinji; Tolba, Mohammed Essa Marghany; Kwansa-Bentum, Bethel

2011-03-01

Different combinations of non-esterified fatty acids (NEFA) had variable effects on intraerythrocytic growth of Plasmodium falciparum. All stages of the parasite cultured in medium supplemented with cis-9-octadecenoic acid (C18:1-cis-9), hexadecanoic acid (C16:0), phospholipids (Pld) and bovine albumin free of NEFA were similar to those grown in complete growth medium. Three typical growth patterns indicating suppressed schizogony (SS), suppressed formation of merozoites (SMF), and inhibited invasion of merozoites (IMI) resulted from culture in other combinations of lipids. Unsaturated or saturated NEFA with longer or shorter carbon chains than C18:1-cis-9 or C16:0, higher degree of unsaturation, and trans-forms mainly resulted in SS and SMF effects. However, IMI or partial IMI was observed with tetradecanoic acid or octadecanoic acid enriched with C18:1-cis-9, and cis-9-hexadecenoic acid plus C16:0. Isoforms of C18:1-cis-9 also mainly resulted in partial IMI. SMF also occurred with C18:1-cis-9 plus C16:0 in the absence of Pld. Thus different NEFA exerted distinct roles in erythrocytic growth of the parasite by sustaining development at different stages. Copyright © 2010 Elsevier Inc. All rights reserved.

Amphiphilic lipid derivatives of 3'-hydroxyurea-deoxythymidine: preparation, properties, molecular self-assembly, simulation and in vitro anticancer activity.

PubMed

Li, Miao; Qi, Shuo; Jin, Yiguang; Yao, Weishang; Zhang, Sa; Zhao, Jingyu

2014-11-01

Lipid derivatives of nucleoside analogs and their nanoassemblies have become the research hotspot due to their unique function in cancer therapy. Six lipid derivatives of 3'-hydroxyurea-deoxythymidine were prepared with zidovudine as the raw material. The 5'-substituted lipid chains in the derivatives were from the various fatty acids including octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid corresponding to the derivatives OHT, DHT, DDHT, TDHT, HDHT and ODHT. The amphiphilic derivatives formed Langmuir monolayers at the air/water interface with different surface pressure-molecular area isotherms depending on the length of lipid chains. The nanoassemblies of OHT, DHT, DDHT, TDHT and HDHT and the nanoscale precipitates of ODHT were obtained after we injected their tetrahydrofuran solutions doped with hydrophilic long chained polymers into water. Electron microscopy showed that the morphology of nanoassemblies may be vesicles or nanotubes depending on the length of lipid chains. The shorter the lipid chains were, the softer the nanoassemblies. Computer simulation supported the experimental results. The nanoassemblies and the nanoscale precipitates showed much higher anticancer effects on SW620 cells than the parent drug hydroxyurea. The nanostructures of the derivatives are promising anticancer nanomedicines. Copyright © 2014 Elsevier B.V. All rights reserved.

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 lowest levels of organic compounds were recorded. This study demonstrates that pollution episodes in Beijing were strongly controlled by wind direction; that is, air quality in Beijing is good when air masses originate from the north and northwest, whereas it deteriorates when the air mass originates from the south and southeast.

Variation in amino acid and lipid composition of latent fingerprints.

PubMed

Croxton, Ruth S; Baron, Mark G; Butler, David; Kent, Terry; Sears, Vaughn G

2010-06-15

The enhancement of latent fingerprints, both at the crime scene and in the laboratory using an array of chemical, physical and optical techniques, permits their use for identification. Despite the plethora of techniques available, there are occasions when latent fingerprints are not successfully enhanced. An understanding of latent fingerprint chemistry and behaviour will aid the improvement of current techniques and the development of novel ones. In this study the amino acid and fatty acid content of 'real' latent fingerprints collected on a non-porous surface was analysed by gas chromatography-mass spectrometry. Squalene was also quantified in addition. Hexadecanoic acid, octadecanoic acid and cis-9-octadecenoic acid were the most abundant fatty acids in all samples. There was, however, wide variation in the relative amounts of each fatty acid in each sample. It was clearly demonstrated that touching sebum-rich areas of the face immediately prior to fingerprint deposition resulted in a significant increase in the amount of fatty acids and squalene deposited in the resulting 'groomed' fingerprints. Serine was the most abundant amino acid identified followed by glycine, alanine and aspartic acid. The significant quantitative differences between the 'natural' and 'groomed' fingerprint samples seen for fatty acids were not observed in the case of the amino acids. This study demonstrates the variation in latent fingerprint composition between individuals and the impact of the sampling protocol on the quantitative analysis of fingerprints. (c) 2010 Elsevier Ireland Ltd. All rights reserved.

Characterization and chemical composition of fatty acids content of watermelon and muskmelon cultivars in Saudi Arabia using gas chromatography/mass spectroscopy

PubMed Central

Albishri, Hassan M.; Almaghrabi, Omar A.; Moussa, Tarek A. A.

2013-01-01

Background: The growth in the production of biodiesel, which is principally fatty acid methyl esters (FAME), has been phenomenal in the last ten years because of the general desire to cut down on the release of greenhouse gases into the atmosphere, and also as a result of the increasing cost of fossil fuels. Objective: Establish whether there is any relationship between two different species (watermelon and muskmelon) within the same family (Cucurbitaceae) on fatty acid compositions and enumerate the different fatty acids in the two species. Materials and Methods: Extraction of fatty acids from the two species and preparation the extract to gas chromatography/mass spectroscopy analysis to determine the fatty acids compositions qualitatively and quantitatively. Results: The analyzed plants (watermelon and muskmelon) contain five saturated fatty acids; tetrdecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid with different concentrations, while muskmelon contains an extra saturated fatty acid named eicosanoic acid. The watermelon plant contains five unsaturated fatty acids while muskmelon contains three only, the two plants share in two unsaturated fatty acids named 9-hexadecenoic acid and 9-octadecenoic acid, the muskmelon plant contains higher amounts of these two acids (2.04% and 10.12%, respectively) over watermelon plant (0.88% and 0.25%, respectively). Conclusion: The chemical analysis of watermelon and muskmelon revealed that they are similar in saturated fatty acids but differ in unsaturated fatty acids which may be a criterion of differentiation between the two plants. PMID:23661995

The molecular distribution of fine particulate organic matter emitted from Western-style fast food cooking

NASA Astrophysics Data System (ADS)

Zhao, Yunliang; Hu, Min; Slanina, Sjaak; Zhang, Yuanhang

The emissions from food cooking could be a significant contributor to atmospheric particulate organic matter (POM) and its chemical composition would vary with different cooking styles. In this study, the chemical composition of POM emitted from Western-style fast food cooking was investigated. A total of six PM 2.5 samples was collected from a commercial restaurant and determined by gas chromatography-mass spectrometry (GC-MS). It is found that the total amount of quantified compounds of per mg POM in Western-style fast food cooking is much higher than that in Chinese cooking. The predominant homologue is fatty acids, accounting for 78% of total quantified POM, with the predominant one being palmitic acid. Dicarboxylic acids display the second highest concentration in the quantified homologues with hexanedioic acid being predominant, followed by nonanedioic acid. Cmax of n-alkanes occurs at C25, but they still appear relative higher concentrations at C29 and C31. In addition, both levoglucosan and cholesterol are quantified. The relationship of concentrations of unsaturated fatty acids (C16 and C18) with a double bond at C9 position and C9 acids indicates the reduction of the unsaturated fatty acids in the emissions could form the C9 acids. Moreover, the nonlinear fit indicates that other C9 species or other compounds are also produced, except for the C9 acids. The potential candidates of tracers for the emissions from Western-fast food cooking could be: tetradecanoic acid, hexadecanoic acid, octadecanoic acid, 9-octadecenoic acid, nonanal, lactones, levoglucosan, hexanedioic acid and nonanedioic acid.

Novel Mechanism of Fatty Acid Sensing in Enteroendocrine Cells: Specific Structures in Oxo-Fatty Acids Produced by Gut Bacteria are Responsible for CCK Secretion in STC-1 Cells via GPR40.

PubMed

Hira, Tohru; Ogasawara, Shono; Yahagi, Asuka; Kamachi, Minami; Li, Jiaxin; Nishimura, Saki; Sakaino, Masayoshi; Yamashita, Takatoshi; Kishino, Shigenobu; Ogawa, Jun; Hara, Hiroshi

2018-06-25

The secretion of gut hormones, such as cholecystokinin (CCK) is stimulated by fatty acids. Although a chain length-dependent mechanism has been proposed, other structural relationships to releasing activity remain unclear. We aimed to elucidate specific structures in fatty acids that are responsible for their CCK-releasing activity, and related sensing mechanisms in enteroendocrine cells. We examined CCK secretory activities in a murine CCK-producing cell line STC-1 by exposing the cells to various modified fatty acids produced by gut lactic acid bacteria. The effects of fatty acids on gastric emptying rate as a CCK-mediated function were examined using acetaminophen- and phenol red-methods in rats. Out of more than thirty octadecanoic (C18)-derived fatty acids tested, five oxo-fatty acids potently stimulated CCK secretion without cytotoxic effects in STC-1 cells. Three fatty acids had a distinct specific structure containing one double-bond, whereas the other two had two double-bonds, nearby an oxo residue. CCK secretion induced by representative fatty acids (10-oxo-trans-11-18:1 and 13-oxo-cis-9,cis-15-18:2) was attenuated by a fatty acid-receptor GPR40 antagonist. Oral administration of 13-oxo-cis-9,cis-15-18:2 lowered the gastric emptying rate in rats in a dose- and structure-dependent manner. These results revealed a novel fatty acid-sensing mechanism in enteroendocrine cells. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Chemical Composition and Vasorelaxant and Antispasmodic Effects of Essential Oil from Rosa indica L. Petals

PubMed Central

Rasheed, Hafiz Majid; Khan, Taous; Wahid, Fazli; Khan, Rasool; Shah, Abdul Jabbar

2015-01-01

Rosa indica L. belongs to the family Rosaceae and is locally known as gulaab. It has different traditional uses in cardiovascular and gastrointestinal disorders but there is no scientific data available in this regard. Therefore, the basic aim of this study was to explore the chemical composition and gastrointestinal and cardiovascular effects of the essential oil obtained from R. indica. The chemical composition of the essential oil was investigated using gas chromatography-mass spectrometry (GC-MS) technique. The cardiovascular and gastrointestinal effects were investigated using electrophysiological measurements. The GC-MS analysis of the essential oil showed various chemical components including acetic acid, mercaptohexyl ester, butanoic acid, 2-methyl-5-oxo-1-cyclopentene-1-yl ester, artemiseole, methyl santonilate, isosteviol, caryophyllene oxide, pentyl phenyl acetate, dihydromyrcene, 1,5-octadecadien, octadecanoic acid, ethyl ester, palmitic acid (2-phenyl-1,3-dioxolan-4-yl methyl ester), santolina epoxide, and 9-farnesene. The electrophysiological measurements revealed that essential oil was more potent against K+ (80 mM) than phenylephrine precontractions using isolated rabbit aorta preparations. In isolated rabbit jejunum preparations, it showed more potency against high K+ induced contractions than spontaneous contractions. Considering these evidences, it can be concluded that R. indica essential oil may work as a complementary and alternative medicine in gastrointestinal and cardiovascular diseases. PMID:26357519

Detection of Androgenic-Mutagenic Compounds and Potential Autochthonous Bacterial Communities during In Situ Bioremediation of Post-methanated Distillery Sludge

PubMed Central

Chandra, Ram; Kumar, Vineet

2017-01-01

Sugarcane-molasses-based post-methanated distillery waste is well known for its toxicity, causing adverse effects on aquatic flora and fauna. Here, it has been demonstrated that there is an abundant mixture of androgenic and mutagenic compounds both in distillery sludge and leachate. Gas chromatography-mass spectrometry (GC-MS) analysis showed dodecanoic acid, octadecanoic acid, n-pentadecanoic acid, hexadecanoic acid, β-sitosterol, stigmasterol, β-sitosterol trimethyl ether, heptacosane, dotriacontane, lanosta-8, 24-dien-3-one, 1-methylene-3-methyl butanol, 1-phenyl-1-propanol, 5-methyl-2-(1-methylethyl) cyclohexanol, and 2-ethylthio-10-hydroxy-9-methoxy-1,4 anthraquinone as major organic pollutants along with heavy metals (all mg kg-1): Fe (2403), Zn (210.15), Mn (126.30, Cu (73.62), Cr (21.825), Pb (16.33) and Ni (13.425). In a simultaneous analysis of bacterial communities using the restriction fragment length polymorphism (RFLP) method the dominance of Bacillus sp. followed by Enterococcus sp. as autochthonous bacterial communities growing in this extremely toxic environment was shown, indicating a primary community for bioremediation. A toxicity evaluation showed a reduction of toxicity in degraded samples of sludge and leachate, confirming the role of autochthonous bacterial communities in the bioremediation of distillery waste in situ. PMID:28567033

Comparative chemical characterization of pigmented and less pigmented cell walls of Alternaria tenuissima.

PubMed

Kishore, Kankipati Hara; Kanjilal, Sanjit; Misra, Sunil; Reddy, Chinnathimma Rajagopal; Murty, Upadyayula Suryanarayana

2005-12-01

Alternaria tenuissima, the parasitic fungus, was obtained from the pruned upper-cut surfaces of mulberry stems. This fungus contains dark pigment because of the presence of melanin in the cell wall. To obtain less-pigmented cell walls, this fungus was grown under dark condition. When the pigmented and less-pigmented cell walls were chemically analyzed, no differences were observed in amino-acid composition, hexoses, or pentoses. However, in pigmented cell walls, higher contents of melanin (2.6%) were found than in less-pigmented cell walls (0.3%). Interestingly, a significant difference was observed in the relative fatty-acid compositions between these two types of cell walls. Among the major fatty acids, there were increased concentrations of tetradecanoic acid (C14:0), hexadecanoic acid (C16:0), 9-hexadecenoic acid (C16: 1,Delta 9), and 9-octadecanoic acid (C18:1,Delta 9) and a concomitant decrease in 9,12-octadecadienoic acid (C18:2,Delta 9,12) in less-pigmented compared with pigmented cell walls. This difference in fatty-acid composition may be related to the higher percentage of melanin in the pigmented than the less-pigmented cell walls. Lesser amounts of 9,12-octadecadienoic acid in less-pigmented cell walls may have been caused by the growth of the fungus under environmental stress conditions. An interesting observation was the presence in pigmented cell walls only of methyl-substituted fatty acids with carbon numbers C14 to C17, but their occurrence could not be ascertained in the present study.

Improvement of lubricant materials using ruthenium isomerization

USDA-ARS?s Scientific Manuscript database

Production of an effective industrial lubricant additive from vegetable oils is a high profile and difficult undertaking. One candidate is alkyl 9(10)-dibutylphosphonostearate, which has been made through a radical transformation of alkyl 9-cis-octadecanoate. It is effective, but still suffers from ...

Extraction and identification of bioactive components in Sida cordata (Burm.f.) using gas chromatography-mass spectrometry.

PubMed

Ganesh, Mani; Mohankumar, Murugan

2017-09-01

Sida cordata (Burm.f.) is a pineal tropical plant in the family Malvaceae that is found throughout India and used to treat various diseases and ailments in many complementary and alternative medicine systems. This study identified the bioactive components present in whole-plant ethanol extracts of S . cordata using gas chromatography-mass spectrometry (GC-MS). Based on their retention times (RT) and mass-to-charge ratios (m/z), 29 bioactive compounds were identified: nonanoic acid, vitamin D 3 , 3-trifluroacetoxypentadecane, α-d-glucopyranoside, O-α-d-glucopyranosyl-(1.fwdarw.3)-α-d-fructofuranosyl,3,7,11,15-tetramethyl-2-hexadecan-1-ol, octadecanoic acid, ethyl ester, phytol, 9,12-octadecadienoic acid, methyl ester (E,E), 9,12,15-octadecadienoic acid, methyl ester (Z,Z,Z), oleic acid, 1,2-15,16-diepoxyhexadecane, 3-hexadecyloxycarbonyl-5-(2-hydroxyethyl)-4-methylimidazolium ion, methoxyacetic acid, 4-tetradecyl ester, 1,2-benzenedicarboxylic acid, mono (2-ethylhexyl) ester, 1-iodo-2-methylundecane, dodecane, 2,6,10-trimethyl-, 2-piperidinone-N-[4-bromo-n-butyl]-, squalene, octadecane-1-(ethenyloxy)-, Z,Z-2,5-pentadecadien-1-ol, 1-hexadecanol, 2-methyl-, spiro[androst-5ene-17,1'-cyclobutan]-2'-one-3-hydroxy-, (3a,17a)-, diethylene glycol monododecyl ether, vitamin E, cholestan-3-ol, 2-methylene-, (3a,5a)-, 2H-pyran, 2-(7-heptadecynyloxy)tetrahydro-, and cis -Z-α-bisabolene epoxide. The presence of various bioactive compounds justifies the use of this plant for treating various ailments by traditional practitioners.

Acyl CoA profiles of transgenic plants that accumulate medium-chain fatty acids indicate inefficient storage lipid synthesis in developing oilseeds.

PubMed

Larson, Tony R; Edgell, Teresa; Byrne, James; Dehesh, Katayoon; Graham, Ian A

2002-11-01

Several Brassica napus lines transformed with genes responsible for the synthesis of medium- or long-chain fatty acids were examined to determine limiting factor(s) for the subsequent accumulation of these fatty acids in seed lipids. Examination of a decanoic acid (10:0) accumulating line revealed a disproportionately high concentration of 10:0 CoA during seed development compared to long-chain acyl CoAs isolated from the same tissues, suggesting that poor incorporation of 10:0 CoA into seed lipids limits 10:0 fatty acid accumulation. This relationship was also seen for dodecanoyl (12:0) CoA and fatty acid in a high 12:0 line, but not for octadecanoic (18:0) CoA and fatty acid in a high 18:0 line. Comparison of 10:0 CoA and fatty acid proportions from seeds at different developmental stages for transgenic B. napus and Cuphea hookeriana, the source plant for the medium-chain thioesterase and 3-ketoacyl-ACP synthase transgenes, revealed that C. hookeriana incorporates 10:0 CoA into seed lipids more efficiently than transgenic B. napus. Furthermore, beta-oxidation and glyoxylate cycle activities were not increased above wild type levels during seed development in the 8:0/10:0 line, suggesting that lipid catabolism was not being induced in response to the elevated 10:0 CoA concentrations. Taken together, these data suggest that transgenic plants that are engineered to synthesize medium-chain fatty acids may lack the necessary mechanisms, such as specific acyltransferases, to incorporate these fatty acids efficiently into seed lipids.

Chemical constituents and antioxidant and biological activities of the essential oil from leaves of Solanum spirale.

PubMed

Keawsa-ard, Sukanya; Liawruangrath, Boonsom; Liawruangrath, Saisunee; Teerawutgulrag, Aphiwat; Pyne, Stephen G

2012-07-01

The essential oil of the leaves Solanium spirale Roxb. was isolated by hydrodistillation and analyzed for the first time using GC and GC-MS. Thirty-nine constituents were identified, constituting 73.36% of the total chromatographical oil components. (E)-Phytol (48.10%), n-hexadecanoic acid (7.34%), beta-selinene (3.67%), alpha-selinene (2.74%), octadecanoic acid (2.12%) and hexahydrofarnesyl acetone (2.00%) were the major components of this oil. The antioxidant activity of the essential oil was evaluated by using the DPPH (1,1-diphenyl-2-picrylhydrazyl) radical scavenging assay. The oil exhibited week antioxidant activity with an IC50 of 41.89 mg/mL. The essential oil showed significant antibacterial activity against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus with MIC values of 43.0 microg/mL and 21.5 microg/mL, respectively. It also showed significant cytotoxicity against KB (oral cancer), MCF-7 (breast cancer) and NCI-H187 (small cell lung cancer) with the IC50 values of 26.42, 19.69, and 24.02 microg/mL, respectively.

Isolation, purification, and identification of antialgal substances in green alga Ulva prolifera for antialgal activity against the common harmful red tide microalgae.

PubMed

Sun, Ying-ying; Wang, Hui; Guo, Gan-lin; Pu, Yin-fang; Yan, Bin-lun; Wang, Chang-hai

2016-01-01

Ten compounds (1~10) were successfully isolated from green algae Ulva prolifera through the combination of silica gel column chromatography, Sephadex LH-20 column chromatography and repeated preparative thin-layer chromatography. These ten compounds showed antialgal activity against red tide microalgae. Among them, compounds 3, 6, and 7 showed stronger antialgal activity against red tide microalgae. Furthermore, their structure was identified on the basis of spectroscopic data. There are three glycoglycerolipids: 1-O-octadecanoic acid-3-O-β-D-galactopyranosyl glycerol (2), 1-O-palmitoyl-3-O-β-D-galactopyranosyl glycerol (4), and 1-O-palmitoyl-2-O-oleoyl-3-O-β-D-galactopyranosyl glycerol (5); two monoglycerides: glycerol monopalmitate (1), 9-hexadecenoic acid, 2,3-dihydroxypropyl ester (3); two terpenoids: loliolide (6) and lsololiolide (7); one lipid-soluble pigments: zeaxanthin (8); one sterol: cholest-5-en-3-ol (9); and one alkaloid: pyrrolopiperazine-2,5-dione (10). These compounds were isolated from U. prolifera for the first time, and compounds 2, 3, 5, and 8 were isolated from marine macroalgae for the first time.

Fatty Acid Composition of Dried Fruits of Sclerocarya birrea, Diospyros blancoi and Landolphia kirkii

PubMed Central

Matemu, Athanasia O.; Adeyemi, Durotoye; Nyoni, Hlengilizwe; Mdee, Ladislaus; Tshabalala, Papiso; Mamba, Bhekie

2017-01-01

Wild fruits are commonly consumed in the rural communities of South Africa. The information on their nutritionally important fatty acids is, however, limited. Three wild fruit species, Diospyros blancoi, Landolphia kirkii and Sclerocarya birrea from Limpopo Province were selected for evaluation of fatty acid content. Fatty acids composition of dried fruits of Diospyros blancoi (Db), Landolphia kirkii (Lk) and ripe and/or overripe Sclerocarya birrea (Sb) were evaluated by a gas chromatography-time of flight-mass spectrometer (GC-TOF-MS). Hexadecanoic acid (C16:0) was found in highest abundance in L. kirkii (57.73–73.55%), followed by S. birrea (55.92–71.31%) and D. blancoi (46.31–62.05%), respectively. Octadecanoic acid (C18:0) was of second highest abundance, with 24.71–100% in D. blancoi, L. kirkii (31.03–41.60%) and S. birrea (9.11–17.0%). The 9-octadecenoic acid (C18:1n-9) was the major unsaturated fatty acid in both S. birrea (5.33–18.82%), D. blancoi (8.22–8.92%), and L. kirkii (3.84–8.63%). The 9,-12-octadecadienoic acid (C18:2n-6) was the major unsaturated fatty acid in D. blancoi (22.34%). The 9,-12,-15-octadecatrienoic acid (C18:3n-3) was found in L. kirkii (3.51%) and S. birrea (2.79%). From the results, saturated fatty acids were the most dominant, whereas mono- and poly-unsaturated fatty acids were the minor constituents. Therefore, presence of nutritionally important essential fatty acids from S. birrea, D. blancoi and L. kirkii has been shown. PMID:29149025

The effects of temperature on the composition and physical properties of the lipids of Pseudomonas fluorescens.

PubMed

Cullen, J; Phillips, M C; Shipley, G G

1971-12-01

1. Pseudomonas fluorescens was grown at various temperatures between 5 degrees C and 33 degrees C. The extractable lipids from organisms at various stages of growth and grown at different temperatures were examined. 2. The extractable lipids contained phosphatidylethanolamine, diphosphatidylglycerol, phosphatidylglycerol, phosphatidylcholine, and an ornithine-containing lipid. The relative amounts of these lipids did not vary significantly during growth or with the changes in growth temperature. 3. The major fatty acids were hexadecanoic, hexadecenoic and octadecenoic acids and the cyclopropane acids methylene-hexadecanoic and methylene-octadecanoic acids. The relative amount of unsaturated acids (including cyclopropane acids) did not change significantly during growth, but increased with decreasing temperature. 4. Phosphatidylethanolamines with different degrees of unsaturation and containing different amounts of cyclopropane acids were isolated from organisms grown at 5 degrees C and 22 degrees C and their surface and phase behaviour in water was investigated. Thermodynamic parameters for fusion and monolayer results for cyclopropane and other fatty acids were examined. 5. The surface pressure-area isotherms of phosphatidylethanolamines containing different amounts of unsaturated fatty acids show small differences but the individual isotherms remain essentially unchanged over the temperature range 5-22 degrees C. X-ray-diffraction methods show that the structures (lamellar+hexagonal) formed in water by phosphatidylethanolamine, isolated from organisms grown at 5 degrees C and 22 degrees C, are identical when compared at the respective growth temperatures. This points to a control mechanism of the physical state of the lipids that is sensitive to the operating temperature of the organism. 6. The molecular packing of cyclopropane acids is intermediate between that of the corresponding cis- and trans-monoenoic acids. However, substitution of a cyclopropane acid for a cis-unsaturated acid has insignificant effects on the molecular packing of phospholipids containing these acids.

Ratios of carbon isotopes in microbial lipids as an indicator of substrate usage.

PubMed

Abraham, W R; Hesse, C; Pelz, O

1998-11-01

The occurrence and abundance of microbial fatty acids have been used for the identification of microorganisms in microbial communities. However, these fatty acids can also be used as indicators of substrate usage. For this, a systematic investigation of the discrimination of the stable carbon isotopes by different microorganisms is necessary. We grew 11 strains representing major bacterial and fungal species with four different isotopically defined carbon sources and determined the isotope ratios of fatty acids of different lipid fractions. A comparison of the differences of delta13C values of palmitic acid (C16:0) with the delta13C values of the substrates revealed that the isotope ratio is independent of the growth stage and that most microorganisms showed enrichment of C16:0 with 13C when growing on glycerol. With the exception of Burkholderia gladioli, all microorganism showed depletion of 13C in C16:0 while incorporating the carbons of glucose, and most of them were enriched with 13C from mannose, with the exception of Pseudomonas fluorescens and the Zygomycotina. Usually, the glycolipid fractions are depleted in 13C compared to the phospholipid fractions. The delta13C pattern was not uniform within the different fatty acids of a given microbial species. Generally, tetradecanoic acid (C14:0) was depleted of 13C compared to palmitic acid (C16:0) while octadecanoic acid (C18:0) was enriched. These results are important for the calibration of a new method in which delta13C values of fatty acids from the environment delineate the use of bacterial substrates in an ecosystem.

Removal of trimethylamine (fishy odor) by C₃ and CAM plants.

PubMed

Boraphech, Phattara; Thiravetyan, Paitip

2015-08-01

From screening 23 plant species, it was found that Pterocarpus indicus (C3) and Sansevieria trifasciata (crassulacean acid metabolism (CAM)) were the most effective in polar gaseous trimethylamine (TMA) uptake, reaching up to 90% uptake of initial TMA (100 ppm) within 8 h, and could remove TMA at cycles 1-4 without affecting photosystem II (PSII) photochemistry. Up to 55 and 45% of TMA was taken up by S. trifasciata stomata and leaf epicuticular wax, respectively. During cycles 1-4, interestingly, S. trifasciata changed its stomata apertures, which was directly induced by gaseous TMA and light treatments. In contrast, for P. indicus the leaf epicuticular wax and stem were the major pathways of TMA removal, followed by stomata; these pathways accounted for 46, 46, and 8%, respectively, of TMA removal percentages. Fatty acids, particularly tetradecanoic (C14) acid and octadecanoic (C18) acid, were found to be the main cuticular wax components in both plants, and were associated with TMA removal ability. Moreover, the plants could degrade TMA via multiple metabolic pathways associated with carbon/nitrogen interactions. In CAM plants, one of the crucial pathways enabled 78% of TMA to be transformed directly to dimethylamine (DMA) and methylamine (MA), which differed from C3 plant pathways. Various metabolites were also produced for further detoxification and mineralization so that TMA was completely degraded by plants.

Trimethylamine (fishy odor) adsorption by biomaterials: effect of fatty acids, alkanes, and aromatic compounds in waxes.

PubMed

Boraphech, Phattara; Thiravetyan, Paitip

2015-03-02

Thirteen plant leaf materials were selected to be applied as dried biomaterial adsorbents for polar gaseous trimethylamine (TMA) adsorption. Biomaterial adsorbents were efficient in adsorbing gaseous TMA up to 100% of total TMA (100 ppm) within 24 h. Sansevieria trifasciata is the most effective plant leaf material while Plerocarpus indicus was the least effective in TMA adsorption. Activated carbon (AC) was found to be lower potential adsorbent to adsorb TMA when compared to biomaterial adsorbents. As adsorption data, the Langmuir isotherm supported that the gaseous TMA adsorbed monolayer on the adsorbent surface and was followed pseudo-second order kinetic model. Wax extracted from plant leaf could also adsorb gaseous TMA up to 69% of total TMA within 24 h. Another 27-63% of TMA was adsorbed by cellulose and lignin that naturally occur in high amounts in plant leaf. Subsequently, the composition appearing in biomaterial wax showed a large quantity of short-chain fatty acids (≤C18) especially octadecanoic acid (C18), and short-chain alkanes (C12-C18) as well as total aromatic components dominated in the wax, which affected TMA adsorption. Hence, it has been demonstrated that plant biomaterial is a superior biosorbent for TMA removal.

Ratios of Carbon Isotopes in Microbial Lipids as an Indicator of Substrate Usage

PubMed Central

Abraham, Wolf-Rainer; Hesse, Christian; Pelz, Oliver

1998-01-01

The occurrence and abundance of microbial fatty acids have been used for the identification of microorganisms in microbial communities. However, these fatty acids can also be used as indicators of substrate usage. For this, a systematic investigation of the discrimination of the stable carbon isotopes by different microorganisms is necessary. We grew 11 strains representing major bacterial and fungal species with four different isotopically defined carbon sources and determined the isotope ratios of fatty acids of different lipid fractions. A comparison of the differences of δ13C values of palmitic acid (C16:0) with the δ13C values of the substrates revealed that the isotope ratio is independent of the growth stage and that most microorganisms showed enrichment of C16:0 with 13C when growing on glycerol. With the exception of Burkholderia gladioli, all microorganism showed depletion of 13C in C16:0 while incorporating the carbons of glucose, and most of them were enriched with 13C from mannose, with the exception of Pseudomonas fluorescens and the Zygomycotina. Usually, the glycolipid fractions are depleted in 13C compared to the phospholipid fractions. The δ13C pattern was not uniform within the different fatty acids of a given microbial species. Generally, tetradecanoic acid (C14:0) was depleted of 13C compared to palmitic acid (C16:0) while octadecanoic acid (C18:0) was enriched. These results are important for the calibration of a new method in which δ13C values of fatty acids from the environment delineate the use of bacterial substrates in an ecosystem. PMID:9797266

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

Uranga, Carla C., E-mail: curanga@cicese.edu.mx; Beld, Joris, E-mail: joris.beld@drexelmed.edu; Mrse, Anthony, E-mail: amrse@ucsd.edu

The Botryosphaeriaceae are a family of trunk disease fungi that cause dieback and death of various plant hosts. This work sought to characterize fatty acid derivatives in a highly virulent member of this family, Lasiodiplodia theobromae. Nuclear magnetic resonance and gas chromatography-mass spectrometry of an isolated compound revealed (Z, Z)-9,12-ethyl octadecadienoate, (trivial name ethyl linoleate), as one of the most abundant fatty acid esters produced by L. theobromae. A variety of naturally produced esters of fatty acids were identified in Botryosphaeriaceae. In comparison, the production of fatty acid esters in the soil-borne tomato pathogen Fusarium oxysporum, and the non-phytopathogenic fungusmore » Trichoderma asperellum was found to be limited. Ethyl linoleate, ethyl hexadecanoate (trivial name ethyl palmitate), and ethyl octadecanoate, (trivial name ethyl stearate), significantly inhibited tobacco seed germination and altered seedling leaf growth patterns and morphology at the highest concentration (0.2 mg/mL) tested, while ethyl linoleate and ethyl stearate significantly enhanced growth at low concentrations, with both still inducing growth at 98 ng/mL. This work provides new insights into the role of naturally esterified fatty acids from L. theobromae as plant growth regulators with similar activity to the well-known plant growth regulator gibberellic acid. - Highlights: • Lasiodiplodia theobromae produces a wide variety of fatty acid esters in natural substrates. • Ethyl stearate and ethyl linoleate inhibit tobacco germination at 0.2 mg/mL. • Ethyl stearate and ethyl linoleate induce tobacco germination at 98 ng/mL. • Tobacco growth increase in ethyl stearate and ethyl linoleate parallels gibberellic acid. • A role as plant growth regulators is proposed for fatty acid esters.« less

Antiproliferative effect of methanolic extraction of tualang honey on human keloid fibroblasts

PubMed Central

2011-01-01

Background Keloid is a type of scar which extends beyond the boundaries of the original wound. It can spread to the surrounding skin by invasion. The use of Tualang honey is a possible approach for keloid treatment. The objective of this study was to determine the antiproliferative effect of methanolic extraction of Tualang honey to primary human keloid fibroblasts and to identify the volatile compounds in methanol extraction of Tualang honey. Methods Crude Tualang honey was extracted with methanol and then dried using rota vapor to remove remaining methanol from honey. Normal and keloid fibroblasts were verified and treated with the extracted honey. Cell proliferation was tested with [3-(4,5-dimethylthiazol-2-yi)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium, inner salt] (MTS) assay. Extraction of Tualang honey using methanol was carried out and the extracted samples were analysed using gas chromatography-mass spectrometry (GC-MS). The result was analysed using SPSS and tested with Kruskal-Wallis and Mann-Whitney tests. Results Methanolic extraction of honey has positive anti proliferative effect on keloid fibroblasts in a dose-dependent manner. The presence of fatty acids such as palmitic acid, stearic acid, oleic acid, linoleic acid and octadecanoic acid may contribute to the anti-proliferative effect in keloid fibroblasts. Conclusions The methanolic honey extraction has an antiproliferative effect on keloid fibroblasts and a range of volatile compounds has been identified from Tualang honey. The antiproliferative effect of keloid fibroblasts towards Tualang honey may involve cell signaling pathway. Identifying other volatile compounds from different organic solvents should be carried out in future. PMID:21943200

Confocal analysis of hepatocellular long-chain fatty acid uptake.

PubMed

Elsing, C; Winn-Börner, U; Stremmel, W

1995-12-01

Transmembrane transport and cytosolic accumulation of fatty acids were investigated using confocal laser scanning microscopy (cLSM). A Zeiss LSM 310 system was used to determine the uptake of the fluorescent fatty acid derivative 12-(N-methyl)-N-[(7-nitrobenz-2-oxa-1,3- diazol-4-yl)amino]octadecanoic acid (12-NBD stearate) (C18) in single rat hepatocytes. Uptake was a saturable process with a Michaelis-Menten constant value of 68 nM. Initial uptake velocity was dependent on extracellular presence of albumin and beta-lactoglobulin. Absence of albumin reduced uptake to 32 +/- 16% (P < 0.01) of control values. In the presence of unlabeled stearate, uptake of 12-NBD stearate was lowered to 49 +/- 12% (P < 0.01). Ion substitution experiments showed no sodium dependency of uptake. Increase in membrane potential led to a pronounced accumulation of the fatty acid derivative within the plasma membrane and in the adjacent cytoplasmic compartment, whereas membrane depolarization had no effect on uptake rates. In separate experiments line scans through representative hepatocytes were analyzed to generate "x-t" plots. 12-NBD stearate showed a fluorescence pattern with prominent staining of the area of the plasma membrane and the adjacent cytoplasm, dependent on the presence of extracellular albumin. For the hepatocellular cytosolic accumulation process of 12-NBD stearate a diffusion constant of 22.2 +/- 6.2 x 10(-9) cm2/s was calculated. In contrast to the long-chain fatty acid derivative 12-NBD stearate, short (C5)- and medium (C11)-chain fatty acids revealed no membrane interaction with hepatocytes. Erythrocytes also lacked a membrane interaction process for 12-NBD stearate. In conclusion, it was demonstrated that cLSM is capable of directly evaluating the cellular fatty acid uptake process at a subcellular level.

The effects of temperature on the composition and physical properties of the lipids of Pseudomonas fluorescens

PubMed Central

Cullen, J.; Phillips, M. C.; Shipley, G. G.

1971-01-01

1. Pseudomonas fluorescens was grown at various temperatures between 5°C and 33°C. The extractable lipids from organisms at various stages of growth and grown at different temperatures were examined. 2. The extractable lipids contained phosphatidylethanolamine, diphosphatidylglycerol, phosphatidylglycerol, phosphatidylcholine, and an ornithine-containing lipid. The relative amounts of these lipids did not vary significantly during growth or with the changes in growth temperature. 3. The major fatty acids were hexadecanoic, hexadecenoic and octadecenoic acids and the cyclopropane acids methylene-hexadecanoic and methylene-octadecanoic acids. The relative amount of unsaturated acids (including cyclopropane acids) did not change significantly during growth, but increased with decreasing temperature. 4. Phosphatidylethanolamines with different degrees of unsaturation and containing different amounts of cyclopropane acids were isolated from organisms grown at 5°C and 22°C and their surface and phase behaviour in water was investigated. Thermodynamic parameters for fusion and monolayer results for cyclopropane and other fatty acids were examined. 5. The surface pressure–area isotherms of phosphatidylethanolamines containing different amounts of unsaturated fatty acids show small differences but the individual isotherms remain essentially unchanged over the temperature range 5–22°C. X-ray-diffraction methods show that the structures (lamellar+hexagonal) formed in water by phosphatidylethanolamine, isolated from organisms grown at 5°C and 22°C, are identical when compared at the respective growth temperatures. This points to a control mechanism of the physical state of the lipids that is sensitive to the operating temperature of the organism. 6. The molecular packing of cyclopropane acids is intermediate between that of the corresponding cis- and trans-monoenoic acids. However, substitution of a cyclopropane acid for a cis-unsaturated acid has insignificant effects on the molecular packing of phospholipids containing these acids. PMID:5004336

Volatile oil composition of Carthamus Tinctorius L. flowers grown in Kazakhstan.

PubMed

Turgumbayeva, Aknur Amanbekovna; Ustenova, Gulbaram Omargazieva; Yeskalieva, Balakyz Kymyzgalievna; Ramazanova, Bakyt Amanullovna; Rahimov, Kairolla Duysenbayevich; Aisa, Hajiakbar; Juszkiewicz, Konrad T

2018-03-14

Carthamus tinctorius L. is commonly known as Safflower. C. tinctorius extracts and oil are important in drug development with numerous pharmacological activities in the world. This plant is cultivated mainly for its seed which is used as edible oil. For a long time, C. tinctorius has been used in traditional medicines as a purgative, analgesic, antipyretic and an antidote to poisoning. It is a useful plant in painful menstrual problems, post-partum haemorrhage and osteoporosis. The subject of this study is the seeds of Kazakhstan species of 'Akmai' safflower, collected in the flowering stage in Southern Kazakhstan. Volatile oil was carry out to study the component composition of Kazakhstan 'AkMai' safflower flowers. Pale yellow oily extracts were obtain by varying the process parameters. The volatile oil obtained by hydrodistillation of the petals Carthamus tinctorius L. was analyzed by gas chromatography/mass spectrometry (GC/MS). The yield of the oil was 0.175 % (v/w). 20 compounds representing 99.81% of the oil were characterized. The volatile oil was found to be rich in undecanoic acid, octane, 2-nonen -1-ol, hexadecanal, dodecanal, dec-2-en-1-ol, nonanoic acid, tetradecanoic acid, 2 pentadecanone, 6,10,14-trimethyl, 1,2-benzenedicarboxylic acid, isobutyl-beta-phenylpropionate, 1.3-cyclohexadiene, myrtenoic acid, octadecanoic acid, heneicosanoic acid, 2(3H)-furanone, 4,4-dipropylheptane, hexcosane,1-eicosanol, as well as heptocosane. Volatile oil from the flowers of the Kazakhstan safflower species 'Ak-Mai' were investigated by GC/MS which allowed the detection of 20 compounds. Biologically active complex of the flower of the Kazakhstan safflower species 'Ak-Mai' was released for the first time by using this oil.

[Analysis of supercritical fluid extracts of Radix caulophylli with gas chromatography-mass spectrometry].

PubMed

Wang, Si-Cen; Chen, Qin-Hua; Wei, Yao-Yuan; Li, Han-Wen; He, Lang-Chong

2007-05-01

To analyze the constituents in supercritical fluid CO2 extraction (SFE-CO2) of Radix caulophylli, the Radix caulophylli was extracted with SFE-CO2, and analyzed by gas chromatography-mass spectrometry (GC-MS). The GC-MS analysis with a DB-5MS capillary column (30 mm x 0.32 mm ID, 0.25 microm film thickness) was used. The inlet temperature was maintained at 280 degrees C. The column oven was held at 80 degrees C for 2 min, then programmed from 80 to 280 degrees C at 5 degrees C x min(-1) and, finally, held for 4 min. Helium at a constant flow rate of 2.0 mL x min(-1) was used as the carrier gas. The mass spectrometry conditions were as follows: ionization energy, 70 eV; ion source temperature, 200 degrees C. The mass selective detector was operated in the TIC mode (m/z was from 40 - 500). For the first time 49 peaks were separated and identified, the compounds were quantitatively determined by normalization method, and the identified compounds represent 97.44% of total GC peak areas. Viz, n-hexadecanoic acid (31.4%), (E, E) -9, 12-octadecadienoic acid (26.54%), (Z)-7-tetradecenal (9.4%), hexadecenoic acid (3.23%), 10-undecenal (3.22%), octadecanoic acid (2.25%), and caulophylline (1.76%) etc. The results will provide important foundation for understanding the constituents and further exploitation of Radix caulophylli.

Profiling of Fatty Acids Composition in Suet Oil Based on GC–EI-qMS and Chemometrics Analysis

PubMed Central

Jiang, Jun; Jia, Xiaobin

2015-01-01

Fatty acid (FA) composition of suet oil (SO) was measured by precolumn methylesterification (PME) optimized using a Box–Behnken design (BBD) and gas chromatography/electron ionization-quadrupole mass spectrometry (GC–EI-qMS). A spectral library (NIST 08) and standard compounds were used to identify FAs in SO representing 90.89% of the total peak area. The ten most abundant FAs were derivatized into FA methyl esters (FAMEs) and quantified by GC–EI-qMS; the correlation coefficient of each FAME was 0.999 and the lowest concentration quantified was 0.01 μg/mL. The range of recovery of the FAMEs was 82.1%–98.7% (relative standard deviation 2.2%–6.8%). The limits of quantification (LOQ) were 1.25–5.95 μg/L. The number of carbon atoms in the FAs identified ranged from 12 to 20; hexadecanoic and octadecanoic acids were the most abundant. Eighteen samples of SO purchased from Qinghai, Anhui and Jiangsu provinces of China were categorized into three groups by principal component analysis (PCA) according to the contents of the most abundant FAs. The results showed SOs samples were rich in FAs with significantly different profiles from different origins. The method described here can be used for quality control and SO differentiation on the basis of the FA profile. PMID:25636032

The Fatty Acid Profile Analysis of Cyperus laxus Used for Phytoremediation of Soils from Aged Oil Spill-Impacted Sites Revealed That This Is a C18:3 Plant Species.

PubMed

Rivera Casado, Noemí Araceli; Montes Horcasitas, María del Carmen; Rodríguez Vázquez, Refugio; Esparza García, Fernando José; Pérez Vargas, Josefina; Ariza Castolo, Armando; Ferrera-Cerrato, Ronald; Gómez Guzmán, Octavio; Calva Calva, Graciano

2015-01-01

The effect of recalcitrant hydrocarbons on the fatty acid profile from leaf, basal corm, and roots of Cyperus laxus plants cultivated in greenhouse phytoremediation systems of soils from aged oil spill-impacted sites containing from 16 to 340 g/Kg total hydrocarbons (THC) was assessed to investigate if this is a C18:3 species and if the hydrocarbon removal during the phytoremediation process has a relationship with the fatty acid profile of this plant. The fatty acid profile was specific to each vegetative organ and was strongly affected by the hydrocarbons level in the impacted sites. Leaf extracts of plants from uncontaminated soil produced palmitic acid (C16), octadecanoic acid (C18:0), unsaturated oleic acids (C18:1-C18:3), and unsaturated eichosanoic (C20:2-C20:3) acids with a noticeable absence of the unsaturated hexadecatrienoic acid (C16:3); this finding demonstrates, for the first time, that C. laxus is a C18:3 plant. In plants from the phytoremediation systems, the total fatty acid contents in the leaf and the corm were negatively affected by the hydrocarbons presence; however, the effect was positive in root. Interestingly, under contaminated conditions, unusual fatty acids such as odd numbered carbons (C15, C17, C21, and C23) and uncommon unsaturated chains (C20:3n6 and C20:4) were produced together with a remarkable quantity of C22:2 and C24:0 chains in the corm and the leaf. These results demonstrate that weathered hydrocarbons may drastically affect the lipidic composition of C. laxus at the fatty acid level, suggesting that this species adjusts the cover lipid composition in its vegetative organs, mainly in roots, in response to the weathered hydrocarbon presence and uptake during the phytoremediation process.

The Fatty Acid Profile Analysis of Cyperus laxus Used for Phytoremediation of Soils from Aged Oil Spill-Impacted Sites Revealed That This Is a C18:3 Plant Species

PubMed Central

Montes Horcasitas, María del Carmen; Rodríguez Vázquez, Refugio; Esparza García, Fernando José; Pérez Vargas, Josefina; Ariza Castolo, Armando; Ferrera-Cerrato, Ronald; Gómez Guzmán, Octavio

2015-01-01

The effect of recalcitrant hydrocarbons on the fatty acid profile from leaf, basal corm, and roots of Cyperus laxus plants cultivated in greenhouse phytoremediation systems of soils from aged oil spill-impacted sites containing from 16 to 340 g/Kg total hydrocarbons (THC) was assessed to investigate if this is a C18:3 species and if the hydrocarbon removal during the phytoremediation process has a relationship with the fatty acid profile of this plant. The fatty acid profile was specific to each vegetative organ and was strongly affected by the hydrocarbons level in the impacted sites. Leaf extracts of plants from uncontaminated soil produced palmitic acid (C16), octadecanoic acid (C18:0), unsaturated oleic acids (C18:1-C18:3), and unsaturated eichosanoic (C20:2-C20:3) acids with a noticeable absence of the unsaturated hexadecatrienoic acid (C16:3); this finding demonstrates, for the first time, that C. laxus is a C18:3 plant. In plants from the phytoremediation systems, the total fatty acid contents in the leaf and the corm were negatively affected by the hydrocarbons presence; however, the effect was positive in root. Interestingly, under contaminated conditions, unusual fatty acids such as odd numbered carbons (C15, C17, C21, and C23) and uncommon unsaturated chains (C20:3n6 and C20:4) were produced together with a remarkable quantity of C22:2 and C24:0 chains in the corm and the leaf. These results demonstrate that weathered hydrocarbons may drastically affect the lipidic composition of C. laxus at the fatty acid level, suggesting that this species adjusts the cover lipid composition in its vegetative organs, mainly in roots, in response to the weathered hydrocarbon presence and uptake during the phytoremediation process. PMID:26473488

Transcriptional Profiling of Sorghum Induced by Methyl Jasmonate, Salicylic Acid, and Aminocyclopropane Carboxylic Acid Reveals Cooperative Regulation and Novel Gene Responses1[w

PubMed Central

Salzman, Ron A.; Brady, Jeff A.; Finlayson, Scott A.; Buchanan, Christina D.; Summer, Elizabeth J.; Sun, Feng; Klein, Patricia E.; Klein, Robert R.; Pratt, Lee H.; Cordonnier-Pratt, Marie-Michèle; Mullet, John E.

2005-01-01

We have conducted a large-scale study of gene expression in the C4 monocot sorghum (Sorghum bicolor) L. Moench cv BTx623 in response to the signaling compounds salicylic acid (SA), methyl jasmonate (MeJA), and the ethylene precursor aminocyclopropane carboxylic acid. Expression profiles were generated from seedling root and shoot tissue at 3 and 27 h, using a microarray containing 12,982 nonredundant elements. Data from 102 slides and quantitative reverse transcription-PCR data on mRNA abundance from 171 genes were collected and analyzed and are here made publicly available. Numerous gene clusters were identified in which expression was correlated with particular signaling compound and tissue combinations. Many genes previously implicated in defense responded to the treatments, including numerous pathogenesis-related genes and most members of the phenylpropanoid pathway, and several other genes that may represent novel activities or pathways. Genes of the octadecanoic acid pathway of jasmonic acid (JA) synthesis were induced by SA as well as by MeJA. The resulting hypothesis that increased SA could lead to increased endogenous JA production was confirmed by measurement of JA content. Comparison of responses to SA, MeJA, and combined SA+MeJA revealed patterns of one-way and mutual antagonisms, as well as synergistic effects on regulation of some genes. These experiments thus help further define the transcriptional results of cross talk between the SA and JA pathways and suggest that a subset of genes coregulated by SA and JA may comprise a uniquely evolved sector of plant signaling responsive cascades. PMID:15863699

New chemical constituents from Oryza sativa straw and their algicidal activities against blue-green algae.

PubMed

Ahmad, Ateeque; Kim, Seung-Hyun; Ali, Mohd; Park, Inmyoung; Kim, Jin-Seog; Kim, Eun-Hye; Lim, Ju-Jin; Kim, Seul-Ki; Chung, Ill-Min

2013-08-28

Five new constituents, 5,4'-dihydroxy-7,3'-dimethoxyflavone-4'-O-β-D-xylopyranosyl-(2a→1b)-2a-O-β-D-xylopyranosyl-(2b→1c)-2b-O-β-D-xylopyranosyl-2c-octadecanoate (1), 5,4'-dihydroxy-7,3'-dimethoxyflavone-4'-O-α-D-xylopyranosyl-(2a→1b)-2a-O-α-D-xylopyranosyl-(2b→1c)-2b-O-α-D-xylopyranosyl-(2c→1d)-2c-O-α-D-xylopyranosyl-2d-octadecanoate (2), kaempferol-3-O-α-D-xylopyranosyl-(2a→1b)-2a-O-α-D-xylopyranosyl-(2b→1c)-2b-O-α-D-xylopyranosyl-(2c→1d)-2c-O-α-D-xylopyranosyl-2d-hexadecanoate (3), methyl salicylate-2-O-α-D-xylopyranosyl-(2a→1b)-2a-O-α-D-xylopyranosyl-(2b→1c)-2b-O-α-D-xylopyranosyl-(2c→1d)-2c-O-α-D-xylopyranosyl-(2d→1e)-2d-O-α-D-xylopyranosyl-(2e→1f)-2e-O-α-D-xylopyranosyl-(2f→1g)-2f-O-α-D-xylopyranosyl-(2g→1h)-2g-O-α-D-xylopyranosyl-2h-geranilan-8',10'-dioic acid-1'-oate (4), and oleioyl-β-D-arabinoside (5), along with eight known compounds, were isolated from a methanol extract of Oryza sativa straw. The structures of the new compounds were elucidated using one- and two-dimensional NMR spectroscopies in combination with IR, ESI/MS, and HR-ESI/FTMS. In bioassays with blue-green algae, the efficacies of the algicidal activities of the five new compounds (1-5) were evaluated at concentrations of 1, 10, and 100 mg/L. Compound 5 had the highest growth inhibition (92.6 ± 0.3%) for Microcystis aeruginosa UTEX 2388 at a concentration of 100 ppm (mg/L). Compound 5 has high potential for the ecofriendly control of weeds and algae harmful to water-logged rice.

Purification and characterization of two polyhydroxyalcanoates from Bacillus cereus.

PubMed

Zribi-Maaloul, Emna; Trabelsi, Imen; Elleuch, Lobna; Chouayekh, Hichem; Ben Salah, Riadh

2013-10-01

This work aimed to study the potential of 155 strains of Bacillus sp., isolated from a collection of Tunisian microorganisms, for polyhydroxyalcanoates production. The strains were submitted to a battery of standard tests commonly used for determining bioplastic properties. The findings revealed that two of the isolates, namely Bacillus US 163 and US 177, provided red excitations at a wavelength of approximately 543 nm. The polyhydroxyalcanoates produced by the two strains were purified. Gas chromatography-mass spectroscopy (GC-MS), Fourier transformed infrared spectroscopy (FTIR), and gel permeation chromatography (GPC) were used to characterize the two biopolymers. Bacillus US 163 was noted to produce a poly methyl-3-hydroxy tetradecanoic acid (P-3HTD) with an average molecular weight of 455 kDa, a completely amorphous homopolymer without crystallinity. The US 177 strain produced a homopolymer of methyl-3-hydroxy octadecanoic acid (P3-HOD) with an average molecular weight of 555 kDa. Exhibiting the highest performance, US 163 and US 177 were submitted to 16S rRNA gene sequencing, and the results revealed that they belonged to the Bacillus cereus species. Overall, the findings indicated that the Bacilli from petroleum soil have a number of promising properties that make them promising candidates for bioplastic production. Copyright © 2013 Elsevier B.V. All rights reserved.

Fruit cuticle lipid composition and water loss in a diverse collection of pepper (Capsicum).

PubMed

Parsons, Eugene P; Popopvsky, Sigal; Lohrey, Gregory T; Alkalai-Tuvia, Sharon; Perzelan, Yaacov; Bosland, Paul; Bebeli, Penelope J; Paran, Ilan; Fallik, Elazar; Jenks, Matthew A

2013-10-01

Pepper (Capsicum spp.) fruits are covered by a relatively thick coating of cuticle that limits fruit water loss, a trait previously associated with maintenance of postharvest fruit quality during commercial marketing. To shed light on the chemical-compositional diversity of cuticles in pepper, the fruit cuticles from 50 diverse pepper genotypes from a world collection were screened for both wax and cutin monomer amount and composition. These same genotypes were also screened for fruit water loss rate and this was tested for associations with cuticle composition. Our results revealed an unexpectedly large amount of variation for the fruit cuticle lipids, with a more than 14-fold range for total wax amounts and a more than 16-fold range for cutin monomer amounts between the most extreme accessions. Within the major wax constituents fatty acids varied from 1 to 46%, primary alcohols from 2 to 19%, n-alkanes from 13 to 74% and triterpenoids and sterols from 10 to 77%. Within the cutin monomers, total hexadecanoic acids ranged from 54 to 87%, total octadecanoic acids ranged from 10 to 38% and coumaric acids ranged from 0.2 to 8% of the total. We also observed considerable differences in water loss among the accessions, and unique correlations between water loss and cuticle constituents. The resources described here will be valuable for future studies of the physiological function of fruit cuticle, for the identification of genes and QTLs associated with fruit cuticle synthesis in pepper fruit, and as a starting point for breeding improved fruit quality in pepper. © 2013 Scandinavian Plant Physiology Society.

Effect of three fatty acids from the leaf extract of Tiliacora triandra on P-glycoprotein function in multidrug-resistant A549RT-eto cell line

PubMed Central

Kaewpiboon, Chutima; Winayanuwattikun, Pakorn; Yongvanich, Tikamporn; Phuwapraisirisan, Preecha; Assavalapsakul, Wanchai

2014-01-01

Background: Cancer cells have the ability to develop resistance to chemotherapy drugs, which then leads to a reduced effectiveness and success of the treatment. Multidrug resistance (MDR) involves the resistance in the same cell/tissue to a diverse range of drugs of different structures. One of the characteristics of MDR is an overexpression of P-glycoprotein (P-gp), which causes the efflux of the accumulated drug out of the cell. The MDR human non-small cell lung carcinoma cell line with a high P-gp expression level (A549RT-eto) was used to investigate the bioactive compounds capable of reversing the etoposide resistance in this cell line. Materials and Methods: The leaves of Tiliacora triandra were sequentially extracted with hexane, dichloromethane, methanol and water. Only the hexane extract reduced the etoposide resistance of the A549RT-eto cell line, and was further fractionated by column chromatography using the TLC-pattern and the restoration of etoposide sensitivity as the selection criteria. Results: The obtained active fraction (F22) was found by nuclear magnetic resonance and gas chromatography-mass spectroscopy analyses to be comprised of a 49.5:19.6:30.9 (w/w/w) mixture of hexadecanoic: octadecanoic acid: (Z)-6-octadecenoic acids. This stoichiometric mixture was recreated using pure fatty acids (MSFA) and gave a similar sensitization to etoposide and enhanced the relative rate of rhodamine-123 accumulation to a similar extent as F22, supporting the action via reducing P-gp activity. In contrast, the fatty acids alone did not show this effect. Conclusion: This is the first report of the biological activity from the leaves of T. triandra as a potential source of a novel chemosensitizer. PMID:25298673

Effect of three fatty acids from the leaf extract of Tiliacora triandra on P-glycoprotein function in multidrug-resistant A549RT-eto cell line.

PubMed

Kaewpiboon, Chutima; Winayanuwattikun, Pakorn; Yongvanich, Tikamporn; Phuwapraisirisan, Preecha; Assavalapsakul, Wanchai

2014-08-01

Cancer cells have the ability to develop resistance to chemotherapy drugs, which then leads to a reduced effectiveness and success of the treatment. Multidrug resistance (MDR) involves the resistance in the same cell/tissue to a diverse range of drugs of different structures. One of the characteristics of MDR is an overexpression of P-glycoprotein (P-gp), which causes the efflux of the accumulated drug out of the cell. The MDR human non-small cell lung carcinoma cell line with a high P-gp expression level (A549RT-eto) was used to investigate the bioactive compounds capable of reversing the etoposide resistance in this cell line. The leaves of Tiliacora triandra were sequentially extracted with hexane, dichloromethane, methanol and water. Only the hexane extract reduced the etoposide resistance of the A549RT-eto cell line, and was further fractionated by column chromatography using the TLC-pattern and the restoration of etoposide sensitivity as the selection criteria. The obtained active fraction (F22) was found by nuclear magnetic resonance and gas chromatography-mass spectroscopy analyses to be comprised of a 49.5:19.6:30.9 (w/w/w) mixture of hexadecanoic: octadecanoic acid: (Z)-6-octadecenoic acids. This stoichiometric mixture was recreated using pure fatty acids (MSFA) and gave a similar sensitization to etoposide and enhanced the relative rate of rhodamine-123 accumulation to a similar extent as F22, supporting the action via reducing P-gp activity. In contrast, the fatty acids alone did not show this effect. This is the first report of the biological activity from the leaves of T. triandra as a potential source of a novel chemosensitizer.

Biodegradation of Endocrine-Disrupting Chemicals and Residual Organic Pollutants of Pulp and Paper Mill Effluent by Biostimulation.

PubMed

Chandra, Ram; Sharma, Pooja; Yadav, Sangeeta; Tripathi, Sonam

2018-01-01

Effluent discharged from the pulp and paper industry contains various refractory and androgenic compounds, even after secondary treatment by activated processes. Detailed knowledge is not yet available regarding the properties of organic pollutants and methods for their bioremediation. This study focused on detecting residual organic pollutants of pulp and paper mill effluent after biological treatment and assessing their degradability by biostimulation. The major compounds identified in the effluent were 2,3,6-trimethylphenol, 2-methoxyphenol (guaiacol), 2,6-dimethoxyphenol (syringol), methoxycinnamic acid, pentadecane, octadecanoic acid, trimethylsilyl ester, cyclotetracosane, 5,8-dimethoxy-6-methyl-2,4-bis(phenylmethyl)napthalen-1-ol, and 1,2-benzendicarboxylic acid diisononyl ester. Most of these compounds are classified as endocrine-disrupting chemicals and environmental toxicants. Some compounds are lignin monomers that are metabolic products from secondary treatment of the discharged effluent. This indicated that the existing industrial process could not further degrade the effluent. Supplementation by carbon (glucose 1.0%) and nitrogen (peptone 0.5%) bio-stimulated the degradation process. The degraded sample after biostimulation showed either disappearance or generation of metabolic products under optimized conditions, i.e., a stirring rate of 150 rpm and temperature of 37 ± 1°C after 3 and 6 days of bacterial incubation. Isolated potential autochthonous bacteria were identified as Klebsiella pneumoniae IITRCP04 (KU715839), Enterobacter cloacae strain IITRCP11 (KU715840), Enterobacter cloacae IITRCP14 (KU715841), and Acinetobacter pittii strain IITRCP19 (KU715842). Lactic acid, benzoic acid, and vanillin, resulting from residual chlorolignin compounds, were generated as potential value-added products during the detoxification of effluent in the biostimulation process, supporting the commercial importance of this process.

Epicuticular lipids induce aggregation in Chagas disease vectors

PubMed Central

Figueiras, Alicia N Lorenzo; Girotti, Juan R; Mijailovsky, Sergio J; Juárez, M Patricia

2009-01-01

Background The triatomine bugs are vectors of the protozoan parasite Trypanosoma cruzi, the causative agent of Chagas disease. Aggregation behavior plays an important role in their survival by facilitating the location of refuges and cohesion of aggregates, helping to keep them safely assembled into shelters during daylight time, when they are vulnerable to predators. There are evidences that aggregation is mediated by thigmotaxis, by volatile cues from their faeces, and by hexane-extractable contact chemoreceptive signals from their cuticle surface. The epicuticular lipids of Triatoma infestans include a complex mixture of hydrocarbons, free and esterified fatty acids, alcohols, and sterols. Results We analyzed the response of T. infestans fifth instar nymphs after exposure to different amounts either of total epicuticular lipid extracts or individual lipid fractions. Assays were performed in a circular arena, employing a binary choice test with filter papers acting as aggregation attractive sites; papers were either impregnated with a hexane-extract of the total lipids, or lipid fraction; or with the solvent. Insects were significantly aggregated around papers impregnated with the epicuticular lipid extracts. Among the lipid fractions separately tested, only the free fatty acid fraction promoted significant bug aggregation. We also investigated the response to different amounts of selected fatty acid components of this fraction; receptiveness varied with the fatty acid chain length. No response was elicited by hexadecanoic acid (C16:0), the major fatty acid component. Octadecanoic acid (C18:0) showed a significant assembling effect in the concentration range tested (0.1 to 2 insect equivalents). The very long chain hexacosanoic acid (C26:0) was significantly attractant at low doses (≤ 1 equivalent), although a repellent effect was observed at higher doses. Conclusion The detection of contact aggregation pheromones has practical application in Chagas disease vector control. These data may be used to help design new tools against triatomine bugs. PMID:19173716

Epicuticular lipids induce aggregation in Chagas disease vectors.

PubMed

Figueiras, Alicia N Lorenzo; Girotti, Juan R; Mijailovsky, Sergio J; Juárez, M Patricia

2009-01-27

The triatomine bugs are vectors of the protozoan parasite Trypanosoma cruzi, the causative agent of Chagas disease. Aggregation behavior plays an important role in their survival by facilitating the location of refuges and cohesion of aggregates, helping to keep them safely assembled into shelters during daylight time, when they are vulnerable to predators. There are evidences that aggregation is mediated by thigmotaxis, by volatile cues from their faeces, and by hexane-extractable contact chemoreceptive signals from their cuticle surface. The epicuticular lipids of Triatoma infestans include a complex mixture of hydrocarbons, free and esterified fatty acids, alcohols, and sterols. We analyzed the response of T. infestans fifth instar nymphs after exposure to different amounts either of total epicuticular lipid extracts or individual lipid fractions. Assays were performed in a circular arena, employing a binary choice test with filter papers acting as aggregation attractive sites; papers were either impregnated with a hexane-extract of the total lipids, or lipid fraction; or with the solvent. Insects were significantly aggregated around papers impregnated with the epicuticular lipid extracts. Among the lipid fractions separately tested, only the free fatty acid fraction promoted significant bug aggregation. We also investigated the response to different amounts of selected fatty acid components of this fraction; receptiveness varied with the fatty acid chain length. No response was elicited by hexadecanoic acid (C16:0), the major fatty acid component. Octadecanoic acid (C18:0) showed a significant assembling effect in the concentration range tested (0.1 to 2 insect equivalents). The very long chain hexacosanoic acid (C26:0) was significantly attractant at low doses (

Antioxidant and antimicrobial activities of ethyl acetate extract, fractions and compounds from stem bark of Albizia adianthifolia (Mimosoideae).

PubMed

Tamokou, Jean de Dieu; Simo Mpetga, Deke James; Keilah Lunga, Paul; Tene, Mathieu; Tane, Pierre; Kuiate, Jules Roger

2012-07-18

Albizia adianthifolia is used traditionally in Cameroon to treat several ailments, including infectious and associated diseases. This work was therefore designed to investigate the antioxidant and antimicrobial activities of ethyl acetate extract, fractions and compounds isolated from the stem bark of this plant. The plant extract was prepared by maceration in ethyl acetate. Its fractionation was done by column chromatography and the structures of isolated compounds were elucidated using spectroscopic data in conjunction with literature data. The 1,1-diphenyl-2-picrylhydrazyl (DPPH) and trolox equivalent antioxidant capacity (TEAC) assays were used to detect the antioxidant activity. Broth micro-dilution method was used for antimicrobial test. Total phenol content was determined spectrophotometrically in the extracts by using Folin-Ciocalteu method. The fractionation of the extract afforded two known compounds: lupeol (1) and aurantiamide acetate (2) together with two mixtures of fatty acids: oleic acid and n-hexadecanoic acid (B₁); n-hexadecanoic acid, octadecanoic acid and docosanoic acid (B₂). Aurantiamide acetate was the most active compound. The total phenol concentration expressed as gallic acid equivalents (GAE) was found to vary from 1.50 to 13.49 μg/ml in the extracts. The antioxidant activities were well correlated with the total phenol content (R² = 0.946 for the TEAC method and R² = 0.980 for the DPPH free-radical scavenging assay). Our results clearly reveal that the ethyl acetate extract from the stem bark of A. adianthifolia possesses antioxidant and antimicrobial principles. The antioxidant activity of this extract as well as that of compound 2 are being reported herein for the first time. These results provide promising baseline information for the potential use of this plant as well as compound 2 in the treatment of oxidative damage and infections associated with the studied microorganisms.

Characterization of Extractable Organic Fine Particulate Matter in the Atmosphere of Houston and Source Apportionment Calculations Using Organic Molecular Markers

NASA Astrophysics Data System (ADS)

Fraser, M. P.; Yue, Z. W.; Buzco, B.

2002-12-01

Samples of atmospheric PM2.5 were collected in Houston, TX every second day during the summer of 2000 as part of the EPA sponsored Houston Fine Particle Matter Supersite program. Sampling occurred at three sites, including one industrial location (HRM-3), one suburban location (Aldine) and one coastal location (La Porte). Twenty samples collected over a 24 hour period have been analyzed to quantify the concentration of 95 individual organic compounds, including: n-alkanes (C20 to C36), aromatic hydrocarbons (PAHs), n-alkanoic acids (C5 to C34), n-alkenoic acids (C18:1 and C18:2), carboxylic diacids (C3 to C10), petroleum biomarkers and others. As a whole, the extractable compounds were dominated by acids, especially by octadecanoic acid and hexadecanoic acid. The measured concentration of n-alkanes exhibited a peak at C29, with carbon preference index (CPI) values in the range of 0.97 to 2.0. Using organic molecular markers, including seven alkanes, four petroleum biomarkers, seven PAH, one alkanoic acid, one alkenoic acid, levoglucosan, and three chemical components (Al, Si and Elemental Carbon), Chemical Mass Balancing (CMB) calculations have been performed on the ambient speciation data. These calculations are used to determine the contribution of seven different primary emission sources including: diesel powered vehicles, gasoline vehicles, wood combustion, fuel oil combustion, road dusts, meat cooking and vegetation waxes. The contribution of diesel powered vehicles and gasoline powered vehicles are the most important primary sources at all three sampling locations, with road dusts important at the industrial location. Meat cooking emissions were significant at all three locations. Wood combustion is an important contribution during a four-day period when uncontrolled wildfires in eastern Texas and Louisiana brought biomass combustion aerosols into the sampling region.

Bioprospecting microbes for single-cell oil production from starchy wastes.

PubMed

Chaturvedi, Shivani; Kumari, Arti; Nain, Lata; Khare, Sunil K

2018-03-16

Production of lipid from oleaginous yeast using starch as a carbon source is not a common practice; therefore, the purpose of this investigation was to explore the capability of starch assimilating microbes to produce oil, which was determined in terms of biomass weight, productivity, and lipid yield. Saccharomyces pastorianus, Rhodotorula mucilaginosa, Rhodotorula glutinis, and fungal isolate Ganoderma wiiroense were screened for the key parameters. The optimization was also performed by one-factor-at-a-time approach. Considering the specific yield of lipid and cell dry weight yield, R. glutinis and R. mucilaginosa showed superiority over other strains. G. wiiroense, a new isolate, would also be a promising strain for starch waste utilization in terms of extracellular and intracellular specific yield of lipids. Extracellular specific yield of lipid was highest in R. glutinis culture (0.025 g g -1 of biomass) followed by R. mucilaginosa (0.022 g g -1 of biomass) and G. wiiroense (0.020 g g -1 of biomass). Intracellular lipid was again highest in R. glutinis (0.048 g g -1 of biomass). The most prominent fatty acid methyl esters among the lipid as detected by GC-MS were saturated lipids mainly octadecanoic acid, tetradecanoate, and hexadecanoate. Extracellular lipid produced on starch substrate waste would be a cost-effective alternative for energy-intensive extraction process in biodiesel industry.

A mouse model of pre-pregnancy maternal obesity combined with offspring exposure to a high-fat diet resulted in cognitive impairment in male offspring.

PubMed

Zhu, Chen; Han, Ting-Li; Zhao, Yalan; Zhou, Xiaobo; Mao, Xun; Qi, Hongbo; Baker, Philip N; Zhang, Hua

2018-04-23

Cognitive impairment is a brain dysfunction characterized by neuropsychological deficits in attention, working memory, and executive function. Maternal obesity and consumption of a high-fat diet (HFD) in the offspring has been suggested to have detrimental consequences for offspring cognitive function through its effect on the hippocampus and prefrontal cortex. Therefore, our study aimed to investigate the effects of maternal obesity and offspring HFD exposure on the brain metabolome of the offspring. In our pilot study, a LepRdb/+ mouse model was used to model pre-pregnancy maternal obesity and the c57bl/6 wildtype was used as a control group. Offspring were fed either a HFD or a low-fat control diet (LFD) after weaning (between 8 and 10 weeks). The Mirrors water maze was performed between 28 and 30 weeks to measure cognitive function. Fatty acid metabolomic profiles of the prefrontal cortex and hippocampus from the offspring at 30-32 weeks were analyzed using gas chromatography-mass spectrometry. The memory of male offspring from obese maternal mice, consuming a HFD post-weaning, was significantly impaired when compared to the control offspring mice. No significant differences were observed in female offspring. In male mice, the fatty acid metabolites in the prefrontal cortex were most affected by maternal obesity, whereas, the fatty acid metabolites in the hippocampus were most affected by the offspring's diet. Hexadecanoic acid and octadecanoic acid were significantly affected in both the hippocampus and pre-frontal cortex, as a result of maternal obesity and a HFD in the offspring. Our findings suggest that the combination of maternal obesity and HFD in the offspring can result in spatial cognitive deficiency in the male offspring, by influencing the fatty acid metabolite profiles in the prefrontal cortex and hippocampus. Further research is needed to validate the results of our pilot study. Copyright © 2018 Elsevier Inc. All rights reserved.

Controlling the release of wood extractives into water bodies by selecting suitable eucalyptus species

NASA Astrophysics Data System (ADS)

Kilulya, K. F.; Msagati, T. A. M.; Mamba, B. B.; Ngila, J. C.; Bush, T.

Pulping industries are increasing worldwide as a result of the increase in the demand for pulp for cellulose derivatives and paper manufacturing. Due to the activities involved in pulping processes, different chemicals from raw materials (wood) and bleaching agents are released in pulp-mill effluent streams discharged into the environment and find their way into water bodies. Large quantities of water and chemicals used in pulping result in large amounts of wastewater with high concentrations of extractives such as unsaturated fatty acids, which are known to be toxic, and plant sterols which affect the development, growth and reproduction of aquatic organisms. This study was aimed at assessing the composition of extractives in two eucalyptus species used for pulp production in South Africa, in order to identify the suitable species with regard to extractive content. Samples from two eucalyptus plant species (Eucalyptus grandis and Eucalyptus dunnii) were collected from three sites and analysed for extractives by first extracting with water, followed by Soxhlet extraction using acetone. Compounds were identified and quantified using gas chromatography-mass spectrometry (GC-MS). Major classes of extractives identified were fatty acids (mainly hexadecanoic acid, 9,12-octadecadienoic, 9-octadecenoic and octadecanoic acids) and sterols (mainly β-sitosterol and stigmastanol). E. dunnii was found to contain higher amounts of the compounds compared to those found in E. grandis in all sampled sites. Principal component analysis (PCA) was performed and explained 92.9% of the total variation using three principal components. It was revealed that the percentage of fatty acids, which has a negative influence on both principal components 2 and 3, was responsible for the difference between the species. E. grandis, which was found to contain low amounts of extractives, was therefore found suitable for pulping with regard to minimal water usage and environment pollution.

Antifouling potential of bacteria isolated from a marine biofilm

NASA Astrophysics Data System (ADS)

Gao, Min; Wang, Ke; Su, Rongguo; Li, Xuzhao; Lu, Wei

2014-10-01

Marine microorganisms are a new source of natural antifouling compounds. In this study, two bacterial strains, Kytococcus sedentarius QDG-B506 and Bacillus cereus QDG-B509, were isolated from a marine biofilm and identified. The bacteria fermentation broth could exert inhibitory effects on the growth of Skeletonema costatum and barnacle larvae. A procedure was employed to extract and identify the antifouling compounds. Firstly, a toxicity test was conducted by graduated pH and liquid-liquid extraction to determine the optimal extraction conditions. The best extraction conditions were found to be pH 2 and 100% petroleum ether. The EC 50 value of the crude extract of K. sedentarius against the test microalgae was 236.7 ± 14.08 μg mL-1, and that of B. cereus was 290.6 ± 27.11 μg mL-1. Secondly, HLB SPE columns were used to purify the two crude extracts. After purification, the antifouling activities of the two extracts significantly increased: the EC 50 of the K. sedentarius extract against the test microalgae was 86.4 ± 3.71 μg mL-1, and that of B. cereus was 92.6 ± 1.47 μg mL-1. These results suggest that the metabolites produced by the two bacterial strains are with high antifouling activities and they should be fatty acid compounds. Lastly, GC-MS was used for the structural elucidation of the compounds. The results show that the antifouling compounds produced by the two bacterial strains are myristic, palmitic and octadecanoic acids.

Polymerase chain reaction system using magnetic beads for analyzing a sample that includes nucleic acid

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

Nasarabadi, Shanavaz

2011-01-11

A polymerase chain reaction system for analyzing a sample containing nucleic acid includes providing magnetic beads; providing a flow channel having a polymerase chain reaction chamber, a pre polymerase chain reaction magnet position adjacent the polymerase chain reaction chamber, and a post pre polymerase magnet position adjacent the polymerase chain reaction chamber. The nucleic acid is bound to the magnetic beads. The magnetic beads with the nucleic acid flow to the pre polymerase chain reaction magnet position in the flow channel. The magnetic beads and the nucleic acid are washed with ethanol. The nucleic acid in the polymerase chain reactionmore » chamber is amplified. The magnetic beads and the nucleic acid are separated into a waste stream containing the magnetic beads and a post polymerase chain reaction mix containing the nucleic acid. The reaction mix containing the nucleic acid flows to an analysis unit in the channel for analysis.« less

40 CFR 721.10125 - Alkenedioic acid, dialkyl ester, reaction products with polyaminocarbomonocycle and alkenoic acid...

Code of Federal Regulations, 2010 CFR

2010-07-01

..., reaction products with polyaminocarbomonocycle and alkenoic acid alkyl ester (generic). 721.10125 Section... Substances § 721.10125 Alkenedioic acid, dialkyl ester, reaction products with polyaminocarbomonocycle and.... (1) The chemical substances identified generically as alkenedioic acid, dialkyl ester, reaction...

40 CFR 721.10125 - Alkenedioic acid, dialkyl ester, reaction products with polyaminocarbomonocycle and alkenoic acid...

Code of Federal Regulations, 2011 CFR

2011-07-01

..., reaction products with polyaminocarbomonocycle and alkenoic acid alkyl ester (generic). 721.10125 Section... Substances § 721.10125 Alkenedioic acid, dialkyl ester, reaction products with polyaminocarbomonocycle and.... (1) The chemical substances identified generically as alkenedioic acid, dialkyl ester, reaction...

Weak Acid Ionization Constants and the Determination of Weak Acid-Weak Base Reaction Equilibrium Constants in the General Chemistry Laboratory

ERIC Educational Resources Information Center

Nyasulu, Frazier; McMills, Lauren; Barlag, Rebecca

2013-01-01

A laboratory to determine the equilibrium constants of weak acid negative weak base reactions is described. The equilibrium constants of component reactions when multiplied together equal the numerical value of the equilibrium constant of the summative reaction. The component reactions are weak acid ionization reactions, weak base hydrolysis…

40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

Code of Federal Regulations, 2010 CFR

2010-07-01

... substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo substituted phenyl azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo...

40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

Code of Federal Regulations, 2011 CFR

2011-07-01

... substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo substituted phenyl azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo...

Effects of calcium soap of rice bran oil fatty acids supplementation alone and with DL-α-tocopherol acetate in lamb diets on performance, digestibility, ruminal parameters and meat quality.

PubMed

Bhatt, R S; Sahoo, A; Karim, S A; Agrawal, A R

2016-06-01

Thirty-six Malpura lambs (28 day old and 6.7 ± 0.25 kg BW) were distributed equally in three groups having six males and six female. They were ad libitum fed individually three different experimental diets containing calcium soap of fatty acids (CA-FA) at 0 (T1 ) and 40 (T2 and T3 ) g/kg concentrate up to six months of age. Animals in T3 were supplemented additionally with 40 mg DL-α-tocopherol acetate/kg of concentrate. The roughage moiety included ad libitum dry Prosopis cineraria and fresh Azadirachata indica leaves. All the lambs were allowed to suckle from their dam up to weaning (90 day of age). Supplementation of Ca-FA improved weight gain and feed conversion ratio during both pre- (28-90 days) and post-weaning (91-180 days) phases; however, no effect of DL-α-tocopherol was observed. Metabolic parameters during post-weaning phase revealed non-significant effect on digestibility but improved nitrogen balance in the test groups. The effect on biochemical attributes did not show any significant alteration in ruminal parameters, blood biochemicals and urinary purine derivatives. Carcass traits revealed higher (p < 0.05) dressing yield and loin eye area with Ca-FA supplementation. The value of thiobarbituric reactive substances for nuggets prepared from frozen carcasses revealed significant (p < 0.05) reduction in T3 compared to the other dietary groups. Fatty acid profile of adipose tissue revealed higher (p < 0.001) 9-octadecanoic, 9-12-octadecadienoic, polyunsaturated fatty acids (PUFA), higher ratio of PUFA/saturated fatty acids (SFA), ω-6/ω-3 and lower SFA in Ca-FA-supplemented groups. It is concluded that supplementation of 40 g/kg calcium soap prepared from industrial grade rice bran oil in lamb ration provided additional energy intake, improved N utilization, gain and feed conversion ratio besides improving dressing yield and meat quality with CLA enriched fatty acid profile. DL-α-tocopherol acetate when supplemented at 40 mg/kg feed reduced lipid oxidation of meat products thus improving its keeping quality. Journal of Animal Physiology and Animal Nutrition © 2015 Blackwell Verlag GmbH.

Infrared Emission from Gas-Aerosol Reactions

DTIC Science & Technology

1982-09-01

Gaseous Amonia Infrared (IR) "Gas-aerosol Reactions Sulfuric Acid- amonia IR Luminescence Exothermic Reactions Octanoic Acid- amonia IR Laser Acid-base...of radiation observed from the reactions of chloro- sulfuric acid aerosol with gaseous amonia and water. Other systems which were screened including

Investigating Students' Reasoning about Acid-Base Reactions

ERIC Educational Resources Information Center

Cooper, Melanie M.; Kouyoumdjian, Hovig; Underwood, Sonia M.

2016-01-01

Acid-base chemistry is central to a wide range of reactions. If students are able to understand how and why acid-base reactions occur, it should provide a basis for reasoning about a host of other reactions. Here, we report the development of a method to characterize student reasoning about acid-base reactions based on their description of…

40 CFR 721.4461 - Hydrofluoric acid, reaction products with octane (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrofluoric acid, reaction products... New Uses for Specific Chemical Substances § 721.4461 Hydrofluoric acid, reaction products with octane... identified generically as a hydrofluoric acid, reaction products with octane (PMN P-99-0052) is subject to...

40 CFR 721.4385 - Hydrofluoric acid, reaction products with heptane.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrofluoric acid, reaction products... Specific Chemical Substances § 721.4385 Hydrofluoric acid, reaction products with heptane. (a) Chemical... hydrofluoric acid, reaction products with heptane (PMN P-98-1036; CAS No. 207409-71-0) is subject to reporting...

40 CFR 721.4461 - Hydrofluoric acid, reaction products with octane (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrofluoric acid, reaction products... New Uses for Specific Chemical Substances § 721.4461 Hydrofluoric acid, reaction products with octane... identified generically as a hydrofluoric acid, reaction products with octane (PMN P-99-0052) is subject to...

40 CFR 721.4385 - Hydrofluoric acid, reaction products with heptane.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrofluoric acid, reaction products... Specific Chemical Substances § 721.4385 Hydrofluoric acid, reaction products with heptane. (a) Chemical... hydrofluoric acid, reaction products with heptane (PMN P-98-1036; CAS No. 207409-71-0) is subject to reporting...

40 CFR 721.9672 - Amides, tall-oil fatty, N-[2-[2-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide...

Code of Federal Regulations, 2011 CFR

2011-07-01

...-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1-piperazineethanamine and sulfur dioxide; fatty acids, tall-oil reaction products with sulfur...)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1...

40 CFR 721.9672 - Amides, tall-oil fatty, N-[2-[2-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide...

Code of Federal Regulations, 2010 CFR

2010-07-01

...-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1-piperazineethanamine and sulfur dioxide; fatty acids, tall-oil reaction products with sulfur...)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1...

40 CFR 721.9672 - Amides, tall-oil fatty, N-[2-[2-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1-piperazineethanamine and sulfur dioxide; fatty acids, tall-oil reaction products with sulfur...)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1...

Second-harmonic generation from Z-type Langmuir-Blodgett films of a transparent dye and a comparison of the properties when the layers are interleaved with poly(t-butyl methacrylate)

NASA Astrophysics Data System (ADS)

Ashwell, Geoffrey J.; Ranjan, Rakesh

1998-10-01

The Langmuir-Blodgett (LB) film structure of E-4-[(N- octadecyl-6,7,8-trihydro-5-isoquinolylidene)methyl]-N,N- dibutylaniline octadecylsulfate is non-centrosymmetric when the dye is deposited on the up-stroke (Z-type) and when the layers are interleaved with poly(t-butyl methacrylate). The second-harmonic intensity increases as I(N)2(omega ) equals I(1)2(omega )N2, where N is the number of active layers, and the intensity is further enhanced when the dye is mixed in a 1 to 1 ratio with octadecanoic acid. The second-order susceptibility and repeat lattice spacing of the mixed LB films are as follows: (chi) zzz(2) equals 76 pm V-1 at 1.064 micrometers and l equals 3.15 nm layer-1 when Z-type; (chi) zzz(2) equals 52 pm V-1 and l equals 4.13 nm bilayer-1 when interleaved. The films are transparent at the fundamental wavelength and have a slight absorbance of ca. 5 X 10-4 per dye layer at 532 nm. The second-harmonic intensity is the strongest to date from such a weakly absorbing LB film and this is attributed to the close proximity of the charge-transfer band and to an optimized packing arrangement.

77 FR 21676 - Silicic Acid, Sodium Salt etc.; Tolerance Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-11

... Silicic acid, sodium salt, reaction products with chlorotrimethylsilane and iso-propyl alcohol, reaction..., reaction products with chlorotrimethylsilane and iso-propyl alcohol, reaction with poly(oxypropylene)-poly... from the requirement of a tolerance for residues of Silicic acid, sodium salt, reaction products with...

40 CFR 721.10189 - Fatty acids, tall-oil, reaction products with (butoxymethyl) oxirane formaldehyde-phenol polymer...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acids, tall-oil, reaction... Substances § 721.10189 Fatty acids, tall-oil, reaction products with (butoxymethyl) oxirane formaldehyde... to reporting. (1) The chemical substance identified generically as fatty acids, tall-oil, reaction...

40 CFR 721.9484 - Dimer acid/rosin amidoamine reaction product (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Dimer acid/rosin amidoamine reaction... Specific Chemical Substances § 721.9484 Dimer acid/rosin amidoamine reaction product (generic). (a... generically as Dimer acid/rosin amidoamine reaction product (PMN P-99-0143) is subject to reporting under this...

40 CFR 721.6181 - Fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acid, reaction product with... Specific Chemical Substances § 721.6181 Fatty acid, reaction product with substituted oxirane, formaldehyde... as fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

40 CFR 721.9460 - Tall oil fatty acids, reaction products with polyamines, alkyl substituted.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Tall oil fatty acids, reaction... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9460 Tall oil fatty acids, reaction... reporting. (1) The chemical substance identified generically as tall oil fatty acids, reaction products with...

40 CFR 721.10189 - Fatty acids, tall-oil, reaction products with (butoxymethyl) oxirane formaldehyde-phenol polymer...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acids, tall-oil, reaction... Substances § 721.10189 Fatty acids, tall-oil, reaction products with (butoxymethyl) oxirane formaldehyde... to reporting. (1) The chemical substance identified generically as fatty acids, tall-oil, reaction...

40 CFR 721.9484 - Dimer acid/rosin amidoamine reaction product (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Dimer acid/rosin amidoamine reaction... Specific Chemical Substances § 721.9484 Dimer acid/rosin amidoamine reaction product (generic). (a... generically as Dimer acid/rosin amidoamine reaction product (PMN P-99-0143) is subject to reporting under this...

40 CFR 721.9460 - Tall oil fatty acids, reaction products with polyamines, alkyl substituted.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Tall oil fatty acids, reaction... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9460 Tall oil fatty acids, reaction... reporting. (1) The chemical substance identified generically as tall oil fatty acids, reaction products with...

40 CFR 721.6181 - Fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acid, reaction product with... Specific Chemical Substances § 721.6181 Fatty acid, reaction product with substituted oxirane, formaldehyde... as fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals.

PubMed

Liu, Matthew J; Wiegel, Aaron A; Wilson, Kevin R; Houle, Frances A

2017-08-10

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular weight gas-phase reaction products and decreasing particle size.

[Effects of low molecular weight organic acids on redox reactions of mercury].

PubMed

Zhao, Shi-Bo; Sun, Rong-Guo; Wang, Ding-Yong; Wang, Xiao-Wen; Zhang, Cheng

2014-06-01

To study the effects of the main component of vegetation root exudates-low molecular weight organic acids on the redox reactions of mercury, laboratory experiments were conducted to investigate the roles of tartaric, citric, and succinic acid in the redox reactions of mercury, and to analyze their interaction mechanism. The results indicated that tartaric acid significantly stimulated the mercury reduction reaction, while citric acid had inhibitory effect. Succinic acid improved the reduction rate at low concentration, and inhibited the reaction at high concentration. The mercury reduction rate by tartaric acid treatment was second-order with respect to Hg2+ concentration, ranging from 0.0014 L x (ng x min)(-1) to 0.005 6 L x (ng x min)(-1). All three organic acids showed a capacity for oxidating Hg(0) in the early stage, but the oxidized Hg(0) was subsequently reduced. The oxidation capacity of the three organic acids was in the order of citric acid > tartaric acid > succinic acid.

78 FR 8040 - National Organic Program; Proposed Amendments to the National List of Allowed and Prohibited...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-05

... oxidizing agent formed by a reaction of hydrogen peroxide with acetic acid in water. The reaction used to... peracetic acid. Peracetic acid is produced from the in situ reaction of acetic acid, an inert ingredient... annotation for both listings of peracetic acid.\\3\\ A second motion to list peracetic acid without any...

D-Galacturonic Acid: A Highly Reactive Compound in Nonenzymatic Browning. 2. Formation of Amino-Specific Degradation Products.

PubMed

Wegener, Steffen; Bornik, Maria-Anna; Kroh, Lothar W

2015-07-22

Thermal treatment of aqueous solutions of D-galacturonic acid and L-alanine at pH 3, 5, and 8 led to rapid and more intensive nonenzymatic browning reactions compared to similar solutions of other uronic acids and to Maillard reactions of reducing sugars. The hemiacetal ring structures of uronic acids had a high impact on browning behavior and reaction pathways. Besides reductic acid (1,2-dihydroxy-2-cyclopenten-1-one), 4,5-dihydroxy-2-cyclopenten-1-one (DHCP), furan-2-carboxaldehyde, and norfuraneol (4-hydroxy-5-methyl-3-(2H)-furanone) could be detected as typical products of nonenzymatic uronic acid browning reactions. 2-(2-Formyl-1H-pyrrole-1-yl)propanoic acid (FPA) and 1-(1-carboxyethyl)-3-hydroxypyridin-1-ium (HPA) were identified as specific reaction products of uronic acids with amine participation like l-alanine. In contrast, the structurally related D-galacturonic acid methyl ester showed less browning activity and degradation under equal reaction conditions. Pectin-specific degradation products such as 5-formyl-2-furanoic acid and 2-furanoic acid were found but could not be verified for d-galacturonic acid monomers alone.

40 CFR 721.10188 - Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acids, tall-oil, reaction... Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (generic). (a... generically as fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (PMN...

40 CFR 721.10188 - Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acids, tall-oil, reaction... Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (generic). (a... generically as fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (PMN...

Aerosol Fragmentation Driven by Coupling of Acid–Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals

DOE PAGES

Liu, Matthew J.; Wiegel, Aaron A.; Wilson, Kevin R.; ...

2017-07-14

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps withmore » physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular weight gas-phase reaction products and decreasing particle size.« less

Aerosol Fragmentation Driven by Coupling of Acid–Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals

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

Liu, Matthew J.; Wiegel, Aaron A.; Wilson, Kevin R.

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps withmore » physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular weight gas-phase reaction products and decreasing particle size.« less

Photochemical reaction of 2-(3-benzoylphenyl)propionic acid (ketoprofen) with basic amino acids and dipeptides.

PubMed

Suzuki, Tadashi; Shinoda, Mio; Osanai, Yohei; Isozaki, Tasuku

2013-08-22

Photoreaction of 2-(3-benzoylphenyl)propionic acid (ketoprofen, KP) with basic amino acids (histidine, lysine, and arginine) and dipeptides (carnosine and anserine) including a histidine moiety in phosphate buffer solution (pH 7.4) has been investigated with transient absorption spectroscopy. With UV irradiation KP(-) gave rise to a carbanion through a decarboxylation reaction, and the carbanion easily abstracted a proton from the surrounding molecule to yield a 3-ethylbenzophenone ketyl biradical (EBPH). The dipeptides as well as the basic amino acids were found to accelerate the proton transfer reaction whereas alanine and glycine had no effect on the reaction, revealing that these amino acids having a protonated side chain act as a proton donor. The formation quantum yield of EBPH was estimated to be fairly large by means of an actinometrical method with benzophenone, and the bimolecular reaction rate constant for the proton transfer between the carbanion and the protonated basic amino acids or the protonated dipeptides was successfully determined. It has become apparent that the bimolecular reaction rate constant for the proton transfer depended on the acid dissociation constant for the side chain of the amino acids for the first time. This reaction mechanism was interpreted by difference of the heat of reaction for each basic amino acid based on the thermodynamical consideration. These results strongly suggest that the side chain of the basic amino acid residue in protein should play an important role for photochemistry of KP in vivo.

40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

Code of Federal Regulations, 2011 CFR

2011-07-01

... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction...

40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

Code of Federal Regulations, 2010 CFR

2010-07-01

... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction...

40 CFR 721.10136 - 2-Propenoic acid, 2-methyl-, 2-hydroxyethyl ester, reaction products with hexakis(alkoxyalkyl...

Code of Federal Regulations, 2010 CFR

2010-07-01

...-hydroxyethyl ester, reaction products with hexakis(alkoxyalkyl)melamine (generic). 721.10136 Section 721.10136... 2-Propenoic acid, 2-methyl-, 2-hydroxyethyl ester, reaction products with hexakis(alkoxyalkyl... substance identified generically as 2-propenoic acid, 2-methyl-, 2-hydroxyethyl ester, reaction products...

40 CFR 721.10136 - 2-Propenoic acid, 2-methyl-, 2-hydroxyethyl ester, reaction products with hexakis(alkoxyalkyl...

Code of Federal Regulations, 2011 CFR

2011-07-01

...-hydroxyethyl ester, reaction products with hexakis(alkoxyalkyl)melamine (generic). 721.10136 Section 721.10136... 2-Propenoic acid, 2-methyl-, 2-hydroxyethyl ester, reaction products with hexakis(alkoxyalkyl... substance identified generically as 2-propenoic acid, 2-methyl-, 2-hydroxyethyl ester, reaction products...

REACTION OF AMINO-ACIDS AND PEPTIDE BONDS WITH FORMALDEHYDE AS MEASURED BY CHANGES IN THE ULTRA-VIOLET SPECTRA,

DTIC Science & Technology

AMINO ACIDS , CHEMICAL REACTIONS), (*PEPTIDES, CHEMICAL REACTIONS), (*FORMALDEHYDE, CHEMICAL REACTIONS), (*ULTRAVIOLET SPECTROSCOPY, PROTEINS), ABSORPTION SPECTRA, CHEMICAL BONDS, AMIDES, CHEMICAL EQUILIBRIUM, REACTION KINETICS

Studies on the oxidation of hexamethylbenzene 1: Oxidation of hexamethylbenzene with nitric acid

NASA Technical Reports Server (NTRS)

Chiba, K.; Tomura, S.; Mizuno, T.

1986-01-01

The oxidative reaction of hexamethylbenzene (HMB) with nitric acid was studied, and the hitherto unknown polymethylbenzenepolycarboxylic acids were isolated: tetramethylphthalic anhydride, tetramethylisophthalic acid, 1,3,5-, 1,2,4- and 1,2,3-trimethylbenzenetricarboxylic acids. When HMB was warmed with 50% nitric acid at about 80 C, tetramethylphthalic anhydride and tetramethylisophthalic acid were initially produced. The continued reaction led to the production of trimethylbenzenetricarboxylic acids, but only slight amounts of dimethylbenzenetetracarboxylic acids were detected in the reaction mixture. Whereas tetramethylphthalic anydride and tetramethylisophthalic acid were obtained, pentamethylbenzoic acid, a possible precursor of them, was scarcely produced. On the other hand, a yellow material extracted with ether from the initial reaction mixture contained bis-(nitromethyl)prehnitene (CH3)4C6(CH2NO2)2, which was easily converted into the phthalic anhydride.

76 FR 8895 - Polymerized Fatty Acid Esters With Aminoalcohol Alkoxylates; Exemption From the Requirement of a...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-02-16

..., reaction products with fatty acid dimers (CAS Reg. No. 1173188-38-9); dimethylaminoethanol, ethoxylated, propoxylated, reaction products with fatty acid dimers (CAS Reg. No. 1173188-42-5 diethylaminoethanol, ethoxylated, reaction product with fatty acid dimers (CAS Reg. No. 1173188-72-1); diethylaminoethanol...

Production of sugars and levulinic acid from marine biomass Gelidium amansii.

PubMed

Jeong, Gwi-Taek; Park, Don-Hee

2010-05-01

This study focused on optimization of reaction conditions for formation of sugars and levulinic acid from marine algal biomass Gelidium amansii using acid catalyst and by using statistical approach. By this approach, optimal conditions for production of sugars and levulinic acid were found as follows: glucose (reaction temperature of 139.4 degrees C, reaction time of 15.0 min, and catalyst concentration of 3.0%), galactose (108.2 degrees C, 45.0 min, and 3.0%), and levulinic acid (160.0 degrees C, 43.1 min, and 3.0%). While trying to optimize the conditions for the production of glucose and galactose, levulinic acid production was found to be minimum. Similarly, the production of glucose and galactose were found to be minimum while optimizing the conditions for the production of levulinic acid. In addition, optimized production of glucose required a higher reaction temperature and shorter reaction time than that of galactose. Levulinic acid was formed at a high reaction temperature, long reaction time, and high catalyst concentration. The combined results of this study may provide useful information to develop more economical and efficient systems for production of sugars and chemicals from marine biomass.

Clustering mechanism of oxocarboxylic acids involving hydration reaction: Implications for the atmospheric models

NASA Astrophysics Data System (ADS)

Liu, Ling; Kupiainen-Määttä, Oona; Zhang, Haijie; Li, Hao; Zhong, Jie; Kurtén, Theo; Vehkamäki, Hanna; Zhang, Shaowen; Zhang, Yunhong; Ge, Maofa; Zhang, Xiuhui; Li, Zesheng

2018-06-01

The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.

40 CFR 721.9400 - Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of phenolic... Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and glyceride... substances identified generically as Reaction product of phenolic pentaerythritol tetraesters with fatty acid...

40 CFR 721.9400 - Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of phenolic... Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and glyceride... substances identified generically as Reaction product of phenolic pentaerythritol tetraesters with fatty acid...

40 CFR 721.9400 - Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of phenolic... Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and glyceride... substances identified generically as Reaction product of phenolic pentaerythritol tetraesters with fatty acid...

40 CFR 721.9400 - Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of phenolic... Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and glyceride... substances identified generically as Reaction product of phenolic pentaerythritol tetraesters with fatty acid...

40 CFR 721.9400 - Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of phenolic... Reaction product of phenolic pentaerythritol tetraesters with fatty acid esters and oils, and glyceride... substances identified generically as Reaction product of phenolic pentaerythritol tetraesters with fatty acid...

40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction products of secondary alkyl... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... substances identified generically as reaction products of secondary alkyl amines with a substituted...

40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction products of secondary alkyl... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... substances identified generically as reaction products of secondary alkyl amines with a substituted...

Cutin-derived CuO reaction products from purified cuticles and tree leaves

NASA Astrophysics Data System (ADS)

Goñi, Miguel A.; Hedges, John I.

1990-11-01

Long chain (C 16-C 18) hydroxy fatty acids are obtained among the nonlignin-derived reaction products from the CuO oxidation of a variety of geochemical samples. In order to investigate the origin of these acids, the CuO reaction products of isolated cuticles and whole leaves were investigated. The reaction products from the CuO oxidation of purified apple ( Malus pumila) cuticle include 16-hydroxy-hexadecanoic acid, 10,16-dihydroxyhexadecanoic acid, 9,10,18-trihydroxyoctadec-12-enoic acid, and 9,10,18-trihydroxyoctadecanoic acid as major components. The distribution of these cutin-derived CuO reaction products is similar to the monomer compositions deduced from traditional methods of cutin analysis. Oxidation of whole English Holly ( Ilex aquifolium) leaves yields cutin-derived acidic reaction products (in addition to lignin-derived phenols) similar to those obtained from oxidation of the corresponding isolated cuticles, indicating that CuO oxidation of bulk plant tissue is a viable procedure of cutin analysis in geochemical applications.

Kinetics of beta-haematin formation from suspensions of haematin in aqueous benzoic acid.

PubMed

Egan, Timothy J; Tshivhase, Mmboneni G

2006-11-14

Kinetics of beta-haematin (synthetic malaria pigment) formation from haematin have been studied in the presence of aqueous benzoic acid and derivatives of benzoic acid. Formation of the beta-haematin product is demonstrated by X-ray diffraction and IR spectroscopy. Reactions were followed by determining the fraction of unreacted haematin at various time points during the process via reaction of extracted aliquots with pyridine. The kinetics can be fitted to the Avrami equation, indicating that the process involves nucleation and growth. Reaction kinetics in stirred benzoic acid are similar to those previously observed in acetic acid, except that benzoic acid is far more active in promoting the reaction than acetic acid. The reaction reaches completion within 2 h in the presence of 0.050 M benzoic acid (pH 4.5, 60 degrees C). This compares with 1 h in the presence of 4.5 M acetic acid and 4 h in the presence of 2 M acetic acid. The reaction rate in benzoic acid is not affected if the stirring rate is decreased to zero, but very vigorous stirring appears to disrupt nucleation. The rate constant for beta-haematin formation in benzoic acid has a linear dependence on benzoic acid concentration and follows Arrhenius behaviour with temperature. There is a bell-shaped dependence on pH. This suggests that the haematin species in which one propionate group is protonated and the other is deprotonated is optimal for beta-haematin formation. When the reaction is conducted in para-substituted benzoic acid derivatives, the log of the rate constant increases linearly with the Hammett constant. These findings suggest that the role of the carboxylic acid may be to disrupt hydrogen bonding and pi-stacking in haematin, facilitating conversion to beta-haematin. The large activation energy for conversion of precipitated haematin to beta-haematin suggests that the reaction in vivo most likely involves direct nucleation from solution and probably does not occur in aqueous medium.

[Study of Reaction Dynamics between Bovine Serum Albumin and Folic Acid by Stopped-Flow/Fluorescence].

PubMed

Ye, San-xian; Luo, Yun-jing; Qiao, Shu-liang; Li, Li; Liu, Cai-hong; Shi, Jian-long; An, Xue-jing

2016-01-01

As a kind of coenzyme of one-carbon enzymes in vivo, folic acid belongs to B vitamins, which can interact with other vitamins and has great significance for converting among amino acids, dividing growth of cells and protein synthesis reactions. Half-life, concentration and reaction rate constant of drugs are important parameters in pharmacokinetic study. In this paper, by utilizing fluorescence spectrophotometer and stopped-flow spectrum analyzer, reaction kinetic parameters between bovine serum albumin(BSA) and folic acid in a bionic system have been investigated, which provide references for parameters of drug metabolism related to folic acid. By using Stern-Volmer equation dealing with fluorescence quenching experiments data, we concluded that under 25, 30, and 37 degrees C, the static quenching constants of folic acid to intrinsic fluorescence from bovine serum albumin were 2.455 x 10(10), 4.900 x 10(10) and 6.427 x 10(10) L x mol(-1) x s(-1) respectively; The results of kinetic reaction rate have shown that the reaction rate of BSA and folic acid are greater than 100 mol x L(-1) x s(-1) at different temperatures, pH and buffering media, illustrating that the quenching mechanism between BSA and folic acid is to form composite static quenching process. Reaction concentration of bovine serum albumin and its initial concentration were equal to the secondary reaction formula, and the correlation coefficient was 0.998 7, while the half-life (t1/2) was 0.059 s at physiological temperature. With the increase of folic acid concentration, the apparent rate constant of this reaction had a linear increasing trend, the BSA fluorescence quenching rate constant catalyzed by folic acid was 3.174 x 10(5) mol x L(-1) x s(-1). Furthermore, with different buffer, the apparent rate constant and reaction rate constant of BSA interacting with folic acid were detected to explore the influence on the reaction under physiological medium, which is of great significance to determine the clinical regimen, forecast the efficacy and toxicity of drugs and rational drug.

Oxidation of phenolic acids by soil iron and manganese oxides

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

Lehmann, R.G.; Cheng, H.H.; Harsh, J.B.

Phenolic acids are intermediary metabolites of many aromatic chemicals and may be involved in humus formation, allelopathy, and nutrient availability. Depending on their structures, six phenolic acids were shown to react at different rates with oxidized forms of Fe and Mn in a Palouse soil (fine-silty, mixed, mesic Pachic Ultic Haploxeroll). Increasing methoxy substitution on the aromatic ring of phenolic acids increased the reaction rate. Reaction rate was also increased for longer carboxyl-containing side chains. After 4 h reaction, little of the applied (10 mg kg/sup -1/ soil) p-hydroxybenzoic or p-coumaric acids had reacted, while 0 to 5, 70, 90,more » and 100% of the vanillic, ferulic, syringic, and sinapic acids, respectively, had reacted. After 72 h under conditions limiting microbial growth, none of the p-hydroxybenzoic, 30% of the p-coumaric, and 50% of the vanillic acids had reacted. The reaction was shown to be predominantly chemical, and not biological, since phenolic acid extractabilities were similar for Palouse soil and for Palouse soil pretreated with LiOBr to remove organic matter. When the Palouse soil was pretreated with a sodium dithionite-citrate solution to remove Fe and Mn oxides, none of the phenolic acids reacted after 1 h. The reaction of sinapic acid with Palouse soil was shown to produce Fe(II) and soluble Mn as reaction products. The reaction of phenolic acids with soil was thus shown to be an oxidation of the phenolic acids, coupled with a reduction of soil Fe and Mn oxides.« less

Characterization of thermal and mechanical properties of opligo(glycerol-glutaric acid)s

USDA-ARS?s Scientific Manuscript database

Dibutyltin oxide was used to catalyze the synthesis of oligo(glycerol-glutaric acid)s in the absence and presence of solvent. Reaction times were either 10h or 24h for reactions performed in DMF and 24h for the neat reaction. The oligomers were obtained on average in 84% yield and were characteriz...

Gas-Phase Anionic σ-Adduct (Trans)formations in Heteroaromatic Systems1

NASA Astrophysics Data System (ADS)

Zimnicka, Magdalena; Danikiewicz, Witold

2015-07-01

Anions of nitroderivatives of thiophene and furan were subjected to the reactions with selected C-H acids in the gas phase. Various structures and reaction pathways were proposed for the observed ionic products. In general, the reactions of heteroaromatic anions with C-H acids may be divided into three groups, depending on the proton affinity difference between C-H acid's conjugate base and heteroaromatic anion (ΔPA). The proton transfer from C-H acid to heteroaromatic anion is a dominant process in the reactions for which ΔPA < 0 kcal mol-1, whereas the reactions with high ΔPA (ΔPA > 16 kcal mol-1) do not lead to any ionic products. The formation of σ-adducts and products of their further transformations according to the VNS, SNAr, cine, and tele substitution mechanisms have been proposed for reactions with moderate ΔPA. The other possible mechanisms as SN2 reaction, nucleophilic addition to the cyano group, ring-opening pathway, and halogenophilic reaction have also been discussed to contribute in the reactions between heteroaromatic anions and C-H acids.

Hydrogeology and chemical quality of water and soil at Carroll Island, Aberdeen Proving Ground, Maryland

USGS Publications Warehouse

Tenbus, F.J.; Phillips, S.W.

1996-01-01

Carroll Island was used for open-air testing of chemical warfare agents from the late 1940's until 1971. Testing and disposal activities weresuspected of causing environmental contamination at 16 sites on the island. The hydrogeology and chemical quality of ground water, surface water, and soil at these sites were investigated with borehole logs, environmental samples, water-level measurements, and hydrologic tests. A surficial aquifer, upper confining unit, and upper confined aquifer were defined. Ground water in the surficial aquifer generally flows from the east-central part of the island toward the surface-water bodies, butgradient reversals caused by evapotranspiration can occur during dry seasons. In the confined aquifer, hydraulic gradients are low, and hydraulic head is affected by tidal loading and by seasonal pumpage from the west. Inorganic chemistry in the aquifers is affected by brackish-water intrusion from gradient reversals and by dissolution ofcarboniferous shell material in the confining unit.The concentrations of most inorganic constituents probably resulted from natural processes, but some concentrations exceeded Federal water-quality regulations and criteria. Organic compounds were detected in water and soil samples at maximum concentrations of 138 micrograms per liter (thiodiglycol in surface water) and 12 micrograms per gram (octadecanoic acid in soil).Concentrations of organic compounds in ground water exceeded Federal drinking-water regulations at two sites. The organic compounds that weredetected in environmental samples were variously attributed to natural processes, laboratory or field- sampling contamination, fallout from industrial air pollution, and historical military activities.

Insecticidal activity of bio-oil from the pyrolysis of straw from Brassica spp.

PubMed

Suqi, Liu; Cáceres, Luis A; Caceres, Luis; Schieck, Katie; McGarvey, Brian D; Booker, Christina J; McGarvey, Brian M; Yeung, Ken K-C; Pariente, Stephane; Briens, Cedric; Berruti, Franco; Scott, Ian M

2014-04-23

Agricultural crop residues can be converted through thermochemical pyrolysis to bio-oil, a sustainable source of biofuel and biochemicals. The pyrolysis bio-oil is known to contain many chemicals, some of which have insecticidal activity and can be a potential source of value-added pest control products. Brassicacae crops, cabbage, broccoli, and mustards, contain glucosinolates and isocyanates, compounds with recognized anti-herbivore activity. In Canada, canola Brassica napus straw is available from over 6 000 000 ha and mustard Brassica carinata and Brassica juncea straw is available from 200 000 ha. The straw can be converted by microbial lignocellulosic enzymes as a substrate for bioethanol production but can also be converted to bio-oil by thermochemical means. Straw from all three species was pyrolyzed, and the insecticidal components in the bio-oil were isolated by bioassay-guided solvent fractionation. Of particular interest were the mustard straw bio-oil aqueous fractions with insecticidal and feeding repellent activity to Colorado potato beetle larvae. Aqueous fractions further analyzed for active compounds were found not to contain many of the undesirable phenol compounds, which were previously found in other bio-oils seen in the dichloromethane (DCM) and ethyl acetate (EA) solvent phases of the present study. Identified within the most polar fractions were hexadecanoic and octadecanoic fatty acids, indicating that separation of these compounds during bio-oil production may provide a source of effective insecticidal compounds.

Biosurfactant from a marine bacterium disrupts biofilms of pathogenic bacteria in a tropical aquaculture system.

PubMed

Hamza, Faseela; Satpute, Surekha; Banpurkar, Arun; Kumar, Ameeta Ravi; Zinjarde, Smita

2017-11-01

Bacterial infections are major constraints in aquaculture farming. These pathogens often adapt to the biofilm mode of growth and resist antibiotic treatments. We have used a non-toxic glycolipid biosurfactant (BS-SLSZ2) derived from a marine epizootic bacterium Staphylococcus lentus to treat aquaculture associated infections in an eco-friendly manner. We found that BS-SLSZ2 contained threose, a four-carbon sugar as the glycone component, and hexadecanoic and octadecanoic acids as the aglycone components. The critical micelle concentration of the purified glycolipid was 18 mg mL-1. This biosurfactant displayed anti-adhesive activity and inhibited biofilm formation by preventing initial attachment of cells onto surfaces. The biosurfactant (at a concentration of 20 μg) was able to inhibit Vibrio harveyi and Pseudomonas aeruginosa biofilms by 80.33 ± 2.16 and 82 ± 2.03%, respectively. At this concentration, it was also able to disrupt mature biofilms of V. harveyi (78.7 ± 1.93%) and P. aeruginosa (81.7 ± 0.59%). The biosurfactant was non-toxic towards Artemia salina. In vivo challenge experiments showed that the glycolipid was effective in protecting A. salina nauplii against V. harveyi and P. aeruginosa infections. This study highlights the significance of marine natural products in providing alternative biofilm controlling agents and decreasing the usage of antibiotics in aquaculture settings. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Functionalization of Carbon Nanotubes via Electrophilic Substitution Reaction in Polyphosphoric Acid

DTIC Science & Technology

2006-07-26

1 Title of proposed research: Functionalization of Carbon Nanotubes via Electrophilic Substitution Reaction in Polyphosphoric Acid Proposer: Jong...Choi, J.-Y.; Tan, L.-S.; Baek, J.-B. “Functionalization of carbon nanotubes via electrophilic substitution reaction in polyphosphoric acid” AFOSR...2006 4. TITLE AND SUBTITLE Functionalization of carbon nanotubes via electrophilic substitution reaction in polyphosphoric acid 5a. CONTRACT

Influence of l-pyroglutamic acid on the color formation process of non-enzymatic browning reactions.

PubMed

Wegener, Steffen; Kaufmann, Martin; Kroh, Lothar W

2017-10-01

Heating aqueous d-glucose model reactions with l-glutamine and l-alanine yielded similar colored solutions. However, size-exclusion chromatography (SEC) revealed that both non-enzymatic browning reactions proceeded differently. Due to a fast occurring cyclization of l-glutamine to pyroglutamic acid, the typical amino-carbonyl reaction was slowed down. However, l-glutamine and l-alanine model reactions showed the same browning index. Closer investigations could prove that l-pyroglutamic acid was able to influence non-enzymatic browning reactions. SEC analyses of d-glucose model reactions with and without l-pyroglutamic acid revealed an increase of low molecular colored compounds in the presence of l-pyroglutamic acid. Polarimetric measurements showed a doubling of d-glucose mutarotation velocity and HPLC analyses of d-fructose formation during thermal treatment indicated a tripling of aldose-ketose transformation in the presence of l-pyroglutamic acid, which are signs of a faster proceeding non-enzymatic browning process. 2-Pyrrolidone showed no such behavior, thus the additional carboxylic group should be responsible for the observed effects. Copyright © 2017 Elsevier Ltd. All rights reserved.

Carbon-Carbon Bond Formation and Hydrogen Production in the Ketonization of Aldehydes.

PubMed

Orozco, Lina M; Renz, Michael; Corma, Avelino

2016-09-08

Aldehydes possess relatively high chemical energy, which is the driving force for disproportionation reactions such as Cannizzaro and Tishchenko reactions. Generally, this energy is wasted if aldehydes are transformed into carboxylic acids with a sacrificial oxidant. Here, we describe a cascade reaction in which the surplus energy of the transformation is liberated as molecular hydrogen for the oxidation of heptanal to heptanoic acid by water, and the carboxylic acid is transformed into potentially industrially relevant symmetrical ketones by ketonic decarboxylation. The cascade reaction is catalyzed by monoclinic zirconium oxide (m-ZrO2 ). The reaction mechanism has been studied through cross-coupling experiments between different aldehydes and acids, and the final symmetrical ketones are formed by a reaction pathway that involves the previously formed carboxylic acids. Isotopic studies indicate that the carboxylic acid can be formed by a hydride shift from the adsorbed aldehyde on the metal oxide surface in the absence of noble metals. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Global Aesthetics Consensus: Avoidance and Management of Complications from Hyaluronic Acid Fillers—Evidence- and Opinion-Based Review and Consensus Recommendations

PubMed Central

Liew, Steven; Sundaram, Hema; De Boulle, Koenraad L.; Goodman, Greg J.; Monheit, Gary; Wu, Yan; Trindade de Almeida, Ada R.; Swift, Arthur; Vieira Braz, André

2016-01-01

Background: Although the safety profile of hyaluronic acid fillers is favorable, adverse reactions can occur. Clinicians and patients can benefit from ongoing guidance on adverse reactions to hyaluronic acid fillers and their management. Methods: A multinational, multidisciplinary group of experts in cosmetic medicine convened the Global Aesthetics Consensus Group to review the properties and clinical uses of Hylacross and Vycross hyaluronic acid products and develop updated consensus recommendations for early and late complications associated with hyaluronic acid fillers. Results: The consensus panel provided specific recommendations focusing on early and late complications of hyaluronic acid fillers and their management. The impact of patient-, product-, and technique-related factors on such reactions was described. Most of these were noted to be mild and transient. Serious adverse events are rare. Early adverse reactions to hyaluronic acid fillers include vascular infarction and compromise; inflammatory reactions; injection-related events; and inappropriate placement of filler material. Among late reactions are nodules, granulomas, and skin discoloration. Most adverse events can be avoided with proper planning and technique. Detailed understanding of facial anatomy, proper patient and product selection, and appropriate technique can further reduce the risks. Should adverse reactions occur, the clinician must be prepared and have tools available for effective treatment. Conclusions: Adverse reactions with hyaluronic acid fillers are uncommon. Clinicians should take steps to further reduce the risk and be prepared to treat any complications that arise. PMID:27219265

Kinetics of reactions of aquacobalamin with aspartic and glutamic acids and their amides in water solutions

NASA Astrophysics Data System (ADS)

Bui, T. T. T.; Sal'nikov, D. S.; Dereven'kov, I. A.; Makarov, S. V.

2017-04-01

The kinetics of aquacobalamin reaction with aspartic and glutamic acids, and with their amides in water solutions, is studied via spectrophotometry. The kinetic and activation parameters of the process are determined. It is shown that the reaction product is cobalamin-amino acid complex. The data are compared to results on the reaction between aquacobalamin and primary amines.

Utilizing two detectors in the measurement of trichloroacetic acid in human urine by reaction headspace gas chromatography.

PubMed

Xie, Wei-Qi; Gong, Yi-Xian; Yu, Kong-Xian

2018-05-16

A reaction headspace gas chromatography (HS-GC) technique was investigated for quantitatively analyzing trichloroacetic acid in human urine. This method is based on the decomposition reaction of trichloroacetic acid under high-temperature conditions. The carbon dioxide and chloroform formed from the decomposition reaction can be respectively detected by the thermal conductivity detection HS-GC and flame ionization detection HS-GC. The reaction can be completed in 60 min at 90°C. This method was used to quantify 25 different human urine samples, which had a range of trichloroacetic acid from 0.52 to 3.47 mg/L. It also utilized two different detectors, the thermal conductivity detector and the flame ionization detector. The present reaction HS-GC method is accurate, reliable and well suitable for batch detection of trichloroacetic acid in human urine. Copyright © 2018 John Wiley & Sons, Ltd.

Aerosol-Forming Reactions of Glyoxal, Methylglyoxal and Amino Acids in Clouds

NASA Astrophysics Data System (ADS)

de Haan, D. O.; Smith, K. W.; Stroik, D. R.; Corrigan, A. L.; Lee, F. E.; Phan, J. T.; Conley, A. C.

2008-12-01

Glyoxal and methylglyoxal are two common aldehydes present in fog and cloud water. Amino acids are present in clouds at similar concentrations. Here we present bulk and aerosol mass spectroscopic data demonstrating that irreversible reactions between glyoxal and amino acids, triggered by droplet evaporation, produce N-derivatized imidazole compounds along with deeply colored Maillard reaction products. These reactions can occur in the dark and in the absence of oxidants. Reactions between methylglyoxal and amino acids produce analogous methylated products plus oligomers with masses up to m/z = 1000. These reactions, which go to completion on the 10-min-timescale of cloud processing, could be significant sources of secondary organic aerosol and humic-like substances (HULIS or brown carbon).

Catalytic effects of inorganic acids on the decomposition of ammonium nitrate.

PubMed

Sun, Jinhua; Sun, Zhanhui; Wang, Qingsong; Ding, Hui; Wang, Tong; Jiang, Chuansheng

2005-12-09

In order to evaluate the catalytic effects of inorganic acids on the decomposition of ammonium nitrate (AN), the heat releases of decomposition or reaction of pure AN and its mixtures with inorganic acids were analyzed by a heat flux calorimeter C80. Through the experiments, the different reaction mechanisms of AN and its mixtures were analyzed. The chemical reaction kinetic parameters such as reaction order, activation energy and frequency factor were calculated with the C80 experimental results for different samples. Based on these parameters and the thermal runaway models (Semenov and Frank-Kamenestkii model), the self-accelerating decomposition temperatures (SADTs) of AN and its mixtures were calculated and compared. The results show that the mixtures of AN with acid are more unsteady than pure AN. The AN decomposition reaction is catalyzed by acid. The calculated SADTs of AN mixtures with acid are much lower than that of pure AN.

[Study on X-ray powder diffraction of various structured zinc titanate prepared by the method of direct precipitation].

PubMed

Guo, Jian; Wang, Zhi-hua; Tao, Dong-liang; Guo, Guang-sheng

2007-05-01

Zinc titanate powders were prepared from Ti(SO4)2, Zn(NO3)2 x (6)H2O and (NH4)2CO3 by the method of direct precipitation. The effects of reaction conditions on the structure of zinc titanate were studied. The sample was analyzed by means of XRD and TG-DTA. The structure of zinc titanate was affected by the reaction subsequence of the formation of titanic acid and zinc carbonate. In the reaction system where titanic acid was generated earlier, collision reaction occurred between the generated zinc carbonate molecule and the surrounding titanic acid molecule. When titanic acid was generated earlier and precipitant (NH4)2CO3 was sufficient, Zn2Ti3O8 was obtained because of the sufficient collision reaction and superfluous titanic acid. In the reaction system where zinc carbonate was generated earlier, collision reaction occurred between the generated titanic acid molecule and the surrounding zinc carbonate molecule. When zinc carbonate was generated earlier and precipitant (NH4)2CO3 was sufficient, Zn2TiO4 was obtained because of the sufficient collision reaction and superfluous zinc carbonate. In addition, the kinds and structure of the production were affected by the dosage of precipitant and the reaction temperature. Zn2Ti3O8 or Zn2TiO4 could be obtained easier when using more precipitant or higher reaction temperature which could cause more sufficient collision reaction. ZnTiO3 could be obtained under the conditions of less precipitant and lower reaction temperature.

Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: selective hydrogenation of alkynes with formic acid.

PubMed

Shen, Ruwei; Chen, Tieqiao; Zhao, Yalei; Qiu, Renhua; Zhou, Yongbo; Yin, Shuangfeng; Wang, Xiangbo; Goto, Midori; Han, Li-Biao

2011-10-26

A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt(3))(4) (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt(3))(4), but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Brϕnsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.

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

Goni, M.A.; Hedges, J.I.

Long chain (C{sub 16}-C{sub 18}) hydroxy fatty acids are obtained among the nonlignin-derived reaction products from the CuO oxidation of a variety of geochemical samples. In order to investigate the origin of these acids, the CuO reaction products of isolated cuticles and whole leaves were investigated. The reaction products from the CuO oxidation of purified apple (Malus pumila) cuticle include 16-hydroxyhexadecanoic acid, 10,16-dihydroxyhexadecanoic acid, 9,10,18-trihydroxyoctadec-12-enoic acid, and 9,10,18-trihydroxyoctadecanoic acid as major components. The distribution of these cutin-derived CuO reaction products is similar to the monomer compositions deduced from traditional methods of cutin analysis. Oxidation of whole English Holly (Ilex aquifolium)more » leaves yields cutin-derived acidic reaction products (in addition to lignin-derived phenols) similar to those obtained from oxidation of the corresponding isolated cuticles, indicating that CuO oxidation of bulk plant tissue is a viable procedure of cutin analysis in geochemical applications.« less

Conformation-dependent chemical reaction of formic acid with an oxygen atom.

PubMed

Khriachtchev, Leonid; Domanskaya, Alexandra; Marushkevich, Kseniya; Räsänen, Markku; Grigorenko, Bella; Ermilov, Alexander; Andrijchenko, Natalya; Nemukhin, Alexander

2009-07-23

Conformation dictates many physical and chemical properties of molecules. The importance of conformation in the selectivity and function of biologically active molecules is widely accepted. However, clear examples of conformation-dependent bimolecular chemical reactions are lacking. Here we consider a case of formic acid (HCOOH) that is a valuable model system containing the -COOH carboxyl functional group, similar to many biomolecules including the standard amino acids. We have found a strong case of conformation-dependent reaction between formic acid and atomic oxygen obtained in cryogenic matrices. The reaction surprisingly leads to peroxyformic acid only from the ground-state trans conformer of formic acid, and it results in the hydrogen-bonded complex for the higher-energy cis conformer.

Imino Acids in the Murchison Meteorite: Evidence of Strecker Reactions

NASA Technical Reports Server (NTRS)

Lerner, N. R.; Cooper, G. W.

2003-01-01

Both alpha-amino acids and alpha-hydroxy acids occur in aqueous extracts of the Murchison carbonaceous meteorite. The Strecker-cyanohydrin reaction, the reaction of carbonyl compounds, cyanide, and ammonia to produce amino and hydroxy acids, has been proposed as a source of such organic acids in meteorites. Such syntheses are consistent with the suggestion that interstellar precursors of meteoritic organic compounds accreted on the meteorite parent body together with other ices. Subsequent internal heating of the parent body melted these ices and led to the formation of larger compounds in synthetic reactions during aqueous alteration, which probably occurred at temperatures between 273K and 298K. In the laboratory, imino acids are observed as important by-products of the Strecker synthesis.

The reaction of iodobenzene-p-sulphonyl chloride (pipsyl chloride) with certain amino acids and peptides, and with insulin

PubMed Central

Fletcher, J. C.

1967-01-01

1. A system of separation using buffered Celite columns is described that enables the pipsyl derivatives of most of the common amino acids to be separated. 2. The reaction of pipsyl chloride with several amino acids not included in previous studies has been investigated. In particular, knowledge of the acid-soluble pipsyl derivatives of arginine, histidine, lysine, tyrosine and cysteic acid has been extended. 3. Reproducible factors have been obtained that enable corrections to be applied for the breakdown of pipsylamino acids on acid hydrolysis. 4. The reaction of pipsyl chloride with peptides has been studied under various conditions. 5. The extent of the reaction between pipsyl chloride and insulin depends on the nature of the solvent–buffer system, and under the best conditions so far found is about 75% complete. 6. In an Appendix, the separation of pipsylamino acids by thin-layer chromatography is described. PMID:16742498

Facile access to amides and hydroxamic acids directly from nitroarenes.

PubMed

Jain, Shreyans K; Aravinda Kumar, K A; Bharate, Sandip B; Vishwakarma, Ram A

2014-09-07

A new method for synthesis of amides and hydroxamic acids from nitroarenes and aldehydes is described. The MnO2 catalyzed thermal deoxygenation of nitrobenzene resulted in formation of a reactive nitroso intermediate which on reaction with aldehydes provided amides and hydroxamic acids. The thermal neat reaction in the presence of 0.01 mmol KOH predominantly led to formation of hydroxamic acid whereas reaction in the presence of 1 mmol acetic acid produced amides as the only product.

GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

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

Barrientos, Carmen; Redondo, Pilar; Largo, Laura

2012-04-01

A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol{sup -1} at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH{sub 3}OH{sup +}, with acetic acid also involves a high barrier (more than 27 kcal mol{sup -1} at the CCSD(T) level). Only the highermore » energy isomer, NH{sub 2}OH{sup +}{sub 2}, leads to a sensibly lower energy barrier (about 2.3 kcal mol{sup -1} at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.« less

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

Sun, Junming; Baylon, Rebecca A.; Liu, Changjun

The effects of surface acidity on the cascade ethanol-to-isobutene conversion were studied using ZnxZryOz catalysts. The ethanol-to-isobutene reaction was found to be limited by the secondary reaction of the key intermediate, acetone, namely the acetone-to-isobutene reaction. Although the catalysts with coexisting Brønsted acidity could catalyze the rate-limiting acetone-to-isobutene reaction, the presence of Brønsted acidity is also detrimental. First, secondary isobutene isomerization is favored, producing a mixture of butene isomers. Second, undesired polymerization and coke formation prevail, leading to rapid catalyst deactivation. Most importantly, both steady-state and kinetic reaction studies as well as FTIR analysis of adsorbed acetone-d6 and D2O unambiguouslymore » showed that a highly active and selective nature of balanced Lewis acid-base pairs was masked by the coexisting Brønsted acidity in the aldolization and self-deoxygenation of acetone to isobutene. As a result, ZnxZryOz catalysts with only Lewis acid-base pairs were discovered, on which nearly a theoretical selectivity to isobutene (~88.9%) was successfully achieved, which has never been reported before. Moreover, the absence of Brønsted acidity in such ZnxZryOz catalysts also eliminates the side isobutene isomerization and undesired polymerization/coke reactions, resulting in the production of high purity isobutene with significantly improved catalyst stability (< 2% activity loss after 200 h time-on-stream). This work not only demonstrates a balanced Lewis acid-base pair for the highly active and selective cascade ethanol-to-isobutene reaction, but also sheds light on the rational design of selective and robust acid-base catalyst for C-C coupling via aldolization reaction.« less

Acid-functionalized polyolefin materials and their use in acid-promoted chemical reactions

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

Oyola, Yatsandra; Tian, Chengcheng; Bauer, John Christopher

An acid-functionalized polyolefin material that can be used as an acid catalyst in a wide range of acid-promoted chemical reactions, wherein the acid-functionalized polyolefin material includes a polyolefin backbone on which acid groups are appended. Also described is a method for the preparation of the acid catalyst in which a precursor polyolefin is subjected to ionizing radiation (e.g., electron beam irradiation) of sufficient power and the irradiated precursor polyolefin reacted with at least one vinyl monomer having an acid group thereon. Further described is a method for conducting an acid-promoted chemical reaction, wherein an acid-reactive organic precursor is contacted inmore » liquid form with a solid heterogeneous acid catalyst comprising a polyolefin backbone of at least 1 micron in one dimension and having carboxylic acid groups and either sulfonic acid or phosphoric acid groups appended thereto.« less

Contribution of the 7β-hydroxysteroid dehydrogenase from Ruminococcus gnavus N53 to ursodeoxycholic acid formation in the human colon.

PubMed

Lee, Ja-Young; Arai, Hisashi; Nakamura, Yusuke; Fukiya, Satoru; Wada, Masaru; Yokota, Atsushi

2013-11-01

Bile acid composition in the colon is determined by bile acid flow in the intestines, the population of bile acid-converting bacteria, and the properties of the responsible bacterial enzymes. Ursodeoxycholic acid (UDCA) is regarded as a chemopreventive beneficial bile acid due to its low hydrophobicity. However, it is a minor constituent of human bile acids. Here, we characterized an UDCA-producing bacterium, N53, isolated from human feces. 16S rDNA sequence analysis identified this isolate as Ruminococcus gnavus, a novel UDCA-producer. The forward reaction that produces UDCA from 7-oxo-lithocholic acid was observed to have a growth-dependent conversion rate of 90-100% after culture in GAM broth containing 1 mM 7-oxo-lithocholic acid, while the reverse reaction was undetectable. The gene encoding 7β-hydroxysteroid dehydrogenase (7β-HSDH), which facilitates the UDCA-producing reaction, was cloned and overexpressed in Escherichia coli. Characterization of the purified 7β-HSDH revealed that the kcat/Km value was about 55-fold higher for the forward reaction than for the reverse reaction, indicating that the enzyme favors the UDCA-producing reaction. As R. gnavus is a common, core bacterium of the human gut microbiota, these results suggest that this bacterium plays a pivotal role in UDCA formation in the colon.

Contribution of the 7β-hydroxysteroid dehydrogenase from Ruminococcus gnavus N53 to ursodeoxycholic acid formation in the human colon[S

PubMed Central

Lee, Ja-Young; Arai, Hisashi; Nakamura, Yusuke; Fukiya, Satoru; Wada, Masaru; Yokota, Atsushi

2013-01-01

Bile acid composition in the colon is determined by bile acid flow in the intestines, the population of bile acid-converting bacteria, and the properties of the responsible bacterial enzymes. Ursodeoxycholic acid (UDCA) is regarded as a chemopreventive beneficial bile acid due to its low hydrophobicity. However, it is a minor constituent of human bile acids. Here, we characterized an UDCA-producing bacterium, N53, isolated from human feces. 16S rDNA sequence analysis identified this isolate as Ruminococcus gnavus, a novel UDCA-producer. The forward reaction that produces UDCA from 7-oxo-lithocholic acid was observed to have a growth-dependent conversion rate of 90–100% after culture in GAM broth containing 1 mM 7-oxo-lithocholic acid, while the reverse reaction was undetectable. The gene encoding 7β-hydroxysteroid dehydrogenase (7β-HSDH), which facilitates the UDCA-producing reaction, was cloned and overexpressed in Escherichia coli. Characterization of the purified 7β-HSDH revealed that the kcat/Km value was about 55-fold higher for the forward reaction than for the reverse reaction, indicating that the enzyme favors the UDCA-producing reaction. As R. gnavus is a common, core bacterium of the human gut microbiota, these results suggest that this bacterium plays a pivotal role in UDCA formation in the colon. PMID:23729502

Phytochemical Analysis and Free Radical Scavenging Activity of Medicinal Plants Gnidia glauca and Dioscorea bulbifera

PubMed Central

Ghosh, Sougata; Derle, Abhishek; Ahire, Mehul; More, Piyush; Jagtap, Soham; Phadatare, Suvarna D.; Patil, Ajay B.; Jabgunde, Amit M.; Sharma, Geeta K.; Shinde, Vaishali S.; Pardesi, Karishma; Dhavale, Dilip D.; Chopade, Balu A.

2013-01-01

Gnidia glauca and Dioscorea bulbifera are traditional medicinal plants that can be considered as sources of natural antioxidants. Herein we report the phytochemical analysis and free radical scavenging activity of their sequential extracts. Phenolic and flavonoid content were determined. Scavenging activity was checked against pulse radiolysis generated ABTS•+ and OH radical, in addition to DPPH, superoxide and hydroxyl radicals by biochemical methods followed by principal component analysis. G. glauca leaf extracts were rich in phenolic and flavonoid content. Ethyl acetate extract of D. bulbifera bulbs and methanol extract of G. glauca stem exhibited excellent scavenging of pulse radiolysis generated ABTS•+ radical with a second order rate constant of 2.33×106 and 1.72×106, respectively. Similarly, methanol extract of G. glauca flower and ethyl acetate extract of D. bulbifera bulb with second order rate constants of 4.48×106 and 4.46×106 were found to be potent scavengers of pulse radiolysis generated OH radical. G. glauca leaf and stem showed excellent reducing activity and free radical scavenging activity. HPTLC fingerprinting, carried out in mobile phase, chloroform: toluene: ethanol (4: 4: 1, v/v) showed presence of florescent compound at 366 nm as well as UV active compound at 254 nm. GC-TOF-MS analysis revealed the predominance of diphenyl sulfone as major compound in G. glauca. Significant levels of n-hexadecanoic acid and octadecanoic acid were also present. Diosgenin (C27H42O3) and diosgenin (3á,25R) acetate were present as major phytoconstituents in the extracts of D. bulbifera. G. glauca and D. bulbifera contain significant amounts of phytochemicals with antioxidative properties that can be exploited as a potential source for herbal remedy for oxidative stress induced diseases. These results rationalize further investigation in the potential discovery of new natural bioactive principles from these two important medicinal plants. PMID:24367520

Phytochemical analysis and free radical scavenging activity of medicinal plants Gnidia glauca and Dioscorea bulbifera.

PubMed

Ghosh, Sougata; Derle, Abhishek; Ahire, Mehul; More, Piyush; Jagtap, Soham; Phadatare, Suvarna D; Patil, Ajay B; Jabgunde, Amit M; Sharma, Geeta K; Shinde, Vaishali S; Pardesi, Karishma; Dhavale, Dilip D; Chopade, Balu A

2013-01-01

Gnidia glauca and Dioscorea bulbifera are traditional medicinal plants that can be considered as sources of natural antioxidants. Herein we report the phytochemical analysis and free radical scavenging activity of their sequential extracts. Phenolic and flavonoid content were determined. Scavenging activity was checked against pulse radiolysis generated ABTS(•+) and OH radical, in addition to DPPH, superoxide and hydroxyl radicals by biochemical methods followed by principal component analysis. G. glauca leaf extracts were rich in phenolic and flavonoid content. Ethyl acetate extract of D. bulbifera bulbs and methanol extract of G. glauca stem exhibited excellent scavenging of pulse radiolysis generated ABTS(•+) radical with a second order rate constant of 2.33 × 10(6) and 1.72 × 10(6), respectively. Similarly, methanol extract of G. glauca flower and ethyl acetate extract of D. bulbifera bulb with second order rate constants of 4.48 × 10(6) and 4.46 × 10(6) were found to be potent scavengers of pulse radiolysis generated OH radical. G. glauca leaf and stem showed excellent reducing activity and free radical scavenging activity. HPTLC fingerprinting, carried out in mobile phase, chloroform: toluene: ethanol (4: 4: 1, v/v) showed presence of florescent compound at 366 nm as well as UV active compound at 254 nm. GC-TOF-MS analysis revealed the predominance of diphenyl sulfone as major compound in G. glauca. Significant levels of n-hexadecanoic acid and octadecanoic acid were also present. Diosgenin (C₂₇H₄₂O₃) and diosgenin (3á,25R) acetate were present as major phytoconstituents in the extracts of D. bulbifera. G. glauca and D. bulbifera contain significant amounts of phytochemicals with antioxidative properties that can be exploited as a potential source for herbal remedy for oxidative stress induced diseases. These results rationalize further investigation in the potential discovery of new natural bioactive principles from these two important medicinal plants.

Students' Understanding of Acid, Base and Salt Reactions in Qualitative Analysis.

ERIC Educational Resources Information Center

Tan, Kim-Chwee Daniel; Goh, Ngoh-Khang; Chia, Lian-Sai; Treagust, David F.

2003-01-01

Uses a two-tier, multiple-choice diagnostic instrument to determine (n=915) grade 10 students' understanding of the acid, base, and salt reactions involved in basic qualitative analysis. Reports that many students did not understand the formation of precipitates and the complex salts, acid/salt-base reactions, and thermal decomposition involved in…

The chemical foundations of nitroalkene fatty acid signaling through addition reactions with thiols.

PubMed

Turell, Lucía; Steglich, Martina; Alvarez, Beatriz

2018-03-22

Nitroalkene fatty acids can be formed in vivo and administered exogenously. They exert pleiotropic signaling actions with cytoprotective and antiinflammatory effects. The presence of the potent electron withdrawing nitro group confers electrophilicity to the adjacent β-carbon. Thiols (precisely, thiolates) are strong nucleophiles and can react with nitroalkene fatty acids through reversible Michael addition reactions. In addition, nitroalkene fatty acids can undergo several other processes including metabolic oxidation, reduction, esterification, nitric oxide release and partition into hydrophobic compartments. The signaling actions of nitroalkenes are mainly mediated by reactions with critical thiols in regulatory proteins. Thus, the thio-Michael addition reaction provides a framework for understanding the molecular basis of the biological effects of nitroalkene fatty acids at the crossroads of thiol signaling and electrophilic lipid signaling. In this review, we describe the reactions of nitroalkene fatty acids in biological contexts. We focus on the Michael addition-elimination reaction with thiols and its mechanism, and extrapolate kinetic and thermodynamic considerations to in vivo settings. Copyright © 2018 Elsevier Inc. All rights reserved.

Magnetite-supported sulfonic acid: a retrievable nanocatalyst for the Ritter reaction and multicomponent reactions

EPA Science Inventory

Magnetite-sulfonic acid (NanocatFe-OSO3H), prepared by wet-impregnation method, serves as a magnetically retrievable sustainable catalyst for the Ritter reaction which can be used in several reaction cycles without any loss of activity.

Lewis acid-Lewis acid heterobimetallic cooperative catalysis: mechanistic studies and application in enantioselective aza-Michael reaction.

PubMed

Yamagiwa, Noriyuki; Qin, Hongbo; Matsunaga, Shigeki; Shibasaki, Masakatsu

2005-09-28

The full details of a catalytic asymmetric aza-Michael reaction of methoxylamine promoted by rare earth-alkali metal heterobimetallic complexes are described, demonstrating the effectiveness of Lewis acid-Lewis acid cooperative catalysis. First, enones were used as substrates, and the 1,4-adducts were obtained in good yield (57-98%) and high ee (81-96%). Catalyst loading was successfully reduced to 0.3-3 mol % with enones. To broaden the substrate scope of the reaction to carboxylic acid derivatives, alpha,beta-unsaturated N-acylpyrroles were used as monodentate, carboxylic acid derivatives. With beta-alkyl-substituted N-acylpyrroles, the reaction proceeded smoothly and the products were obtained in high yield and good ee. Transformation of the 1,4-adducts from enones and alpha,beta-unsaturated N-acylpyrroles afforded corresponding chiral aziridines and beta-amino acids. Detailed mechanistic studies, including kinetics, NMR analysis, nonlinear effects, and rare earth metal effects, are also described. The Lewis acid-Lewis acid cooperative mechanism, including the substrate coordination mode, is discussed in detail.

Reaction of 3-Amino-1,2,4-Triazole with Diethyl Phosphite and Triethyl Orthoformate: Acid-Base Properties and Antiosteoporotic Activities of the Products.

PubMed

Miszczyk, Patrycja; Wieczorek, Dorota; Gałęzowska, Joanna; Dziuk, Błażej; Wietrzyk, Joanna; Chmielewska, Ewa

2017-02-08

The reaction of diethyl phosphite with triethyl orthoformate and a primary amine followed by hydrolysis is presented, and the reaction was suitable for the preparation of (aminomethylene)bisphosphonates. 3-Amino-1,2,4-triazole was chosen as an interesting substrate for this reaction because it possesses multiple groups that can serve as the amino component in the reaction-namely, the side-chain and triazole amines. This substrate readily forms 1,2,4-triazolyl-3-yl-aminomethylenebisphosphonic acid (compound 1 ) as a major product, along with N -ethylated bisphosphonates as side products. The in vitro antiproliferative effects of the synthesized aminomethylenebisphosphonic acids against J774E macrophages were determined. These compounds exhibit similar activity to zoledronic acid and higher activity than incadronic acid.

Synthesis of structured triacylglycerols enriched in n-3 fatty acids by immobilized microbial lipase.

PubMed

Araújo, Maria Elisa Melo Branco de; Campos, Paula Renata Bueno; Alberto, Thiago Grando; Contesini, Fabiano Jares; Carvalho, Patrícia de Oliveira

The search for new biocatalysts has aroused great interest due to the variety of micro-organisms and their role as enzyme producers. Native lipases from Aspergillus niger and Rhizopus javanicus were used to enrich the n-3 long-chain polyunsaturated fatty acids content in the triacylglycerols of soybean oil by acidolysis with free fatty acids from sardine oil in solvent-free media. For the immobilization process, the best lipase/support ratios were 1:3 (w/w) for Aspergillus niger lipase and 1:5 (w/w) for Rhizopus javanicus lipase using Amberlite MB-1. Both lipases maintained constant activity for 6 months at 4°C. Reaction time, sardine-free fatty acids:soybean oil mole ratio and initial water content of the lipase were investigated to determine their effects on n-3 long-chain polyunsaturated fatty acids incorporation into soybean oil. Structured triacylglycerols with 11.7 and 7.2% of eicosapentaenoic acid+docosahexaenoic acid were obtained using Aspergillus niger lipase and Rhizopus javanicus lipase, decreasing the n-6/n-3 fatty acids ratio of soybean oil (11:1 to 3.5:1 and 4.7:1, respectively). The best reaction conditions were: initial water content of lipase of 0.86% (w/w), sardine-free faty acids:soybean oil mole ratio of 3:1 and reaction time of 36h, at 40°C. The significant factors for the acidolysis reaction were the sardine-free fatty acids:soybean oil mole ratio and reaction time. The characterization of structured triacylglycerols was obtained using easy ambient sonic-spray ionization mass spectrometry. The enzymatic reaction led to the formation of many structured triacylglycerols containing eicosapentaenoic acid, docosahexaenoic acid or both polyunsaturated fatty acids. Copyright © 2016 Sociedade Brasileira de Microbiologia. Published by Elsevier Editora Ltda. All rights reserved.

Adverse drug reactions induced by valproic acid.

PubMed

Nanau, Radu M; Neuman, Manuela G

2013-10-01

Valproic acid is a widely-used first-generation antiepileptic drug, prescribed predominantly in epilepsy and psychiatric disorders. VPA has good efficacy and pharmacoeconomic profiles, as well as a relatively favorable safety profile. However, adverse drug reactions have been reported in relation with valproic acid use, either as monotherapy or polytherapy with other antiepileptic drugs or antipsychotic drugs. This systematic review discusses valproic acid adverse drug reactions, in terms of hepatotoxicity, mitochondrial toxicity, hyperammonemic encephalopathy, hypersensitivity syndrome reactions, neurological toxicity, metabolic and endocrine adverse events, and teratogenicity. Copyright © 2013 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

40 CFR 721.9485 - Dimer acid/polymerized rosin amidoamine reaction product (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... amidoamine reaction product (generic). 721.9485 Section 721.9485 Protection of Environment ENVIRONMENTAL... reaction product (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as Dimer acid/polymerized rosin amidoamine reaction product (PMN...

40 CFR 721.9485 - Dimer acid/polymerized rosin amidoamine reaction product (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... amidoamine reaction product (generic). 721.9485 Section 721.9485 Protection of Environment ENVIRONMENTAL... reaction product (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as Dimer acid/polymerized rosin amidoamine reaction product (PMN...

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 reaction. The intrinsic catalytic qualities of FeS and NiS are also explored in the absence of CO. It was shown that the addition of NiS has a minimal effect in the product distribution, whereas the addition of FeS leads to the formation of hydrogenated and sulfur-containing products (thioethers). These results point to a simple hydrothermal redox pathway for citric acid synthesis that may have provided a geochemical ignition point for the reductive citrate cycle.

The Heterogeneous Oxidation of Organic Droplets -Temperature and Physical Phase Effects

NASA Astrophysics Data System (ADS)

Hung, H.; Tang, C.; Lin, L.

2008-12-01

The heterogeneous reactions of oleic acid droplets with ozone are studied at different temperatures to imitating the atmospheric condition. The reactions are monitored concomitantly by using attenuated total reflectance Fourier Transform infrared spectroscopy (ATR-FT-IR) for the organic species and UV-VIS spectrometry for the ozone concentration, in order to investigate reaction rate discrepancies reported in literature as well as the oxidation mechanism, temperature and physical phase effects. The less and semi- volatile products are identified and resolved by a liquid chromatography and a gas chromatography mass spectrometer, respectively. The identified products are predominantly composed by nananoic acid and azelaic acid and might be due to propagation reactions possibly initiated by a secondary reaction such as the stabilized Criegee intermediates reacting with oleic acid. For temperature effect, the oxidation rate decreases with temperature when the oleic acid droplets are in the same physical phases. As oleic acid turns into the solid phase, the oxidation mechanism is observed to be different from the liquid phase. Furthermore, the concentration of ozone was monitored to examine the kinetics of the oxidation reaction. The integrated ozone profile recorded by UV-VIS spectrometry shows that the consumed ozone represents only approximately 12% of total oleic acid for the solid cases at 4°C in contrast to 30% for the liquid cases at 25°C, and hence confirmed the existence of secondary reactions.

Interchange reaction of disulfides and denaturation of oxytocin by copper(II)/ascorbic acid/O2 system.

PubMed

Inoue, H; Hirobe, M

1987-05-29

The interchange reaction of disulfides was caused by the copper(II)/ascorbic acid/O2 system. The incubation of two symmetric disulfides, L-cystinyl-bis-L-phenylalanine (PP) and L-cystinyl-bis-L-tyrosine (TT), with L-ascorbic acid and CuSO4 in potassium phosphate buffer (pH 7.2, 50 mM) resulted in the formation of an asymmetric disulfide, L-cystinyl-L-phenylalanine-L-tyrosine (PT), and the final ratio of PP:PT:TT was 1:2:1. As the reaction was inhibited by catalase and DMSO only at the initial time, hydroxyl radical generated by the copper(II)/ascorbic acid/O2 system seemed to be responsible for the initiation of the reaction. Oxytocin and insulin were denatured by this system, and catalase and DMSO similarly inhibited these denaturations. As the composition of amino acids was unchanged after the reaction, hydroxyl radical was thought to cause the cleavage and/or interchange reaction of disulfides to denature the peptides.

Disproportionation of rosin on an industrial Pd/C catalyst: reaction pathway and kinetic model discrimination.

PubMed

Souto, Juan Carlos; Yustos, Pedro; Ladero, Miguel; Garcia-Ochoa, Felix

2011-02-01

In this work, a phenomenological study of the isomerisation and disproportionation of rosin acids using an industrial 5% Pd on charcoal catalyst from 200 to 240°C is carried out. Medium composition is determined by elemental microanalysis, GC-MS and GC-FID. Dehydrogenated and hydrogenated acid species molar amounts in the final product show that dehydrogenation is the main reaction. Moreover, both hydrogen and non-hydrogen concentration considering kinetic models are fitted to experimental data using a multivariable non-linear technique. Statistical discrimination among the proposed kinetic models lead to the conclusion hydrogen considering models fit much better to experimental results. The final kinetic model involves first-order isomerisation reactions of neoabietic and palustric acids to abietic acid, first-order dehydrogenation and hydrogenation of this latter acid, and hydrogenation of pimaric acids. Hydrogenation reactions are partial first-order regarding the acid and hydrogen. Copyright © 2010 Elsevier Ltd. All rights reserved.

Lipozyme RM IM-catalyzed acidolysis of Cinnamomum camphora seed oil with oleic acid to produce human milk fat substitutes enriched in medium-chain fatty acids.

PubMed

Zou, Xian-Guo; Hu, Jiang-Ning; Zhao, Man-Li; Zhu, Xue-Mei; Li, Hong-Yan; Liu, Xiao-Ru; Liu, Rong; Deng, Ze-Yuan

2014-10-29

In the present study, a human milk fat substitute (HMFS) enriched in medium-chain fatty acids (MCFAs) was synthesized through acidolysis reaction from Cinnamomum camphora seed oil (CCSO) with oleic acid in a solvent-free system. A commercial immobilized lipase, Lipozyme RM IM, from Rhizomucor miehei, was facilitated as a biocatalyst. Effects of different reaction conditions, including substrate molar ratio, enzyme concentration, reaction temperature, and reaction time were investigated using response surface methodology (RSM) to obtain the optimal oleic acid incorporation. After optimization, results showed that the maximal incorporation of oleic acid into HMFS was 59.68%. Compared with CCSO, medium-chain fatty acids at the sn-2 position of HMFS accounted for >70%, whereas oleic acid was occupied predominantly at the sn-1,3 position (78.69%). Meanwhile, triacylglycerol (TAG) components of OCO (23.93%), CCO (14.94%), LaCO (13.58%), OLaO (12.66%), and OOO (11.13%) were determined as the major TAG species in HMFS. The final optimal reaction conditions were carried out as follows: substrate molar ratio (oleic acid/CCSO), 5:1; enzyme concentration, 12.5% (w/w total reactants); reaction temperature, 60 °C; and reaction time, 28 h. The reusability of Lipozyme RM IM in the acidolysis reaction was also evaluated, and it was found that it could be reused up to 9 times without significant loss of activities. Urea inclusion method was used to separate and purify the synthetic product. As the ratio of HMFS/urea increased to 1:2, the acid value lowered to the minimum. In a scale-up experiment, the contents of TAG and total tocopherols in HMFS (modified CCSO) were 77.28% and 12.27 mg/100 g, respectively. All of the physicochemical indices of purified product were within food standards. Therefore, such a MCFA-enriched HMFS produced by using the acidolysis method might have potential application in the infant formula industry.

Model Experiment of Thermal Runaway Reactions Using the Aluminum-Hydrochloric Acid Reaction

ERIC Educational Resources Information Center

Kitabayashi, Suguru; Nakano, Masayoshi; Nishikawa, Kazuyuki; Koga, Nobuyoshi

2016-01-01

A laboratory exercise for the education of students about thermal runaway reactions based on the reaction between aluminum and hydrochloric acid as a model reaction is proposed. In the introductory part of the exercise, the induction period and subsequent thermal runaway behavior are evaluated via a simple observation of hydrogen gas evolution and…

Study of stability of methotrexate in acidic solution spectrofluorimetric determination of methotrexate in pharmaceutical preparations through acid-catalyzed degradation reaction.

PubMed

Sabry, Suzy M; Abdel-Hady, M; Elsayed, M; Fahmy, Osama T; Maher, Hadir M

2003-07-14

Study of the degradation reaction of methotrexate (MTX) in acidic solution was carried out. Optimization of the experimental parameters of MTX acid hydrolysis was investigated. Spectrofluorimetric method for determination of MTX through measurement of its acid-degradation product, 4-amino-4-deoxy-10-methylpteroic acid (AMP), was developed. Stability of the standard solution of MTX prepared in sulfuric acid was discussed in the view of accelerated stability analysis. Two other comparative spectroflourimetric methods based on measuring the fluorescence intensities from either a condensation reaction with acetylacetone-formaldehyde (Hantzsch reaction) or a reaction with fluorescamine were also described. Beer's law validation, accuracy, precision, limits of detection, limits of quantification, and other aspects of analytical merit are presented in the text. The proposed methods were successfully applied for the analysis of MTX in pure drug and tablets dosage form. The sensitivity of the developed methods was favorable, so it was possible to be adopted for determination of MTX in plasma samples for routine use in high-dose MTX therapy.

Enzymatic Pretreatment Coupled with the Addition of p-Hydroxyanisole Increased Levulinic Acid Production from Steam-Exploded Rice Straw Short Fiber.

PubMed

Ma, Li-Tong; Zhao, Zhi-Min; Yu, Bin; Chen, Hong-Zhang

2016-11-01

Levulinic acid production, directly from lignocellulosic biomass, resulted in low yields due to the poor substrate accessibility and occurrence of side reactions. The effects of reaction conditions, enzymatic pretreatment, and inhibitor addition on the conversion of steam-exploded rice straw (SERS) short fiber to levulinic acid catalyzed by solid superacid were investigated systematically. The results indicated that the optimal reaction conditions were temperature, time, and solid superacid concentration combinations of 200 °C, 15 min, and 7.5 %. Enzymatic pretreatment improved the substrate accessibility to solid superacid catalyst, and p-hydroxyanisole inhibitor reduced the side reactions during reaction processes, which helped to increase levulinic acid yield. The levulinic acid yield reached 25.2 % under the optimal conditions, which was 61.5 % higher than that without enzymatic pretreatment and inhibitor addition. Therefore, enzymatic pretreatment coupled with the addition of p-hydroxyanisole increased levulinic acid production effectively, which contributed to the value-added utilization of lignocellulosic biomass.

Nitrosation and nitration of fulvic acid, peat and coal with nitric acid

USGS Publications Warehouse

Thorn, Kevin A.; Cox, Larry G.

2016-01-01

Nitrohumic acids, produced from base extraction of coals and peats oxidized with nitric acid, have received considerable attention as soil ammendments in agriculture. The nitration chemistry however is incompletely understood. Moreover, there is a need to understand the reaction of nitric acid with natural organic matter (NOM) in general, in the context of a variety of environmental and biogeochemical processes. Suwannee River NOM, Suwannee River fulvic acid, and Pahokee Peat fulvic acid were treated with 15N-labeled nitric acid at concentrations ranging from 15% to 22% and analyzed by liquid and solid state 15N NMR spectroscopy. Bulk Pahokee peat and Illinois #6 coal were also treated with nitric acid, at 29% and 40% respectively, and analyzed by solid state 15N NMR spectroscopy. In addition to nitro groups from nitration of aromatic carbon, the 15N NMR spectra of all five samples exhibited peaks attributable to nitrosation reactions. These include nitrosophenol peaks in the peat fulvic acid and Suwannee River samples, from nitrosation of phenolic rings, and N-nitroso groups in the peat samples, from nitrosation of secondary amides or amines, the latter consistent with the peat samples having the highest naturally abundant nitrogen contents. Peaks attributable to Beckmann and secondary reactions of the initially formed oximes were present in all spectra, including primary amide, secondary amide, lactam, and nitrile nitrogens. The degree of secondary reaction product formation resulting from nitrosation reactions appeared to correlate inversely with the 13C aromaticities of the samples. The nitrosation reactions are most plausibly effected by nitrous acid formed from the reduction of nitric acid by oxidizable substrates in the NOM and coal samples.

Nitrosation and Nitration of Fulvic Acid, Peat and Coal with Nitric Acid

PubMed Central

Thorn, Kevin A.; Cox, Larry G.

2016-01-01

Nitrohumic acids, produced from base extraction of coals and peats oxidized with nitric acid, have received considerable attention as soil ammendments in agriculture. The nitration chemistry however is incompletely understood. Moreover, there is a need to understand the reaction of nitric acid with natural organic matter (NOM) in general, in the context of a variety of environmental and biogeochemical processes. Suwannee River NOM, Suwannee River fulvic acid, and Pahokee Peat fulvic acid were treated with 15N-labeled nitric acid at concentrations ranging from 15% to 22% and analyzed by liquid and solid state 15N NMR spectroscopy. Bulk Pahokee peat and Illinois #6 coal were also treated with nitric acid, at 29% and 40% respectively, and analyzed by solid state 15N NMR spectroscopy. In addition to nitro groups from nitration of aromatic carbon, the 15N NMR spectra of all five samples exhibited peaks attributable to nitrosation reactions. These include nitrosophenol peaks in the peat fulvic acid and Suwannee River samples, from nitrosation of phenolic rings, and N-nitroso groups in the peat samples, from nitrosation of secondary amides or amines, the latter consistent with the peat samples having the highest naturally abundant nitrogen contents. Peaks attributable to Beckmann and secondary reactions of the initially formed oximes were present in all spectra, including primary amide, secondary amide, lactam, and nitrile nitrogens. The degree of secondary reaction product formation resulting from nitrosation reactions appeared to correlate inversely with the 13C aromaticities of the samples. The nitrosation reactions are most plausibly effected by nitrous acid formed from the reduction of nitric acid by oxidizable substrates in the NOM and coal samples. PMID:27175784

Microwave-Assisted Rapid Enzymatic Synthesis of Nucleic Acids.

PubMed

Hari Das, Rakha; Ahirwar, Rajesh; Kumar, Saroj; Nahar, Pradip

2016-07-02

Herein we report microwave-induced enhancement of the reactions catalyzed by Escherichia coli DNA polymerase I and avian myeloblastosis virus-reverse transcriptase. The reactions induced by microwaves result in a highly selective synthesis of nucleic acids in 10-50 seconds. In contrast, same reactions failed to give desired reaction products when carried out in the same time periods, but without microwave irradiation. Each of the reactions was carried out for different duration of microwave exposure time to find the optimum reaction time. The products produced by the respective enzyme upon microwave irradiation of the reaction mixtures were identical to that produced by the conventional procedures. As the microwave-assisted reactions are rapid, microwave could be a useful alternative to the conventional and time consuming procedures of enzymatic synthesis of nucleic acids.

Lewis Acid-Assisted Photoinduced Intermolecular Coupling between Acylsilanes and Aldehydes: A Formal Cross Benzoin-Type Condensation.

PubMed

Ishida, Kento; Tobita, Fumiya; Kusama, Hiroyuki

2018-01-12

Intermolecular carbon-carbon bond-forming reaction between readily available acylsilanes and aldehydes was achieved under photoirradiation conditions with assistance of a catalytic amount of Lewis acid. Nucleophilic addition of photochemically generated siloxycarbenes to aldehydes followed by 1,4-silyl migration afforded synthetically useful α-siloxyketones. Electrophilic activation of aldehydes by Lewis acid is highly important to realize this reaction efficiently, otherwise the yield of the desired coupling products were significantly decreased. Noteworthy is that a formal cross benzoin-type reaction using acylsilanes was achieved under Lewis acidic conditions. This is the first example of Lewis acid-catalyzed reaction of photochemically generated siloxycarbenes with electrophiles. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High School Forum: "Invitations to Enquiry": The Calcite/Acid Reaction.

ERIC Educational Resources Information Center

Herron, J. Dudley, Ed.; Driscoll, D. R.

1979-01-01

Describes a high school chemistry experiment which involves the reaction between calcite and hydrochloric and sulfuric acids. This reaction can be carried out as a projected demonstration and on an individual basis. (HM)

The utilization of leftover as acid catalyst to catalyse the transesterification and esterification reactions

NASA Astrophysics Data System (ADS)

Leung, K. K.; Yau, Y. H.

2017-08-01

Biodiesel (Fatty Acid Methyl Ester, FAME) is a green and renewable energy. It is carbon neutral and produces less air pollutants in combustion. In my project, the selected feedstock of biodiesel production is grease trap oil (GTO). It is extracted from restaurants, and needs pre-treatment. The triglycerides and free fatty acid (FFA) are the main components of GTO. Both triglycerides and free fatty acid can be converted to biodiesel (Fatty Acid Methyl Ester) by transesterification and esterification, through reaction with alcohol (methanol) and catalyst. In the processes, acidic catalyst is chosen to speed up the reactions. The catalyst used In the study, a heterogeneous solid acid is applied. It is waste cooked rice (WCR) collected from leftover. The WCR powder is pyrolysed in 400°C furnace 15 hours and blown with nitrogen gas (incomplete carbonization). The WCR black powder is then mixed with concentrated sulphuric acid and heat in 160°C furnace 15 hours and continuous blown with nitrogen gas (sulphonation). This heterogeneous solid acid is used in the both transesterification and esterification to produce FAME. Moreover, in the optimal reaction conditions, this catalyst offers a stable catalytic effect. After 20 times usage in optimal reaction condition, the catalytic activity remains unchanged.

Candida rugosa lipase LIP1-catalyzed transesterification to produce human milk fat substitute.

PubMed

Srivastava, Anita; Akoh, Casimir C; Chang, Shu-Wei; Lee, Guan-Chiun; Shaw, Jei-Fu

2006-07-12

Structured lipids (SLs) containing palmitic and oleic acids were synthesized by transesterification of tripalmitin with either oleic acid or methyl oleate as acyl donor. This SL with palmitic acid at the sn-2 position and oleic acid at sn-1,3 positions is similar in structure to human milk fat triacylglycerol. LIP1, an isoform of Candida rugosa lipase (CRL), was used as biocatalyst. The effects of reaction temperature, substrate molar ratio, and time on incorporation of oleic acid were investigated. Reaction time and temperature were set at 6, 12, and 24 h, and 35, 45, and 55 degrees C, respectively. Substrate molar ratio was varied from 1:1 to 1:4. The highest incorporation of oleic acid (37.7%) was at 45 degrees C with methyl oleate as acyl donor. Oleic acid resulted in slightly lesser (26.3%) incorporation. Generally, higher percentage incorporation of oleic acid was observed with methyl oleate (transesterification) than with oleic acid (acidolysis). In both cases percentage incorporation increased with reaction time. Incorporation decreased with increase in temperature above 45 degrees C. Initially, oleic acid incorporation increased with increase in substrate molar ratio up to 1:3. LIP1 was also compared with Lipozyme RM IM as biocatalysts. The tested reaction parameters were selected on the basis of maximum incorporation of C18:1 obtained during optimization of LIP1 reaction conditions. Reaction temperature was maintained at 45, 55, and 65 degrees C. Lipozyme RM IM gave highest oleic acid incorporation (49.4%) at 65 degrees C with methyl oleate as acyl donor. Statistically significant (P < 0.05) differences were observed for both enzymes. SL prepared using Lipozyme RM IM may be more suitable for possible use in human milk fat substitutes.

Deoxygenation of Palmitic and Lauric Acids over Pt/ZIF-67 Membrane/Zeolite 5A Bead Catalysts.

PubMed

Yang, Liqiu; Carreon, Moises A

2017-09-20

The deoxygenation of palmitic and lauric acids over 0.5 wt % Pt/ZIF-67 membrane/zeolite 5A bead catalysts is demonstrated. Almost complete conversion (% deoxygenation of ≥95%) of these two fatty acids was observed over both fresh and recycled catalyst after a 2 h reaction time. The catalysts displayed high selectivity to pentadecane and undecane via decarboxylation reaction pathway even at low 0.5 wt % Pt loading. Selectivity to pentadecane and undecane as high as ∼92% and ∼94% was observed under CO 2 atmosphere when palmitic and lauric acids were used respectively as reactants. Depending on the reaction gas atmosphere, two distinctive reaction pathways were observed: decarboxylation and hydrodeoxygenation. Specifically, it was found that decarboxylation reaction pathway was more favorable in the presence of helium and CO 2 , while hydrodeoxygenation pathway strongly competed against the decarboxylation pathway when hydrogen was employed during the deoxygenation reactions. Esters were identified as the key reaction intermediates leading to decarboxylation and hydrodeoxygenation pathways.

Further links between the maximum hardness principle and the hard/soft acid/base principle: insights from hard/soft exchange reactions.

PubMed

Chattaraj, Pratim K; Ayers, Paul W; Melin, Junia

2007-08-07

Ayers, Parr, and Pearson recently showed that insight into the hard/soft acid/base (HSAB) principle could be obtained by analyzing the energy of reactions in hard/soft exchange reactions, i.e., reactions in which a soft acid replaces a hard acid or a soft base replaces a hard base [J. Chem. Phys., 2006, 124, 194107]. We show, in accord with the maximum hardness principle, that the hardness increases for favorable hard/soft exchange reactions and decreases when the HSAB principle indicates that hard/soft exchange reactions are unfavorable. This extends the previous work of the authors, which treated only the "double hard/soft exchange" reaction [P. K. Chattaraj and P. W. Ayers, J. Chem. Phys., 2005, 123, 086101]. We also discuss two different approaches to computing the hardness of molecules from the hardness of the composing fragments, and explain how the results differ. In the present context, it seems that the arithmetic mean of fragment softnesses is the preferable definition.

Preparation of bis-(1(2)H-tetrazol-5-yl)-amine monohydrate

DOEpatents

Naud, Darren L [Los Alamos, NM; Hiskey, Michael A [Los Alamos, NM

2003-05-27

A process of preparing bis-(1(2)H-tetrazol-5-yl)-amine monohydrate is provided including combining a dicyanamide salt, an azide salt and water to form a first reaction mixture, adding a solution of a first strong acid characterized as having a pKa of less than about 1 to said first reaction mixture over a period of time characterized as providing a controlled reaction rate so as to gradually form hydrazoic acid without loss of significant quantities of hydrazoic acid from the solution while heating the first reaction mixture at temperatures greater than about 65.degree. C., heating the resultant reaction mixture at temperatures greater than about 65.degree. C. for a period of time sufficient to substantially completely form a reaction product, treating the reaction product with a solution of a second strong acid to form a product of bis-(1(2)H-tetrazol-5-yl)-amine monohydrate, and, recovering the bis-(1(2)H-tetrazol-5-yl)-amine monohydrate product.

Fluorogenic, catalytic, photochemical reaction for amplified detection of nucleic acids.

PubMed

Dutta, Subrata; Fülöp, Annabelle; Mokhir, Andriy

2013-09-18

Photochemical, nucleic acid-induced reactions, which are controlled by nontoxic red light, are well-suited for detection of nucleic acids in live cells, since they do not require any additives and can be spatially and temporally regulated. We have recently described the first reaction of this type, in which a phenylselenyl derivative of thymidine (5'-PhSeT-ODNa) is cleaved in the presence of singlet oxygen (Fülöp, A., Peng, X., Greenberg, M. M., Mokhir, A. (2010) A nucleic acid directed, red light-induced chemical reaction. Chem. Commun. 46, 5659-5661). The latter reagent is produced upon exposure of a photosensitizer 3'-PS-ODNb (PS = Indium(III)-pyropheophorbide-a-chloride: InPPa) to >630 nm light. In 2012 we reported on a fluorogenic version of this reaction (Dutta, S., Flottmann, B., Heilemann, M., Mokhir, A. (2012) Hybridization and reaction-based, fluorogenic nucleic acid probes. Chem. Commun. 47, 9664-9666), which is potentially applicable for the detection of nucleic acids in cells. Unfortunately, its yield does not exceed 25% and no catalytic turnover could be observed in the presence of substrate excess. This problem occurs due to the efficient, competing oxidation of the substrate containing an electron rich carbon-carbon double bonds (SCH═CHS) in the presence of singlet oxygen with formation of a noncleavable product (SCH═CHSO). Herein we describe a related, but substantially improved photochemical, catalytic transformation of a fluorogenic, organic substrate, which consists of 9,10-dialkoxyanthracene linked to fluorescein, with formation of a bright fluorescent dye. In highly dilute solution this reaction occurs only in the presence of a nucleic acid template. We developed three types of such a reaction and demonstrated that they are high yielding and generate over 7.7 catalytic turnovers, are sensitive to single mismatches in nucleic acid targets, and can be applied for determination of both the amount of nucleic acids and potentially their localization.

Lipase-catalyzed synthesis of fattythioic acids from palm oil.

PubMed

Al-Mulla, Emad A Jaffar

2011-01-01

The present work focuses on the synthesis of fattythioic acids (FTAs) by a one-step lipase catalyzed reaction of palm oil with carbonothioic S,S-acid using Lipozyme. The product was characterized using Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance ((1)H NMR) technique and elemental analysis. The effects of various reaction parameters such as reaction time, temperature, amount of enzyme, molar ratio of substrates, and various organic solvents of the reaction system were investigated. The optimum conditions to produce FTAs were respectively, incubation time, 20 h, temperature, 40°C, amount of enzyme, 0.05 g and molar ratio of carbonothioic S,S-acid to palm oil, 5.0:1.0. Hexane was the best solvent for this reaction. The conversion of the products at optimum conditions was around 91%.

Thermodynamics of axial substitution and kinetics of reactions with amino acids for the paddlewheel complex tetrakis(acetato)chloridodiruthenium(II,III).

PubMed

Santos, Rodrigo L S R; van Eldik, Rudi; de Oliveira Silva, Denise

2012-06-18

The known paddlewheel, tetrakis(acetato)chloridodiruthenium(II,III), offers a versatile synthetic route to a novel class of antitumor diruthenium(II,III) metallo drugs, where the equatorial ligands are nonsteroidal anti-inflammatory carboxylates. This complex was studied here as a soluble starting prototype model for antitumor analogues to elucidate the reactivity of the [Ru(2)(CH(3)COO)(4)](+) framework. Thermodynamic studies on equilibration reactions for axial substitution of water by chloride and kinetic studies on reactions of the diaqua complexes with the amino acids glycine, cysteine, histidine, and tryptophan were performed. The standard thermodynamic reaction parameters ΔH°, ΔS°, and ΔV° were determined and showed that both of the sequential axial substitution reactions are enthalpy driven. Kinetic rate laws and rate constants were determined for the axial substitution reactions of coordinated water by the amino acids that gave the corresponding aqua(amino acid)-Ru(2) substituted species. The results revealed that the [Ru(2)(CH(3)COO)(4)](+) paddlewheel framework remained stable during the axial ligand substitution reactions and was also mostly preserved in the presence of the amino acids.

Reaction kinetics of free fatty acids esterification in palm fatty acid distillate using coconut shell biochar sulfonated catalyst

NASA Astrophysics Data System (ADS)

Hidayat, Arif; Rochmadi, Wijaya, Karna; Budiman, Arief

2015-12-01

Recently, a new strategy of preparing novel carbon-based solid acids has been developed. In this research, the esterification reactions of Palm Fatty Acid Distillate (PFAD) with methanol, using coconut shell biochar sulfonated catalyst from biomass wastes as catalyst, were studied. In this study, the coconut shell biochar sulfonated catalysts were synthesized by sulfonating the coconut shell biochar using concentrated H2SO4. The kinetics of free fatty acid (FFA) esterification in PFAD using a coconut shell biochar sulfonated catalyst was also studied. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%w, and reaction temperature of 60°C. The proposed kinetic model shows a reversible second order reaction and represents all the experimental data satisfactorily, providing deeper insight into the kinetics of the reaction.

Process for chemical reaction of amino acids and amides yielding selective conversion products

DOEpatents

Holladay, Jonathan E [Kennewick, WA

2006-05-23

The invention relates to processes for converting amino acids and amides to desirable conversion products including pyrrolidines, pyrrolidinones, and other N-substituted products. L-glutamic acid and L-pyroglutamic acid provide general reaction pathways to numerous and valuable selective conversion products with varied potential industrial uses.

The kinetics of the 2π+2π photodimerisation reactions of single-crystalline derivatives of trans-cinnamic acid: A study by infrared microspectroscopy

NASA Astrophysics Data System (ADS)

Jenkins, Samantha L.; Almond, Matthew J.; Atkinson, Samantha D. M.; Drew, Michael G. B.; Hollins, Peter; Mortimore, Joanne L.; Tobin, Mark J.

2006-04-01

The kinetics of the photodimerisation reactions of the 2- and 4-β-halogeno-derivatives of trans-cinnamic acid (where the halogen is fluorine, chlorine or bromine) have been investigated by infrared microspectroscopy. It is found that none of the reactions proceed to 100% yield. This is in line with a reaction mechanism developed by Wernick and his co-workers that postulates the formation of isolated monomers within the solid, which cannot react. β-4-Bromo and β-4-chloro- trans-cinnamic acids show approximately first order kinetics, although in both cases the reaction accelerates somewhat as it proceeds. First order kinetics is explained in terms of a reaction between one excited- and one ground-state monomer molecule, while the acceleration of the reaction implies that it is promoted as defects are formed within the crystal. By contrast β-2-chloro- trans-cinnamic acid shows a strongly accelerating reaction which models closely to the contracting cube equation. β-2-Fluoro- and β-4-fluoro- trans-cinnamic acids show a close match to first order kinetics. The 4-fluoro-derivative, however, shows a reaction that proceeds via a structural intermediate. The difference in behaviour between the 2-fluoro- and 4-fluoro-derivative may be due to different C-H⋯F hydrogen bonds observed within these single-crystalline starting materials.

Phenol-Urea-Formaldehyde (PUF) co-condensed wood adhesives

Treesearch

Bunichiro Tomita; Chung-Yun Hse

1998-01-01

The reaction of urea with methylolphenol under acidic conditions was investigated. The alternating copolymer of urea and phenol could be synthesized by the reaction of urea and 2,4,6-trimethylolphenol. The reactions of urea with polymethylolphenol mixtures also were investigated by changing the reaction conditions, such as the molar ratio and acidity. The co-...

Synthesis of acetic acid via methanol hydrocarboxylation with CO2 and H2

PubMed Central

Qian, Qingli; Zhang, Jingjing; Cui, Meng; Han, Buxing

2016-01-01

Acetic acid is an important bulk chemical that is currently produced via methanol carbonylation using fossil based CO. Synthesis of acetic acid from the renewable and cheap CO2 is of great importance, but state of the art routes encounter difficulties, especially in reaction selectivity and activity. Here we report a route to produce acetic acid from CO2, methanol and H2. The reaction can be efficiently catalysed by Ru–Rh bimetallic catalyst using imidazole as the ligand and LiI as the promoter in 1,3-dimethyl-2-imidazolidinone (DMI) solvent. It is confirmed that methanol is hydrocarboxylated into acetic acid by CO2 and H2, which accounts for the outstanding reaction results. The reaction mechanism is proposed based on the control experiments. The strategy opens a new way for acetic acid production and CO2 transformation, and represents a significant progress in synthetic chemistry. PMID:27165850

Synthesis of acetic acid via methanol hydrocarboxylation with CO2 and H2.

PubMed

Qian, Qingli; Zhang, Jingjing; Cui, Meng; Han, Buxing

2016-05-11

Acetic acid is an important bulk chemical that is currently produced via methanol carbonylation using fossil based CO. Synthesis of acetic acid from the renewable and cheap CO2 is of great importance, but state of the art routes encounter difficulties, especially in reaction selectivity and activity. Here we report a route to produce acetic acid from CO2, methanol and H2. The reaction can be efficiently catalysed by Ru-Rh bimetallic catalyst using imidazole as the ligand and LiI as the promoter in 1,3-dimethyl-2-imidazolidinone (DMI) solvent. It is confirmed that methanol is hydrocarboxylated into acetic acid by CO2 and H2, which accounts for the outstanding reaction results. The reaction mechanism is proposed based on the control experiments. The strategy opens a new way for acetic acid production and CO2 transformation, and represents a significant progress in synthetic chemistry.

Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids.

PubMed

Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim

2013-11-01

This review provides a comprehensive treatment of literature data dealing with asymmetric synthesis of α-amino-β-hydroxy and α,β-diamino acids via homologation of chiral Ni(II) complexes of glycine Schiff bases using aldol and Mannich-type reactions. These reactions proceed with synthetically useful chemical yields and thermodynamically controlled stereoselectivity and allow direct introduction of two stereogenic centers in a single operation with predictable stereochemical outcome. Furthermore, new application of Ni(II) complexes of α-amino acids Schiff bases for deracemization of racemic α-amino acids and (S) to (R) interconversion providing additional synthetic opportunities for preparation of enantiomerically pure α-amino acids, is also reviewed. Origin of observed diastereo-/enantioselectivity in the aldol, Mannich-type and deracemization reactions, generality and limitations of these methodologies are critically discussed.

Kinetics of nonoxidative leaching of galena in perchloric, hydrobromic, and hydrochloric acid solutions

NASA Astrophysics Data System (ADS)

Núñez, C.; Espiell, F.; García-Zayas, J.

1988-08-01

Several kinetic studies are presented on the nonoxidative leaching of galena with solutions of hydrocloric, hydrobromic, and perchloric acid. The kinetic parameters were set up in terms of the mean ionic activities of the electrolytes. The apparent order of reaction for the mean ionic activity of perchloric acid is one. For hydrochloric acid the order of reaction over a wide range of concentrations is 3/2 with respect to its mean activity. For hydrobromic acid, whose anion has greater complex-forming power for lead than HC1, the order of reaction is 2. Activation energies are 64.4 kJ/mole for HC1, 71.5 kJ/mole for HC104, and 66.5 kJ mole for HBr. The complete kinetic equations are given for the three reactions.

Modeling and simulation of enzymatic gluconic acid production using immobilized enzyme and CSTR-PFTR circulation reaction system.

PubMed

Li, Can; Lin, Jianqun; Gao, Ling; Lin, Huibin; Lin, Jianqiang

2018-04-01

Production of gluconic acid by using immobilized enzyme and continuous stirred tank reactor-plug flow tubular reactor (CSTR-PFTR) circulation reaction system. A production system is constructed for gluconic acid production, which consists of a continuous stirred tank reactor (CSTR) for pH control and liquid storage and a plug flow tubular reactor (PFTR) filled with immobilized glucose oxidase (GOD) for gluconic acid production. Mathematical model is developed for this production system and simulation is made for the enzymatic reaction process. The pH inhibition effect on GOD is modeled by using a bell-type curve. Gluconic acid can be efficiently produced by using the reaction system and the mathematical model developed for this system can simulate and predict the process well.

Different catalytic effects of a single water molecule: the gas-phase reaction of formic acid with hydroxyl radical in water vapor.

PubMed

Anglada, Josep M; Gonzalez, Javier

2009-12-07

The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).

An efficient and heterogeneous recyclable silicotungstic acid with modified acid sites as a catalyst for conversion of fructose and sucrose into 5-hydroxymethylfurfural in superheated water.

PubMed

Jadhav, Arvind H; Kim, Hern; Hwang, In Taek

2013-03-01

Acidity modified silver exchanged silicotungstic acid (AgSTA) catalyst was prepared and characterized by X-ray diffraction, FT-IR spectroscopy, Raman spectroscopy, FT-IR pyridine adsorption, SEM imaging, EDX mapping, and antimicrobial activity was also tested. The catalytic activity was evaluated for the dehydration of fructose and sucrose in superheated water. As a result, 98% conversion of fructose with 85.7% HMF yield and 87.4% HMF selectivity in 120 min reaction time at 120 °C reaction temperature using 10 wt.% of AgSTA catalyst was achieved. While, 92% sucrose conversion with 62.5% of HMF yield was obtained from sucrose at uniform condition in 160 min. The effect of reaction parameters, such as reaction temperature, time, catalyst dosage, and effect acidity on HMF yield was also investigated. The AgSTA catalyst was separated from the reaction mixture by filtration process at end of the reaction and reused eight times without loss of catalytic activity. Copyright © 2013 Elsevier Ltd. All rights reserved.

Modeling the oxidation kinetics of sono-activated persulfate's process on the degradation of humic acid.

PubMed

Songlin, Wang; Ning, Zhou; Si, Wu; Qi, Zhang; Zhi, Yang

2015-03-01

Ultrasound degradation of humic acid has been investigated in the presence of persulfate anions at ultrasonic frequency of 40 kHz. The effects of persulfate anion concentration, ultrasonic power input, humic acid concentration, reaction time, solution pH and temperature on humic acid removal efficiency were studied. It is found that up to 90% humic acid removal efficiency was achieved after 2 h reaction. In this system, sulfate radicals (SO₄⁻·) were considered to be the mainly oxidant to mineralize humic acid while persulfate anion can hardly react with humic acid directly. A novel kinetic model based on sulfate radicals (SO₄⁻·) oxidation was established to describe the humic acid mineralization process mathematically and chemically in sono-activated persulfate system. According to the new model, ultrasound power, persulfate dosage, solution pH and reaction temperature have great influence on humic acid degradation. Different initial concentration of persulfate anions and humic acid, ultrasonic power, initial pH and reaction temperature have been discussed to valid the effectiveness of the model, and the simulated data showed new model had good agreement with the experiments data.

Combined effects of lead and acid rain on photosynthesis in soybean seedlings.

PubMed

Hu, Huiqing; Wang, Lihong; Liao, Chenyu; Fan, Caixia; Zhou, Qing; Huang, Xiaohua

2014-10-01

To explore how lead (Pb) and acid rain simultaneously affect plants, the combined effects of Pb and acid rain on the chlorophyll content, chlorophyll fluorescence reaction, Hill reaction rate, and Mg(2+)-ATPase activity in soybean seedlings were investigated. The results indicated that, when soybean seedlings were treated with Pb or acid rain alone, the chlorophyll content, Hill reaction rate, Mg(2+)-ATPase activity, and maximal photochemical efficiency (F(v)/F(m)) were decreased, while the initial fluorescence (F 0) and maximum quantum yield (Y) were increased, compared with those of the control. The combined treatment with Pb and acid rain decreased the chlorophyll content, Hill reaction rate, Mg(2+)-ATPase activity, F(v)/F(m), and Y and increased F 0 in soybean seedlings. Under the combined treatment with Pb and acid rain, the two factors showed additive effects on the chlorophyll content in soybean seedlings and exhibited antagonistic effects on the Hill reaction rate. Under the combined treatment with high-concentration Pb and acid rain, the two factors exhibited synergistic effects on the Mg(2+)-ATPase activity, F 0, F v/F m, as well as Y. In summary, the inhibition of the photosynthetic process is an important physiological basis for the simultaneous actions of Pb and acid rain in soybean seedlings.

Optimization of biodiesel production process using recycled vegetable oil

NASA Astrophysics Data System (ADS)

Lugo, Yarely

Petro diesel toxic emissions and its limited resources have created an interest for the development of new energy resources, such as biodiesel. Biodiesel is traditionally produced by a transesterification reaction between vegetable oil and an alcohol in the presence of a catalyst. However, this process is slow and expensive due to the high cost of raw materials. Low costs feedstock oils such as recycled and animal fats are available but they cannot be transesterified with alkaline catalysts due to high content of free fatty acids, which can lead to undesirable reactions such as saponification. In this study, we reduce free fatty acids content by using an acid pre-treatment. We compare sulfuric acid, hydrochloric acid and ptoluenesulfonic acid (PTSA) to pre-treat recycled vegetable oil. PTSA removes water after 60 minutes of treatment at room temperature or within 15 minutes at 50°C. The pretreatment was followed by a transesterification reaction using alkaline catalyst. To minimize costs and accelerate reaction, the pretreatment and transesterification reaction of recycle vegetable oil was conducted at atmospheric pressure in a microwave oven. Biodiesel was characterized using a GC-MS method.

Impact of the propylene glycol-water-borax coolant on material recovery operations

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

Duerksen, W.K.; Taylor, P.A.

1983-05-01

The reaction of the propylene glycol-water-borax coolant with nitric acid has now been studied in some detail. This document is intended to provide a summary of the results. Findings are summarized under nine headings. Tests have also been conducted to determine if the new coolant would have any adverse effects on the uranium recycle systems. Experiments were scientifically designed after observation of the production operations so that accurate response to the immediate production concerns could be provided. Conclusions from these studies are: formation of glycol nitrates is very improbable; the reaction of concentrated (70%) nitric acid with pure propylene glycolmore » is very violent and hazardous; dilution of the nitric acid-glycol mixture causes a drastic decrease in the rate and intensity of the reaction; the mechanism of the nitric acid propylene glycol reaction is autocatalytic in nitrous acid; no reaction is observed between coolant and 30% nitric acid unless the solution is heated; the coolant reacts fairly vigorously with 55% nitric acid after a concentration-dependent induction time; experiments showed that the dissolution of uranium chips that had been soaked in coolant proceeded at about the same rate as if the chips had not previously contacted glycol; thermodynamic calculations show that the enthalpy change (heat liberated) by the reaction of nitric acid (30%) with propylene glycol is smaller than if the same amount of nitric acid reacted with uranium. Each of these conclusions is briefly discussed. The effect of new coolant on uranium recycle operations is then briefly discussed.« less

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system - a review

NASA Astrophysics Data System (ADS)

Zahardis, J.; Petrucci, G. A.

2007-02-01

The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquid-phase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN). The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation.

Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

ERIC Educational Resources Information Center

Antunes, Bruno M.; Cardoso, Simao P.; Silva, Carlos M.; Portugal, Ines

2011-01-01

A low-cost experiment to carry out the second-order reversible reaction of acetic acid esterification with ethanol to produce ethyl acetate is presented to illustrate concepts of kinetics and reactor modeling. The reaction is performed in a batch reactor, and the acetic acid concentration is measured by acid-base titration versus time. The…

Preparation of 4-amino-2,4-dioxobutanoic acid

DOEpatents

Unkefer, Pat J.; Martinez, Rodolfo A.; Glass, David R.

2015-06-02

A process for synthesizing 4-amino-2,4-dioxobutanoic acid involves reacting diethyl oxalate with sodium ethoxide in ethanol to form a reaction mixture, and afterward adding ethyl cyanoacetate to the reaction mixture and allowing a reaction to proceed under conditions suitable to form a first reaction product of the formula diethyl-2-cyano-3-hydroxy-butenedioate, and then isolating the diethyl-2-cyano-3-hydroxybutenedioate, and afterward reacting the diethyl-2-cyano-3-hydroxy-butenedioate with aqueous sodium hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoic acid.

Preparation of 4-amino-2,4-dioxobutanoic acid

DOEpatents

Unkefer, Pat J.; Martinez, Rodolfo A.; Glass, David R.

2016-03-22

A process for synthesizing 4-amino-2,4-dioxobutanoic acid involves reacting diethyl oxalate with an alkoxide in ethanol to form a reaction mixture, and afterward adding ethyl cyanoacetate to the reaction mixture and allowing a reaction to proceed under conditions suitable to form a first reaction product of the formula diethyl 2-cyano-3-hydroxy-butenedioate, and then isolating the diethyl 2-cyano-3-hydroxy-butenedioate, and afterward reacting the diethyl-2-cyano-3-hydroxy-butenedioate with an aqueous hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoic acid.

Exploring Nested Reaction Fronts to Understand How Oxygen Cracks Rocks, Carbonic and Sulfuric Acids Dissolve Rocks, and Water Transports Rocks during Weathering

NASA Astrophysics Data System (ADS)

Brantley, S. L.; Gu, X.; Sullivan, P. L.; Kim, H.; Stinchcomb, G. E.; Lebedeva, M.; Balashov, V. N.

2016-12-01

To first order, weathering is the reaction of rocks with oxidants (oxygen, nitrate, etc.), acids (carbonic, sulfuric, and organic acids), and water. To explore weathering we have been studying the depth intervals in soils, saprolite, and weathering rock where mineral reactions are localized - "reaction fronts". We limit the study to ridges or catchments in climates where precipitation is greater than potential evapotranspiration. For example, in the Susquehanna Shale Hills Critical Zone Observatory, we observe reaction fronts that generally define very rough surfaces in 3D that mimic the land surface topography, although with lower relief. Overall, the fronts form nested curved surfaces. In Shale Hills, the deepest reaction fronts are oxidation of pyrite, and dissolution of carbonate. The carbonate is inferred to dissolve at least partly due to the sulfuric acid produced by the pyrite. In addition to pyrite, chlorite also starts to oxidize at the water table. We hypothesize that these dissolution and oxidation reactions open pores and cause microfracturing that open the rock to infiltration of advecting meteoric waters. At much shallower depths, illite is observed to dissolve. In Shale Hills, these reaction fronts - pyrite, carbonate, illite - separate over meters beneath the ridges. Such separated reaction fronts have also been observed in other fractured lithologies where oxidation is the deepest reaction and is associated with weathering-induced fractures. In contrast, in some massive mafic rocks, reaction fronts are almost co-located. By studying the geometry of reaction fronts, it may be possible to elucidate the relative importance of how oxygen cracks rocks; carbonic, organic, and sulfuric acids dissolve rocks; and water mobilizes rock materials during weathering.

Preparation of Silica Nanoparticles Through Microwave-assisted Acid-catalysis

PubMed Central

Lovingood, Derek D.; Owens, Jeffrey R.; Seeber, Michael; Kornev, Konstantin G.; Luzinov, Igor

2013-01-01

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle diameters ranging from 30-250 nm by varying the reaction conditions. Through the selection of a microwave compatible solvent, silicic acid precursor, catalyst, and microwave irradiation time, these microwave-assisted methods were capable of overcoming the previously reported shortcomings associated with synthesis of silica nanoparticles using microwave reactors. The siloxane precursor was hydrolyzed using the acid catalyst, HCl. Acetone, a low-tan δ solvent, mediates the condensation reactions and has minimal interaction with the electromagnetic field. Condensation reactions begin when the silicic acid precursor couples with the microwave radiation, leading to silica nanoparticle sol formation. The silica nanoparticles were characterized by dynamic light scattering data and scanning electron microscopy, which show the materials' morphology and size to be dependent on the reaction conditions. Microwave-assisted reactions produce silica nanoparticles with roughened textured surfaces that are atypical for silica sols produced by Stöber's methods, which have smooth surfaces. PMID:24379052

Helicase-dependent amplification of nucleic acids.

PubMed

Cao, Yun; Kim, Hyun-Jin; Li, Ying; Kong, Huimin; Lemieux, Bertrand

2013-10-11

Helicase-dependent amplification (HDA) is a novel method for the isothermal in vitro amplification of nucleic acids. The HDA reaction selectively amplifies a target sequence by extension of two oligonucleotide primers. Unlike the polymerase chain reaction (PCR), HDA uses a helicase enzyme to separate the deoxyribonucleic acid (DNA) strands, rather than heat denaturation. This allows DNA amplification without the need for thermal cycling. The helicase used in HDA is a helicase super family II protein obtained from a thermophilic organism, Thermoanaerobacter tengcongensis (TteUvrD). This thermostable helicase is capable of unwinding blunt-end nucleic acid substrates at elevated temperatures (60° to 65°C). The HDA reaction can also be coupled with reverse transcription for ribonucleic acid (RNA) amplification. The products of this reaction can be detected during the reaction using fluorescent probes when incubations are conducted in a fluorimeter. Alternatively, products can be detected after amplification using a disposable amplicon containment device that contains an embedded lateral flow strip. Copyright © 2013 John Wiley & Sons, Inc.

Application of solid-acid catalyst and marine macro-algae Gracilaria verrucosa to production of fermentable sugars.

PubMed

Jeong, Gwi-Taek; Kim, Sung-Koo; Park, Don-Hee

2015-04-01

In this study, the hydrolysis of marine macro-algae Gracilaria verrucosa with a solid-acid catalyst was investigated. To optimize the hydrolysis, four reaction factors, including liquid-to-solid ratio, catalyst loading, reaction temperature, and reaction time, were investigated. In the results, the highest total reducing sugar (TRS) yield, 61 g/L (51.9%), was obtained under the following conditions: 1:7.5 solid-to-liquid ratio, 15% (w/v) catalyst loading, 140 °C reaction temperature, and 150 min reaction time. Under these conditions, 10.7 g/L of 5-HMF and 2.5 g/L of levulinic acid (LA) were generated. The application of solid-acid catalyst and marine macro-algae resources shows a very high potential for production of fermentable sugars. Copyright © 2015 Elsevier Ltd. All rights reserved.

Citric Acid-Modified Fenton's Reaction for the Oxidation of Chlorinated Ethylenes in Soil Solution Systems

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

Seol, Yongkoo; Javandel, Iraj

Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in-situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varyingmore » H{sub 2}O{sub 2} concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H{sub 2}O{sub 2} relative to iron catalysts (Fe{sup 2+}/H{sub 2}O{sub 2} < 1/330) would result in lowering the efficiency of contaminant removal by iron chelations in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.« less

Citric acid-modified Fenton's reaction for the oxidation of chlorinated ethylenes in soil solution systems.

PubMed

Seol, Yongkoo; Javandel, Iraj

2008-06-01

Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H2O2 concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H2O2 relative to iron catalysts (Fe2+/H2O2<1/330) would result in lowering the efficiency of contaminant removal by iron chelation in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.

Synthesis biolubricant from rubber seed oil

NASA Astrophysics Data System (ADS)

Hung, Nguyen Tran Dong; Tuyen, Dang Thi Hong; Viet, Tran Tan

2017-09-01

The objective was biolubricant preparation from rubber seed oil (RSO) using polymerization reactor with/without catalyst in batch reactor. Before become reactant in polymerization reaction, a non-edible rubber seed oil was converted into methyl ester by esterification/tranesterification reaction with methanol and acid/base catalyst. The polymerization reaction parameters investigated were reaction time, temperature and weight ratio (catalyst with feed), and their effect on the bio lubricant formation. The result show significant conversion of methyl ester to bio lubricant in the temperature reaction of 160°C, reaction time of 2h min and ratio of super acid catalyst (tetrafluoroboric acid-sHBF4) of 3 %w/w. The resulting products were confirmed by GC-MS, FTIR spectroscopy and also analyzed for the viscosity. The best viscosity value of RSOFAME polymer was 110.6 cSt when the condition polymerization reaction were 160 °C, reaction time 3h, 6 wt% mass ratio of oil:catalyst.

Koch–Haaf reaction of adamantanols in an acid-tolerant hastelloy-made microreactor

PubMed Central

Mukai, Yu

2011-01-01

Summary The Koch–Haaf reaction of adamantanols was successfully carried out in a microflow system at room temperature. By combining an acid-tolerant hastelloy-made micromixer, a PTFE tube, and a hastelloy-made microextraction unit, a packaged reaction-to-workup system was developed. By means of the present system, the multigram scale synthesis of 1-adamantanecarboxylic acid was achieved in ca. one hour operation. PMID:21977213

Synthesis of aminocarbonyl N-acylhydrazones by a three-component reaction of isocyanides, hydrazonoyl chlorides, and carboxylic acids.

PubMed

Giustiniano, Mariateresa; Meneghetti, Fiorella; Mercalli, Valentina; Varese, Monica; Giustiniano, Francesco; Novellino, Ettore; Tron, Gian Cesare

2014-10-17

A novel one-pot multicomponent synthesis of α-aminocarbonyl N-acylhydrazones starting from readily available hydrazonoyl chlorides, isocyanides, and carboxylic acids is reported. The strategy exploits the ability of the carboxylic acid as a third component to suppress all competing reactions between nitrile imines and isocyanides, channeling the course of the reaction toward the formation of this novel class of compounds.

Analysis of Reaction between α-Lipoic Acid and 2-Chloro-1-methylquinolinium Tetrafluoroborate Used as a Precolumn Derivatization Technique in Chromatographic Determination of α-Lipoic Acid.

PubMed

Godlewska, Magdalena; Odachowska, Angelika; Turkowicz, Monika; Karpinska, Joanna

2015-01-01

The present study offers results of analysis concerning the course of reaction between reduced α-lipoic acid (LA) and 2-chloro-1-methylquinolinium tetrafluoroborate (CMQT). In water environments, the reaction between CMQT and hydrophilic thiols proceeds very rapidly and the resultant products are stable. For the described analysis, optimum reaction conditions, such as concentration of the reducing agent, environment pH, and concentration of the reagent were carefully selected. The spectrophotometric assay was carried out measuring absorbance at λ = 348 nm (i.e., the spectral band of the obtained reaction product). Furthermore, the calibration curve of lipoic acid was registered. It was concluded that the Lambert-Beer law was observed within the range 1-10 μmol L(-1). Later, the reaction between LA and CMQT was used as precolumn derivatization in a chromatographic determination of the lipoic acid in the range 2.5-50 μmol L(-1). Practical applicability of the designed methods was evaluated by determining lipoic acid in Revitanerv pharmaceutical preparation which contains 300 mg LA in a single capsule. The error of the determination did not exceed 0.5% in relation to the declared value.

Analysis of Reaction between α-Lipoic Acid and 2-Chloro-1-methylquinolinium Tetrafluoroborate Used as a Precolumn Derivatization Technique in Chromatographic Determination of α-Lipoic Acid

PubMed Central

Godlewska, Magdalena; Odachowska, Angelika; Turkowicz, Monika; Karpinska, Joanna

2015-01-01

The present study offers results of analysis concerning the course of reaction between reduced α-lipoic acid (LA) and 2-chloro-1-methylquinolinium tetrafluoroborate (CMQT). In water environments, the reaction between CMQT and hydrophilic thiols proceeds very rapidly and the resultant products are stable. For the described analysis, optimum reaction conditions, such as concentration of the reducing agent, environment pH, and concentration of the reagent were carefully selected. The spectrophotometric assay was carried out measuring absorbance at λ = 348 nm (i.e., the spectral band of the obtained reaction product). Furthermore, the calibration curve of lipoic acid was registered. It was concluded that the Lambert-Beer law was observed within the range 1–10 μmol L−1. Later, the reaction between LA and CMQT was used as precolumn derivatization in a chromatographic determination of the lipoic acid in the range 2.5–50 μmol L−1. Practical applicability of the designed methods was evaluated by determining lipoic acid in Revitanerv pharmaceutical preparation which contains 300 mg LA in a single capsule. The error of the determination did not exceed 0.5% in relation to the declared value. PMID:26504616

Effect of Amine Modification on the Properties of Zirconium-Carboxylic Acid Based Materials and Their Applications as NO2 Adsorbents at Ambient Conditions

DTIC Science & Technology

2014-01-06

as a source of –SH [23]. Nitrogen dioxide (NO2) is an acidic , corrosive , and toxic gas present in the atmosphere. The main sources of NO2 pollution is...occurring are the Lewis acid –base reactions. These reactions are facilitated by the formation of nitric Schematic reaction between the urea incorporated in...of zirconium– carboxylic acid based materials and their applications as NO2 adsorbents at ambient conditions Zirconium–carboxylic ligand-based porous

PRODUCTION OF TRIFLUOROACETIC ACID COMPOUNDS

DOEpatents

Haworth, W.N.; Stacey, M.

1949-08-30

A process is described for the preparation of trifluoroacetic acid. Acetone vapor diluted wlth nitrogen and fluorine also diluted with nltrogen are fed separately at a temperature of about 210 deg C into a reaction vessel containing a catalyst mass selected from-the group consisting of silver and gold. The temperature in the reaction vessel is maintained in the range of 200 deg to 250 deg C. The reaction product, trifluoroacetyl fluoride, is absorbed in aqueous alkali solution. Trifluoroacetic acid is recovered from the solution by acidification wlth an acid such as sulfuric followed by steam distillation.

The reaction of formic acid with RaneyTM copper

NASA Astrophysics Data System (ADS)

Callear, Samantha K.; Silverwood, Ian P.; Chutia, Arunabhiram; Catlow, C. Richard A.; Parker, Stewart F.

2016-04-01

The interaction of formic acid with RaneyTM Cu proves to be complex. Rather than the expected generation of a monolayer of bidentate formate, we find the formation of a Cu(II) compound. This process occurs by direct reaction of copper and formic acid; in contrast, previous methods are by solution reaction. This is a rare example of formic acid acting as an oxidant rather than, as more commonly found, a reductant. The combination of diffraction, spectroscopic and computational methods has allowed this unexpected process to be characterized.

One-pot synthesis of β-acetamido ketones using boric acid at room temperature.

PubMed

Karimi-Jaberi, Zahed; Mohammadi, Korosh

2012-01-01

β-acetamido ketones were synthesized in excellent yields through one-pot condensation reaction of aldehydes, acetophenones, acetyl chloride, and acetonitrile in the presence of boric acid as a solid heterogeneous catalyst at room temperature. It is the first successful report of boric acid that has been used as solid acid catalyst for the preparation of β-acetamido ketones. The remarkable advantages offered by this method are green catalyst, mild reaction conditions, simple procedure, short reaction times, and good-to-excellent yields of products.

One-Pot Synthesis of β-Acetamido Ketones Using Boric Acid at Room Temperature

PubMed Central

Karimi-Jaberi, Zahed; Mohammadi, Korosh

2012-01-01

β-acetamido ketones were synthesized in excellent yields through one-pot condensation reaction of aldehydes, acetophenones, acetyl chloride, and acetonitrile in the presence of boric acid as a solid heterogeneous catalyst at room temperature. It is the first successful report of boric acid that has been used as solid acid catalyst for the preparation of β-acetamido ketones. The remarkable advantages offered by this method are green catalyst, mild reaction conditions, simple procedure, short reaction times, and good-to-excellent yields of products. PMID:22666168

Ambient cure polyimide foams. [thermal resistant foams

NASA Technical Reports Server (NTRS)

Sawko, P. M.; Riccitiello, S. R.; Hamermesh, C. L. (Inventor)

1978-01-01

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, (pyromellitic dianhydride) with an aromatic polyisocyanate, (polymethylene polyphenylisocyanate), in the presence of an inorganic acid and furfuryl alcohol. Usable acids include dilute sulfuric acid, dilute nitric acid, hydrochloric acid, polyphosphoric acid, and phosphoric acid, with the latter being preferred. The dianhydride and the isocyanate in about equimolar proportions constitute about 50% of the reaction mixture, the rest being made up with the acid and the alcohol in a ratio of about 1:10. An exothermic reaction between the acid and the alcohol provides the heat necessary for the other components to polymerize without recourse to external heat sources. The mixture can be sprayed on any surface to form polymeric foam in locations where the application of heat is not practical or possible, for instance, between walls or on mine tunnel surfaces.

Biotransformation of β-keto nitriles to chiral (S)-β-amino acids using nitrilase and ω-transaminase.

PubMed

Mathew, Sam; Nadarajan, Saravanan Prabhu; Sundaramoorthy, Uthayasuriya; Jeon, Hyunwoo; Chung, Taeowan; Yun, Hyungdon

2017-04-01

To enzymatically synthesize enantiomerically pure β-amino acids from β-keto nitriles using nitrilase and ω-transaminase. An enzyme cascade system was designed where in β-keto nitriles are initially hydrolyzed to β-keto acids using nitrilase from Bradyrhizobium japonicum and subsequently β-keto acids were converted to β-amino acids using ω-transaminases. Five different ω-transaminases were tested for this cascade reaction, To enhance the yields of β-amino acids, the concentrations of nitrilase and amino donor were optimized. Using this enzymatic reaction, enantiomerically pure (S)-β-amino acids (ee > 99%) were generated. As nitrilase is the bottleneck in this reaction, molecular docking analysis was carried out to depict the poor affinity of nitrilase towards β-keto acids. A novel enzymatic route to generate enantiomerically pure aromatic (S)-β-amino acids from β-keto nitriles is demonstrated for the first time.

System for chemically digesting low level radioactive, solid waste material

DOEpatents

Cowan, Richard G.; Blasewitz, Albert G.

1982-01-01

An improved method and system for chemically digesting low level radioactive, solid waste material having a high through-put. The solid waste material is added to an annular vessel (10) substantially filled with concentrated sulfuric acid. Concentrated nitric acid or nitrogen dioxide is added to the sulfuric acid within the annular vessel while the sulfuric acid is reacting with the solid waste. The solid waste is mixed within the sulfuric acid so that the solid waste is substantilly fully immersed during the reaction. The off gas from the reaction and the products slurry residue is removed from the vessel during the reaction.

Preparation and characterization Al3+-bentonite Turen Malang for esterification fatty acid (palmitic acid, oleic acid and linoleic acid)

NASA Astrophysics Data System (ADS)

Abdulloh, Abdulloh; Aminah, Nanik Siti; Triyono, Mudasir, Trisunaryanti, Wega

2016-03-01

Catalyst preparation and characterization of Al3+-bentonite for esterification of palmitic acid, oleic acid and linoleic acid has been done. Al3+-bentonite catalyst was prepared from natural bentonite of Turen Malang through cation exchange reaction using AlCl3 solution. The catalysts obtained were characterized by XRD, XRF, pyridine-FTIR and surface area analyser using the BET method. Catalyst activity test of Al3+-bentonite for esterification reaction was done at 65°C using molar ratio of metanol-fatty acid of 30:1 and 0.25 g of Al3+-bentonite catalyst for the period of ½, 1, 2, 3, 4 and 5 hours. Based on the characterization results, the Al3+-bentonite Turen Malang catalyst has a d-spacing of 15.63 Ǻ, acid sites of Brönsted and Lewis respectively of 230.79 µmol/g and 99.39 µmol/g, surface area of 507.3 m2/g and the average of radius pore of 20.09 Å. GC-MS analysis results of the oil phase after esterification reaction showed the formation of biodiesel (FAME: Fatty acid methyl ester), namely methyl palmitate, methyl oleate and methyl linoleate. The number of conversions resulted in esterification reaction using Al3+-bentonite Turen Malang catalyst was 74.61%, 37.75%, and 20, 93% for the esterification of palmitic acid, oleic acid and linoleic acid respectively.

Chemo-Enzymatic Synthesis of Each Enantiomer of Orthogonally-Protected 4,4-Difluoroglutamic Acid – A Candidate Monomer for Chiral Brønsted-Acid Peptide-Based Catalysts

PubMed Central

Li, Yang

2011-01-01

We have accomplished an asymmetric synthesis of each enantiomer of 4,4-difluoroglutamic acid. This α-amino acid has been of interest in medicinal chemistry circles. Key features of the synthesis include highly scalable procedures, a Reformatsky-based coupling reaction, and straightforward functional group manipulations to make the parent amino acid. Enantioenrichment derives from an enzymatic resolution of the synthetic material. Conversion of the optically enriched compounds to orthogonally protected forms allows selective formation of peptide bonds. 4,4- Difluoroglutamic acid, in a suitably protected form, is also shown to exhibit enhanced catalytic activity in both an oxidation reaction and a reduction reaction, in comparison to the analogous glutamic acid derivative. PMID:22039908

Liquid-phase oxidation of cyclohexanone over cerium oxide catalyst

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

Shen, H.C.; Weng, H.S.

Catalytic oxidation of cyclohexanone in the liquid phase with glacial acetic acid as the solvent over cerium oxide was studied between 5 and 15 atm and 98 and 118 {degrees} C in a batch reactor. The products were adipic acid, glutaric acid, succinic acid, caprolactone, carbon oxides, etc. The reaction undergoes a short induction period prior to a rapid reaction regime. In both regimes, the reaction is independent of oxygen pressure when the system pressure is above 10 atm. The induction period is inversely proportional to both of the catalyst weight and cyclohexanone concentration.During the rapid reaction regime, the reactionmore » rate was found to be proportional to the 0.5 power of the catalyst weight and to the 1.5 power of the cyclohexanone concentration. Reaction mechanisms and rate expressions are proposed. The carbon oxides produced in this study were much lower than those previously reported. The cerium oxide catalyst is stable during the reaction.« less

Effects of operational conditions on sludge degradation and organic acids formation in low-critical wet air oxidation.

PubMed

Chung, Jinwook; Lee, Mikyung; Ahn, Jaehwan; Bae, Wookeun; Lee, Yong-Woo; Shim, Hojae

2009-02-15

Wet air oxidation processes are to treat highly concentrated organic compounds including refractory materials, sludge, and night soil, and usually operated at supercritical water conditions of high temperature and pressure. In this study, the effects of operational conditions including temperature, pressure, and oxidant dose on sludge degradation and conversion into subsequent intermediates such as organic acids were investigated at low critical wet oxidation conditions. The reaction time and temperature in the wet air oxidation process was shown an important factor affecting the liquefaction of volatile solids, with more significant effect on the thermal hydrolysis reaction rather than the oxidation reaction. The degradation efficiency of sludge and the formation of organic acids were improved with longer reaction time and higher reaction temperature. For the sludge reduction and the organic acids formation under the wet air oxidation, the optimal conditions for reaction temperature, time, pressure, and oxidant dose were shown approximately 240 degrees C, 30min, 60atm, and 2.0L/min, respectively.

Kinetics on cocondensation between phenol and urea through formaldehyde II.

Treesearch

Yasunori Yoshida; Bunichiro Tomita; Chung-Yun Hse

1995-01-01

The chemical kinetics of the concurrent reactions of 2,4,6-trimethylolphenol with urea, where o- and p-methylol groups reacted simultaneously with urea, were analyzed on four kinds of catalysts: namely, sulfuric acid, hydrochloric acid, nitric acid, and oxalic acid. The results were summarized as follows: (1) assuming that each reaction follows the second-...

Temperature regulated Brønsted acidic ionic liquid-catalyze esterification of oleic acid for biodiesel application

NASA Astrophysics Data System (ADS)

Rafiee, Ezzat; Mirnezami, Fakhrosadat

2017-02-01

By combining phosphotungstic acid (PW) and SO3H- functioned zwitterion, heteropoly anion-based Brønsted acidic ionic liquids (HPA-ILs) were successfully obtained. Scanning electron microscopy and energy dispersive X-ray spectroscopy were provided the morphology and composition of the prepared material. Catalytic performance and reusability of the catalysts were evaluated through an esterification reaction between oleic acid and methanol for production of biodiesel. Relationship between catalytic activities and acidity of the catalysts have been discussed by potentiometric titration. The results showed that HPA-ILs had good activity and reusability. HPA-ILs dissolved in the reaction mixture during the reaction process and could be precipitated and separated from products at lower temperature.

Theoretical study on keto-enol tautomerisation of glutarimide for exploration of the isomerisation reaction pathway of glutamic acid in proteins using density functional theory

NASA Astrophysics Data System (ADS)

Fukuyoshi, Shuichi; Nakayoshi, Tomoki; Takahashi, Ohgi; Oda, Akifumi

2017-03-01

In order to elucidate the reason why glutamic acid residues have lesser racemisation reactivity than asparaginic acid, we investigated the racemisation energy barrier of piperidinedione, which is the presumed intermediate of the isomerisation reaction of L-Glu to D-Glu, by density functional theory calculations. In two-water-molecule-assisted racemisation, the activation barrier for keto-enol isomerisation was 28.1 kcal/mol. The result showed that the activation barrier for the racemisation of glutamic acid residues was not different from that for the racemisation of aspartic acid residues. Thus, glutamic acid residues can possibly cause the racemisation reaction if the cyclic intermediate stably exists.

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system a review

NASA Astrophysics Data System (ADS)

Zahardis, J.; Petrucci, G. A.

2006-11-01

The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the primary products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. Anomalies in the relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide polymers. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei. The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, a series of atmospheric implications of oxidative processing of particulate containing fatty acids is presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semisolids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation. Other effects, including the potential role of aldehydic products of ozonolysis in increasing the oxidative capacity of the troposphere, are also discussed.

Degradation pathway of the naphthalene azo dye intermediate 1-diazo-2- naphthol-4-sulfonic acid using Fenton's reagent.

PubMed

Zhu, Nanwen; Gu, Lin; Yuan, Haiping; Lou, Ziyang; Wang, Liang; Zhang, Xin

2012-08-01

Degradation of naphthalene dye intermediate 1-diazo-2- naphthol-4-sulfonic acid (1,2,4-Acid) by Fenton process has been studied in depth for the purpose of learning more about the reactions involved in the oxidation of 1,2,4-Acid. During 1,2,4-Acid oxidation, the solution color initially takes on a dark red, then to dark black associated with the formation of quinodial-type structures, and then goes to dark brown and gradually disappears, indicating a fast degradation of azo group. The observed color changes of the solution are a result of main reaction intermediates, which can be an indicator of the level of oxidization reached. Nevertheless, complete TOC removal is not accomplished, in accordance with the presence of resistant carboxylic acids at the end of the reaction. The intermediates generated along the reaction time have been identified and quantified. UPLC-(ESI)-TOF-HRMS analysis allows the detection of 19 aromatic compounds of different size and complexity. Some of them share the same accurate mass but appear at different retention time, evidencing their different molecular structures. Heteroatom oxidation products like SO(4)(2-) have also been quantified and explanations of their release are proposed. Short-chain carboxylic acids are detected at long reaction time, as a previous step to complete the process of dye mineralization. Finally, considering all the findings of the present study and previous related works, the evolution from the original 1,2,4-Acid to the final products is proposed in a general reaction scheme. Copyright © 2012 Elsevier Ltd. All rights reserved.

Reaction of N-acetylneuraminic acid derivatives with perfluorinated anhydrides: a short access to N-perfluoracylated glycals with antiviral properties.

PubMed

Rota, Paola; Allevi, Pietro; Mattina, Roberto; Anastasia, Mario

2010-08-21

An efficient short protocol for the preparation of N-perfluoroacylated glycals of neuraminic acid, by simple short treatment of differently protected N-acetylneuraminic acid with perfluorinated anhydrides in acetonitrile at 135 degrees C, is reported, together with a rationalitazion of the reaction that allows the alternative formation of N-perfluoroacylated 1,7-lactones to be previewed under the same reaction conditions.

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid.

PubMed

Aw, Alex; Fritz, Marshall; Napoline, Jonathan W; Pollet, Pamela; Liotta, Charles L

2017-11-15

Continuous flow technology has been identified as instrumental for its environmental and economic advantages leveraging superior mixing, heat transfer and cost savings through the "scaling out" strategy as opposed to the traditional "scaling up". Herein, we report the reaction of diphenyldiazomethane with p-nitrobenzoic acid in both batch and flow modes. To effectively transfer the reaction from batch to flow mode, it is essential to first conduct the reaction in batch. As a consequence, the reaction of diphenyldiazomethane was first studied in batch as a function of temperature, reaction time, and concentration to obtain kinetic information and process parameters. The glass flow reactor set-up is described and combines two types of reaction modules with "mixing" and "linear" microstructures. Finally, the reaction of diphenyldiazomethane with p-nitrobenzoic acid was successfully conducted in the flow reactor, with up to 95% conversion of the diphenyldiazomethane in 11 min. This proof of concept reaction aims to provide insight for scientists to consider flow technology's competitiveness, sustainability, and versatility in their research.

Degradation of folic acid wastewater by electro-Fenton with three-dimensional electrode and its kinetic study

PubMed Central

Xiaochao, Gu; Jin, Tian; Xiaoyun, Li; Bin, Zhou; Xujing, Zheng; Jin, Xu

2018-01-01

The three-dimensional electro-Fenton method was used in the folic acid wastewater pretreatment process. In this study, we researched the degradation of folic acid and the effects of different parameters such as the air sparging rate, current density, pH and reaction time on chemical oxygen demand (COD) removal in folic acid wastewater. A four-level and four-factor orthogonal test was designed and optimal reaction conditions to pretreat folic acid wastewater by three-dimensional electrode were determined: air sparge rate 0.75 l min−1, current density 10.26 mA cm−2, pH 5 and reaction time 90 min. Under these conditions, the removal of COD reached 94.87%. LC-MS results showed that the electro-Fenton method led to an initial folic acid decomposition into p-aminobenzoyl-glutamic acid (PGA) and xanthopterin (XA); then part of the XA was oxidized to pterine-6-carboxylic acid (PCA) and the remaining part of XA was converted to pterin and carbon dioxide. The kinetics analysis of the folic acid degradation process during pretreatment was carried out by using simulated folic acid wastewater, and it could be proved that the degradation of folic acid by using the three-dimensional electro-Fenton method was a second-order reaction process. This study provided a reference for industrial folic acid treatment. PMID:29410807

The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery

NASA Astrophysics Data System (ADS)

Nicholson, John W.; Wilson, Alan

2004-09-01

This article describes the history of the reaction converting carboxylic acids to ketones. The reaction has been rediscovered several times, yet has actually been known for centuries. The best known version of the process is the Dakin West reaction (1928), which applies to α-amino acids and also involves the simultaneous conversion of the amine group to amido functionality. Unlike other examples, this particular reaction has attracted a reasonable amount of attention and it appears to be better known than the conversion of simple carboxylic acids to ketones. However, this reaction was described as long ago as 1612, when Beguin published an account of it in his book, Tyrocinium Chymicum . Since then, many chemists have rediscovered the reaction, apparently independently. One of the earliest modern accounts was by W. H. Perkin, Sr., in 1886, who made various simple ketones by refluxing the appropriate carboxylic acids with base. However, this work has been largely ignored, including by his son, W. H. Perkin, Jr., who used a more complicated base-catalyzed ketonization to prepare small ring compounds in the early years of the 20th century. Other articles detailing the application of ketonization to organic acids are discussed, including our own work, which employed the process to crosslink carboxylated polymers for possible technical application in coatings. Despite its relative obscurity, the reaction was used by Woodward et al. in the total synthesis of strychnine, reported in 1963, and this is discussed in detail at the end of the article. See Featured Molecules .

Effects of medium-chain triacylglycerols on Maillard reaction in bread baking.

PubMed

Toyosaki, Toshiyuki

2018-06-01

To investigate the relationship between the fatty acid composition of medium-chain triacylglycerols (MCTs) and the Maillard reaction induced during bread baking, a comparison with various fatty acids was conducted. Saturated fatty acids had a remarkable inhibitory effect on the amount of advanced glycation end products (AGEs) generated from the Maillard reaction in bread baking compared to unsaturated fatty acids. The amount of AGEs produced by each fatty acid (mg kg -1 ) was as follows: C18:0, 18.7; C12:0, 35.2; C16:0, 21.4; C18:0, 38.2; C18:1, 68.7; C18:2, 80.1; C20:4, 80.8; C22:4, 89.8. Saturated fatty acids were possibly involved in the Maillard reaction and, as a result, acted to inhibit it. In the case of unsaturated fatty acids, amounts of AGEs during the Maillard reaction in baking tended to increase as the degree of unsaturation increased. In other words, there was a positive correlation between the degree of unsaturation and the amount of AGEs. It was also confirmed that the air pore distribution in baked bread was closely related to AGEs. These results led us to conclude that the fatty acid composition of the added lipids also influences properties that determine the tastiness of bread. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Covalent binding of aniline to humic substances. 1. Kinetic studies

USGS Publications Warehouse

Weber, E.J.; Spidle, D.L.; Thorn, K.A.

1996-01-01

The reaction kinetics for the covalent binding of aniline with reconstituted IHSS humic and fulvic acids, unfractionated DOM isolated from Suwannee River water, and whole samples of Suwannee River water have been investigated. The reaction kinetics in each of these systems can be adequately described by a simple second-order rate expression. The effect of varying the initial concentration of aniline on reaction kinetics suggested that approximately 10% of the covalent binding sites associated with Suwannee River fulvic acid are highly reactive sites that are quickly saturated. Based on the kinetic parameters determined for the binding of aniline with the Suwannee River fulvic and humic acid isolates, it was estimated that 50% of the aniline concentration decrease in a Suwannee River water sample could be attributed to reaction with the fulvic and humic acid components of the whole water sample. Studies with Suwannee River fulvic acid demonstrated that the rate of binding decreased with decreasing pH, which parallels the decrease in the effective concentration of the neutral form, or reactive nucleophilic species of aniline. The covalent binding of aniline with Suwannee River fulvic acid was inhibited by prior treatment of the fulvic acid with hydrogen sulfide, sodium borohydride, or hydroxylamine. These observations are consistent with a reaction pathway involving nucleophilic addition of aniline to carbonyl moieties present in the fulvic acid.

Acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with alcohols.

PubMed

Tait, Katrina; Horvath, Alysia; Blanchard, Nicolas; Tam, William

2017-01-01

The acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicylic alkene using alcohol nucleophiles were investigated. Although this acid-catalyzed ring-opening reaction did not cleave the cyclopropane unit as planned, this represent the first examples of ring-openings of cyclopropanated 3-aza-2-oxabicyclo[2.2.1]alkenes that lead to the cleavage of the C-O bond instead of the N-O bond. Different acid catalysts were tested and it was found that pyridinium toluenesulfonate in methanol gave the best yields in the ring-opening reactions. The scope of the reaction was successfully expanded to include primary, secondary, and tertiary alcohol nucleophiles. Through X-ray crystallography, the stereochemistry of the product was determined which confirmed an S N 2-like mechanism to form the ring-opened product.

Characterization of the products formed by the reaction of trichlorocyanuric acid with 2-propanol.

PubMed

Sandercock, P Mark L; Barnett, Julie S

2009-11-01

We report a recent investigation into the death of a cat that was initially thought to involve intentionally burning the animal via the use of an ignitable liquid. The exposure of the animal to flame was ruled out. Instead, forensic investigation revealed the intentional mixing together of a common outdoor swimming pool chlorinator, trichlorocyanuric acid (TCCA), and 2-propanol (aka, isopropyl alcohol or rubbing alcohol). The reaction of these two chemicals resulted in the formation of cyanuric acid residue, hydrochloric acid, and the evolution of a significant volume of chlorine gas. Further alpha-chlorination side reactions also occurred between 2-propanol and TCCA to produce a variety of chlorinated 2-propanone species that were detected on the submitted evidence. The identification of the products of both the main reaction and the side reactions allowed the authors to determine what chemicals were originally mixed together by the culprit.

Reactivity of amino acid anions with nitrogen and oxygen atoms.

PubMed

Wang, Zhe-Chen; Li, Ya-Ke; He, Sheng-Gui; Bierbaum, Veronica M

2018-02-14

For many decades, astronomers have searched for biological molecules, including amino acids, in the interstellar medium; this endeavor is important for investigating the hypothesis of the origin of life from space. The space environment is complex and atomic species, such as nitrogen and oxygen atoms, are widely distributed. In this work, the reactions of eight typical deprotonated amino acids (glycine, alanine, cysteine, proline, aspartic acid, histidine, tyrosine, and tryptophan) with ground state nitrogen and oxygen atoms are studied by experiment and theory. These amino acid anions do not react with nitrogen atoms. However, the reactions of these ions with oxygen atoms show an intriguing variety of ionic products and the reaction rate constants are of the order of 10 -10 cm 3 s -1 . Density functional calculations provide detailed mechanisms of the reactions, and demonstrate that spin conversion is essential for some processes. Our study provides important data and insights for understanding the kinetic and dynamic behavior of amino acids in space environments.

Amino Acid Degradations Produced by Lipid Oxidation Products.

PubMed

Hidalgo, Francisco J; Zamora, Rosario

2016-06-10

Differently to amino acid degradations produced by carbohydrate-derived reactive carbonyls, amino acid degradations produced by lipid oxidation products are lesser known in spite of being lipid oxidation a major source of reactive carbonyls in food. This article analyzes the conversion of amino acids into Strecker aldehydes, α-keto acids, and amines produced by lipid-derived free radicals and carbonyl compounds, as well as the role of lipid oxidation products on the reactions suffered by these compounds: the formation of Strecker aldehydes and other aldehydes from α-keto acids; the formation of Strecker aldehydes and olefins from amines; the formation of shorter aldehydes from Strecker aldehydes; and the addition reactions suffered by the olefins produced from the amines. The relationships among all these reactions and the effect of reaction conditions on them are discussed. This knowledge should contribute to better control food processing in order to favor the formation of desirable beneficial compounds and to inhibit the production of compounds with deleterious properties.

Efficient synthesis of anacardic acid analogues and their antibacterial activities.

PubMed

Mamidyala, Sreeman K; Ramu, Soumya; Huang, Johnny X; Robertson, Avril A B; Cooper, Matthew A

2013-03-15

Anacardic acid derivatives exhibit a broad range of biological activities. In this report, an efficient method for the synthesis of anacardic acid derivatives was explored, and a small set of salicylic acid variants synthesised retaining a constant hydrophobic element (a naphthyl tail). The naphthyl side chain was introduced via Wittig reaction and the aldehyde installed using directed ortho-metalation reaction of the substituted o-anisic acids. The failure of ortho-metalation using unprotected carboxylic acid group compelled us to use directed ortho-metalation in which a tertiary amide was used as a strong ortho-directing group. In the initial route, tertiary amide cleavage during final step was challenging, but cleaving the tertiary amide before Wittig reaction was beneficial. The Wittig reaction with protected carboxylic group (methyl ester) resulted in side-products whereas using sodium salt resulted in higher yields. The novel compounds were screened for antibacterial activity and cytotoxicity. Although substitution on the salicylic head group enhanced antibacterial activities they also enhanced cytotoxicity. Copyright © 2013 Elsevier Ltd. All rights reserved.

Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

PubMed

Fawzy, Ahmed

2016-03-15

The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biotransformation of caffeoyl quinic acids from green coffee extracts by Lactobacillus johnsonii NCC 533.

PubMed

Bel-Rhlid, Rachid; Thapa, Dinesh; Kraehenbuehl, Karin; Hansen, Carl Erik; Fischer, Lutz

2013-01-01

The potential of Lactobacillus johnsonii NCC 533 to metabolize chlorogenic acids from green coffee extract was investigated. Two enzymes, an esterase and a hydroxycinnamate decarboxylase (HCD), were involved in this biotransformation. The complete hydrolysis of 5-caffeoylquinic acid (5-CQA) into caffeic acid (CA) by L. johnsonii esterase occurred during the first 16 h of reaction time. No dihydrocaffeic acid was identified in the reaction mixture. The decarboxylation of CA into 4-vinylcatechol (4-VC) started only when the maximum concentration of CA was reached (10 μmol/ml). CA was completely transformed into 4-VC after 48 h of incubation. No 4-vinylphenol or other derivatives could be identified in the reaction media. In this study we demonstrate the capability of L. johnsonii to transform chlorogenic acids from green coffee extract into 4-VC in two steps one pot reaction. Thus, the enzymatic potential of certain lactobacilli might be explored to generate flavor compounds from plant polyphenols.

Sour Science.

ERIC Educational Resources Information Center

Whetzel, Joan

1999-01-01

Presents four activities that involve chemical reactions with vinegar, lemon juice, or orange juice. These activities can be used to teach about acid-base reactions and acids as chemical catalysts. (WRM)

Catalytical Conversion of Carbohydrates into Lactic Acid via Hydrothermal Reaction

NASA Astrophysics Data System (ADS)

Wei, Zhen; Jin, Fangming; Zhang, Guangyi; Zhang, Shiping; Yao, Guodong

2010-11-01

This paper focuses on catalytical conversion of carbohydrates into lactic acid, under the hydrothermal conditions, which may have a promising future for its high speediness and effectiveness. The catalysis of ZnO was investigated to improve the lactic acid yields. The results showed that the lactic acid yields increased immensely by the addition of ZnO. The effects of the reaction time and the addition amount of ZnO on the conversion of carbohydrates to lactic acid were studied. The highest lactic acid yields reached up to 28% starting from glucose after the reaction time of 60 s under the conditions of 0.2 mmol ZnO, 300° C, the filling rate of 35%, and over 30% starting from fructose at the same temperature and filling rate when the reaction time of 40 s and 2.0 mmol ZnO were employed. The collaborative effects of ZnO and NaOH used as the catalysts together at the same time were also studied. Furthermore, the catalytic mechanism of ZnO in the hydrothermal conversion of carbohydrates into lactic acid was discussed.

Phospholipase a properties of several snake venom preparations.

PubMed

Nutter, L J; Privett, O S

1966-07-01

The hydrolytic properties of the venoms of seven species of snakes,Crotalus adamanteus, Ancistrodon contortrix, Naja naja, Bothrops atrox, Ophiophagus hannah, Crotalus atrox andVipera russeli, were studied with purified lecithins and mixtures of lecithins of known fatty acid and class composition as substrates.The relative rates of hydrolysis of the fatty acids by the above venoms were studied by analysis of the products of the reaction at intervals during the course of the reaction. Of the seven venoms studied, that ofOphiophagus hannah was the only one which did not give some degree of preferential rate of hydrolysis of individual fatty acids.In general, saturated fatty acids were liberated faster than unsaturated fatty acids; differences in the rates of the hydrolysis of individual saturate and unsaturated fatty acids were also observed. Individual classes of lecithin were also hydrolyzed at different rates. For the determination of the distribution of the fatty acids between the alpha- and beta-position of lecithin, the reaction should be carried to completion. If the reaction requires a prolonged time to go to completion, it should be carried out under nitrogen to prevent autoxidation.

Investigation and kinetic evaluation of the reactions of hydroxymethylfurfural with amino and thiol groups of amino acids.

PubMed

Hamzalıoğlu, Aytül; Gökmen, Vural

2018-02-01

In this study, reactions of hydroxymethylfurfural (HMF) with selected amino acids (arginine, cysteine and lysine) were investigated in HMF-amino acid (high moisture) and Coffee-amino acid (low moisture) model systems at 5, 25 and 50°C. The results revealed that HMF reacted efficiently and effectively with amino acids in both high and low moisture model systems. High-resolution mass spectrometry (HRMS) analyses of the reaction mixtures confirmed the formations of Michael adduct and Schiff base of HMF with amino acids. Calculated pseudo-first order reaction rate constants were in the following order; k Cysteine >k Arginine >k Lysine for high moisture model systems. Comparing to these rate constants, the k Cysteine decreased whereas, k Arginine and k Lysine increased under the low moisture conditions of Coffee-amino acid model systems. The temperature dependence of the rate constants was found to obey the Arrhenius law in a temperature range of 5-50°C under both low and high moisture conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetics of browning and correlations between browning degree and pyrazine compounds in l-ascorbic acid/acidic amino acid model systems.

PubMed

Yu, Ai-Nong; Zhou, Yong-Yan; Yang, Yi-Ni

2017-04-15

The kinetics of browning and the correlation between browning products (BPs) and pyrazine compounds were investigated by heating equimolar l-ascorbic acid (ASA)/acidic amino acids under weak alkaline conditions at 120-150°C for 10-120min. The formations of BPs and pyrazine compounds from the reaction were monitored by UV-vis and SPME-GC-FID, respectively. The formation of BPs in both ASA/l-glutamic acid and ASA/l-aspartic acid model reaction systems followed zero order reaction kinetics with activation energies (E a ) of 90.13 and 93.38kJ/mol, respectively. ASA/l-aspartic acid browned at a slightly higher rate than ASA/l-glutamic acid. The total concentration of pyrazine compounds was highly and positively correlated with that of BPs. Based on the observed kinetic data, the formation mechanisms of BPs and pyrazine compounds were proposed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Furfural production using ionic liquids: A review.

PubMed

Peleteiro, Susana; Rivas, Sandra; Alonso, José Luis; Santos, Valentín; Parajó, Juan Carlos

2016-02-01

Furfural, a platform chemical with a bright future, is commercially obtained by acidic processing of xylan-containing biomass in aqueous media. Ionic liquids (ILs) can be employed in processed for furfural manufacture as additives, as catalysts and/or as reaction media. Depending on the IL utilized, externally added catalysts (usually, Lewis acids, Brönsted acids and/or solid acid catalysts) can be necessary to achieve high reaction yields. Oppositely, acidic ionic liquids (AILs) can perform as both solvents and catalysts, enabling the direct conversion of suitable substrates (pentoses, pentosans or xylan-containing biomass) into furfural. Operating in IL-containing media, the furfural yields can be improved when the product is continuously removed along the reaction (for example, by stripping or extraction), to avoid unwanted side-reactions leading to furfural consumption. These topics are reviewed, as well as the major challenges involved in the large scale utilization of ILs for furfural production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Kinetics of gas phase formic acid decomposition on platinum single crystal and polycrystalline surfaces

NASA Astrophysics Data System (ADS)

Detwiler, Michael D.; Milligan, Cory A.; Zemlyanov, Dmitry Y.; Delgass, W. Nicholas; Ribeiro, Fabio H.

2016-06-01

Formic acid dehydrogenation turnover rates (TORs) were measured on Pt(111), Pt(100), and polycrystalline Pt foil surfaces at a total pressure of 800 Torr between 413 and 513 K in a batch reactor connected to an ultra-high vacuum (UHV) system. The TORs, apparent activation energies, and reaction orders are not sensitive to the structure of the Pt surface, within the precision of the measurements. CO introduced into the batch reactor depressed the formic acid dehydrogenation TOR and increased the reaction's apparent activation energies on Pt(111) and Pt(100), consistent with behavior predicted by the Temkin equation. Two reaction mechanisms were explored which explain the formic acid decomposition mechanism on Pt, both of which include dissociative adsorption of formic acid, rate limiting formate decomposition, and quasi-equilibrated hydrogen recombination and CO adsorption. No evidence was found that catalytic supports used in previous studies altered the reaction kinetics or mechanism.

Rapid hybridization of nucleic acids using isotachophoresis

PubMed Central

Bercovici, Moran; Han, Crystal M.; Liao, Joseph C.; Santiago, Juan G.

2012-01-01

We use isotachophoresis (ITP) to control and increase the rate of nucleic acid hybridization reactions in free solution. We present a new physical model, validation experiments, and demonstrations of this assay. We studied the coupled physicochemical processes of preconcentration, mixing, and chemical reaction kinetics under ITP. Our experimentally validated model enables a closed form solution for ITP-aided reaction kinetics, and reveals a new characteristic time scale which correctly predicts order 10,000-fold speed-up of chemical reaction rate for order 100 pM reactants, and greater enhancement at lower concentrations. At 500 pM concentration, we measured a reaction time which is 14,000-fold lower than that predicted for standard second-order hybridization. The model and method are generally applicable to acceleration of reactions involving nucleic acids, and may be applicable to a wide range of reactions involving ionic reactants. PMID:22733732

Ultrafast photodimerization dynamics in α-cyano-4-hydroxycinnamic and sinapinic acid crystals

NASA Astrophysics Data System (ADS)

Hoyer, Theo; Tuszynski, Wilfried; Lienau, Christoph

2007-07-01

We report a sub-picosecond time-resolved fluorescence spectroscopic study of different cinnamic acid crystals, model systems for solid-state photodimerization reactions. For α-cyano-4-hydroxycinnamic acid (α-CHC), we identify the emission spectra of both monomers and dimers, allowing us to directly probe the photoinduced dynamics of both species. The dimerization occurs on a timescale of 10 ps and results in a long-lived dimer product, stable for hours. For sinapinic acid, we find an extremely fast, sub-picosecond dimerization reaction and a short-lived dimer. This first sub-picosecond time-resolved dimerization study in cinnamic acid crystals provides a new basis for relating their structural properties and microscopic reaction dynamics.

The photodimerisation of the α- and β-forms of trans-cinnamic acid: a study of single crystals by vibrational microspectroscopy

NASA Astrophysics Data System (ADS)

Atkinson, Samantha D. M.; Almond, Matthew J.; Hollins, Peter; Jenkins, Samantha L.

2003-02-01

Infrared and Raman microspectroscopy have been used to follow the photodimerisation reactions of single crystals, the α- and β-forms of trans-cinnamic acid. This approach allows the starting materials and products—α-truxillic acid that has Ci symmetry and β-truxinic acid, which has Cs symmetry—to be identified. It also allows the topotactic nature of the reaction to be confirmed. Attempts to produce the poorly-defined unreactive γ-form of trans-cinnamic acid resulted only in a mixture of the α- and β-forms. The findings suggest a wide role for these spectroscopic methods in monitoring solid-state organic reactions.

[Studies on the oxidation reaction of octanol-2 with nitric acid by infrared spectroscopy].

PubMed

Zhang, G; Zhao, G; Wang, Y; Zhang, Q; Zhang, S; Lu, F

1998-04-01

In this paper, the reaction process of oxidation of octanol-2 with nitric acid has been studied by IR spectroscopy. It is found that the main components of non-sapoifiable matter are different in different oxidation degrees. The relation between oxidation products and the amount of nitric acid are investigated,the reaction mechanism has also been studied. Experimental results show that the oxidation process of octanol-2 is as follows: first, octanol-2 is oxidated to octanone-2, or to nitrate, nitrite and nitrile copmpounds, then these compounds are reoxidated to caproic acid in the meantime some by-products, such as valeric, enanthic acids are also found in oxidated products.

Cross ketonization of Cuphea sp. oil with acetic acid over a composite oxide of Fe, Ce, and Al

USDA-ARS?s Scientific Manuscript database

The objective of this work was to demonstrate the viability of the cross ketonization reaction with the triacylglycerol from Cuphea sp. and acetic acid in a fixed-bed plug-flow reactor. The seed oil from Cuphea sp. contains up to 71% decanoic acid and the reaction of this fatty acid residue with ac...

Hydrolysis kinetics of secoisolariciresinol diglucoside oligomers from flaxseed.

PubMed

Yuan, Jian-Ping; Li, Xin; Xu, Shi-Ping; Wang, Jiang-Hai; Liu, Xin

2008-11-12

Flaxseed is the richest dietary source of the lignan secoisolariciresinol diglucoside (SDG) and contains the largest amount of SDG oligomers, which are often hydrolyzed to break the ester linkages for the release of SDG and the glycosidic bonds for the release of secoisolariciresinol (SECO). The alkaline hydrolysis reaction kinetics of SDG oligomers from flaxseed and the acid hydrolysis process of SDG and other glucosides were investigated. For the kinetic modeling, a pseudo-first-order reaction was assumed. The results showed that the alkaline hydrolysis of SDG oligomers followed first-order reaction kinetics under mild alkaline hydrolytic conditions and that the concentration of sodium hydroxide had a strong influence on the activation energy of the alkaline hydrolysis of SDG oligomers. The results also indicated that the main acid hydrolysates of SDG included secoisolariciresinol monoglucoside (SMG), SECO, and anhydrosecoisolariciresinol (anhydro-SECO) and that the extent and the main hydrolysates of the acid hydrolysis reaction depended on the acid concentration, hydrolysis temperature, and time. In addition, the production and change of p-coumaric acid glucoside, ferulic acid glucoside and their methyl esters and p-coumaric acid, ferulic acid, and their methyl esters during the process of hydrolysis was also investigated.

CHROMATOGRAPHIC SEPARATION AND IDENTIFICATION OF PRODUCTS FROM THE REACTION OF DIMETHYLARSINIC ACID WITH HYDROGEN SULFIDE

EPA Science Inventory

The reaction of dimethylarsinic acid (DMAV) with hydrogen sulfide (H2S) is of biological significance and may be implicated in the overall toxicity and carcinogenicity of arsenic. The course of the reaction in aqueous phase was monitored and an initial product, dimethylthioarsin...

Comparing Amide-Forming Reactions Using Green Chemistry Metrics in an Undergraduate Organic Laboratory

ERIC Educational Resources Information Center

Fennie, Michael W.; Roth, Jessica M.

2016-01-01

In this laboratory experiment, upper-division undergraduate chemistry and biochemistry majors investigate amide-bond-forming reactions from a green chemistry perspective. Using hydrocinnamic acid and benzylamine as reactants, students perform three types of amide-forming reactions: an acid chloride derivative route; a coupling reagent promoted…

Synthesis of pyroglutamic acid derivatives via double michael reactions of alkynones.

PubMed

Scansetti, Myriam; Hu, Xiangping; McDermott, Benjamin P; Lam, Hon Wai

2007-05-24

In the presence of substoichiometric quantities of potassium tert-butoxide and an additional metal salt, amide-tethered diacids undergo double Michael reactions with alkynones to provide highly functionalized pyroglutamic acid derivatives. The metal salt was found to play an important role in improving the diastereoselectivities of the reactions.

INVESTIGATION OF ARSINE-GENERATING REACTIONS USING DEUTERIUM-LABELED REAGENTS AND MASS SPECTROMETRY

EPA Science Inventory

Mass spectrometry was used to detect transfer of deuterium from labeled reagents to arsines following hydride-generation reactions. The arsine gases liberated from the reactions of arsenite, arsenate, methylarsonic acid, and dimethylarsinic acid with HC1 and NaBD4 in H2O, or with...

21 CFR 184.1505 - Mono- and diglycerides.

Code of Federal Regulations, 2010 CFR

2010-04-01

... fatty acids include lauric, linoleic, myristic, oleic, palmitic, and stearic. Mono- and diglycerides are manufactured by the reaction of glycerin with fatty acids or the reaction of glycerin with triglycerides in the... fatty acids, and free glycerin that contains at least 90 percent-by-weight glycerides. (b) The...

40 CFR 721.1645 - Benzenesulfonic acid, 4-methyl-, reaction products with oxirane mono[(C10-16-alkyloxy)methyl...

Code of Federal Regulations, 2011 CFR

2011-07-01

...-, reaction products with oxirane mono[(C10-16-alkyloxy)methyl] derivatives and 2,2,4(or 2,4,4)-trimethyl-1,6... Specific Chemical Substances § 721.1645 Benzenesulfonic acid, 4-methyl-, reaction products with oxirane...-methyl-, reaction products with oxirane mono[(C10-16-alkyloxy)methyl] derivatives and 2,2,4(or 2,4,4...

40 CFR 721.1645 - Benzenesulfonic acid, 4-methyl-, reaction products with oxirane mono[(C10-16-alkyloxy)methyl...

Code of Federal Regulations, 2010 CFR

2010-07-01

...-, reaction products with oxirane mono[(C10-16-alkyloxy)methyl] derivatives and 2,2,4(or 2,4,4)-trimethyl-1,6... Specific Chemical Substances § 721.1645 Benzenesulfonic acid, 4-methyl-, reaction products with oxirane...-methyl-, reaction products with oxirane mono[(C10-16-alkyloxy)methyl] derivatives and 2,2,4(or 2,4,4...

Synthesis of 5,5-Diphenyl-4-penten-2-One: A Variation on a Classic Organic Synthesis Laboratory

ERIC Educational Resources Information Center

Alber, Joshua P.; DeGrand, Michael J.; Cermak, Diana M.

2011-01-01

The Grignard reaction and the addition of protecting groups are standard reactions in an organic chemistry course. Organic students learn about the "quench" step of the Grignard reaction using acid and water and the acid-catalyzed hydrolysis to remove the protecting group, yet in the lecture students find these two reactions to be confusing in…

A stimuli-responsive fluorescence platform for simultaneous determination of D-isoascorbic acid and Tartaric acid based on Maillard reaction product

NASA Astrophysics Data System (ADS)

Zhao, Yanmei; Yuan, Haiyan; Zhang, Xinling; Yang, Jidong

2018-05-01

An activatable fluorescence monitoring platform based on a novel Maillard reaction product from D-glucose and L-arginine was prepared through a facile one-pot approach and applied for simultaneous detection of D-isoascorbic acid and tartaric acid. In this work, the new Maillard reaction product GLA was first obtained, and its fluorescence intensity can be effectively quenched by KMnO4, resulting from a new complex (GLA-KMnO4) formation between GLA and KMnO4. Upon addition of D-isoascorbic acid or tartaric acid, an enhanced fluorescence was observed under the optimumed experimental conditions, indicating a stimuli-responsive fluorescence turn on platform for D-isoascorbic acid or tartaric acid can be developed. The corresponding experimental results showed that this turn on fluorescence sensing platform has a high sensitivity for D-isoascorbic acid or tartaric acid, because the detection limits were 5.9 μM and 21.5 μM, respectively. Additionally, this proposed sensing platform was applied to simultaneously detection of D-isoascorbic acid and tartaric acid in real tap water samples with satisfactory results.

Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

PubMed

Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng

2014-08-01

The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable. Copyright © 2014. Published by Elsevier B.V.

Electrocatalysis of fuel cell reactions: Investigation of alternate electrolytes

NASA Technical Reports Server (NTRS)

Chin, D. T.; Hsueh, K. L.; Chang, H. H.

1983-01-01

Oxygen reduction and transport properties of the electrolyte in the phosphoric acid fuel cell are studied. A theoretical expression for the rotating ring-disk electrode technique; the intermediate reaction rate constants for oxygen reduction on platinum in phosphoric acid electrolyte; oxygen reduction mechanism in trifluoromethanesulfonic acid (TFMSA), considered as an alternate electrolyte for the acid fuel cells; and transport properties of the phosphoric acid electrolyte at high concentrations and temperatures are covered.

Mechanism of ascorbic acid interference in biochemical tests that use peroxide and peroxidase to generate chromophore.

PubMed

Martinello, Flávia; Luiz da Silva, Edson

2006-11-01

Ascorbic acid interferes negatively in peroxidase-based tests (Trinder method). However, the precise mechanism remains unclear for tests that use peroxide, a phenolic compound and 4-aminophenazone (4-AP). We determined the chemical mechanism of this interference, by examining the effects of ascorbic acid in the reaction kinetics of the production and reduction of the oxidized chromophore in urate, cholesterol, triglyceride and glucose tests. Reaction of ascorbic acid with the Trinder method constituents was also verified. Ascorbic acid interfered stoichiometrically with all tests studied. However, it had two distinct effects on the reaction rate. In the urate test, ascorbic acid decreased the chromophore formation with no change in its production kinetics. In contrast, in cholesterol, triglyceride and glucose tests, an increase in the lag phase of color development occurred. Of all the Trinder constituents, only peroxide reverted the interference. In addition, ascorbic acid did not interfere with oxidase activity nor reduce significantly the chromophore formed. Peroxide depletion was the predominant chemical mechanism of ascorbic acid interference in the Trinder method with phenolics and 4-AP. Distinctive effects of ascorbic acid on the reaction kinetics of urate, cholesterol, glucose and triglyceride might be due to the rate of peroxide production by oxidases.

Enzymatic routes for the synthesis of ursodeoxycholic acid.

PubMed

Eggert, Thorsten; Bakonyi, Daniel; Hummel, Werner

2014-12-10

Ursodeoxycholic acid, a secondary bile acid, is used as a drug for the treatment of various liver diseases, the optimal dose comprises the range of 8-10mg/kg/day. For industrial syntheses, the structural complexity of this bile acid requires the use of an appropriate starting material as well as the application of regio- and enantio-selective enzymes for its derivatization. Most strategies for the synthesis start from cholic acid or chenodeoxycholic acid. The latter requires the conversion of the hydroxyl group at C-7 from α- into β-position in order to obtain ursodeoxycholic acid. Cholic acid on the other hand does not only require the same epimerization reaction at C-7 but the removal of the hydroxyl group at C-12 as well. There are several bacterial regio- and enantio-selective hydroxysteroid dehydrogenases (HSDHs) to carry out the desired reactions, for example 7α-HSDHs from strains of Clostridium, Bacteroides or Xanthomonas, 7β-HSDHs from Clostridium, Collinsella, or Ruminococcus, or 12α-HSDH from Clostridium or from Eggerthella. However, all these bioconversion reactions need additional steps for the regeneration of the coenzymes. Selected multi-step reaction systems for the synthesis of ursodeoxycholic acid are presented in this review. Copyright © 2014 Elsevier B.V. All rights reserved.

Method for the continuous production of hydrogen

DOEpatents

Getty, John Paul; Orr, Mark T.; Woodward, Jonathan

2002-01-01

The present invention is a method for the continuous production of hydrogen. The present method comprises reacting a metal catalyst with a degassed aqueous organic acid solution within a reaction vessel under anaerobic conditions at a constant temperature of .ltoreq.80.degree. C. and at a pH ranging from about 4 to about 9. The reaction forms a metal oxide when the metal catalyst reacts with the water component of the organic acid solution while generating hydrogen, then the organic acid solution reduces the metal oxide thereby regenerating the metal catalyst and producing water, thus permitting the oxidation and reduction to reoccur in a continual reaction cycle. The present method also allows the continuous production of hydrogen to be sustained by feeding the reaction with a continuous supply of degassed aqueous organic acid solution.

Oxidation of isoniazid by quinolinium dichromate in an aqueous acid medium and kinetic determination of isoniazid in pure and pharmaceutical formulations.

PubMed

Kulkarni, Raviraj M; Bilehal, Dinesh C; Nandibewoor, Sharanappa T

2004-04-01

The kinetics of oxidation of isoniazid in acidic medium was studied spectrophotometrically. The reaction between QDC and isoniazid in acid medium exhibits (4:1) stoichiometry (QDC:isoniazid). The reaction showed first order kinetics in quinolinium dichromate (QDC) concentration and an order of less than unity in isoniazid (INH) and acid concentrations. The oxidation reaction proceeds via a protonated QDC species, which forms a complex with isoniazid. The latter decomposes in a slow step to give a free radical derived from isoniazid and an intermediate chromium(V), which is followed, by subsequent fast steps to give the products. The reaction constants involved in the mechanism are evaluated. Isoniazid was analyzed by kinetic methods in pure and pharmaceutical formulations.

Investigation and application of multiple reactions between molybdoniobium heteropoly acid and di- or trimethylthionines

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

Mirzoyam, F.B.; Karapetyan, A.A.

1986-03-01

This paper presents the results of the study and use of reactions of molybdoniobic acid (MNA) with di- and trimethylthiones (DMT and TMT, respectively). It was found that light absorption of acetone solutions of the products of outer-sphere interaction between MNA and DMT or TMT enabled the determination of optimum acidity for MNA formation. Reaction between TMT and MNA gives two different compounds containing two and five associated dye cations, different in molar extinction coefficient and optimum reaction acidity (pH 0.05-0.25 and 0.35-0.90). Formation of the 6th and 8th molybdenum series with an identical composition of the outer sphere ismore » shown. A highly sensitive photometric method for determining niobium has been developed.« less

Preparation and characterization of (10)B boric acid with high purity for nuclear industry.

PubMed

Zhang, Weijiang; Liu, Tianyu; Xu, Jiao

2016-01-01

Boric acid is often added into coolant as neutron capture agent for pressurized water reactor, whose amount is influenced by its abundance and purity. Therefore, the preparation of enriched (10)B boric acid with high purity is beneficial to nuclear industry. (10)B is also used in developing tumor-specific boronated drugs in boron neutron capture therapy. The boronated drug can be administered to patient intravenously, intratumorally, or deposited at tumor site in surgical excision. Thus, enriched (10)B boric acid is of practical significance in the field of medicine. Self-made boron trifluoride-methanol-complex solution was selected as one of the experimental reagents, and the preparation of (10)B acid was realized by one-step reaction for the complexes with water and calcium chloride. The determination of electrical conductivity in reaction process proves that the optimum reaction time was 16-20 h. Furthermore, the effect of reaction time, ratio of calcium chloride to complex as well as the amount of water on the purity and yield of boric acid was investigated. Finally, the optimum reaction time was 20 h, the optimal solid-liquid ratio (molar ratio) was 3:1, and the amount of water was 1 L of deionized water for each mol of the complex. H2O2 was added in the reaction process to remove Fe(2+). After recrystallization, IR spectra of (10)B boric acid was measured and compared with standard to verify the product of boric acid. The feasibility of the preparation method was determined by the detection of XRD of boric acid. To observe the morphology by polarizing microscope, crystal structure was obtained. The purity of the final product is 99.95 %, and the yield is 96.47 %. The ion concentration of boric acid accords with the national standard of high purity, which was determined by ICP.

Determination of arrhenius and thermodynamic parameters for the aqueous reaction of the hydroxyl radical with lactic acid.

PubMed

Martin, Leigh R; Mezyk, Stephen P; Mincher, Bruce J

2009-01-08

Lactic acid is a major component of the TALSPEAK process planned for use in the separation of trivalent lanthanide and actinide elements. This acid acts both as a buffer and to protect the actinide complexant from radiolytic damage. However, there is little kinetic information on the reaction of water radiolysis species with lactic acid, particularly under the anticipated process conditions of aerated aqueous solution at pH approximately 3, where oxidizing reactions are expected to dominate. Here we have determined temperature-dependent reaction rate constants for the reactions of the hydroxyl radical with lactic acid and the lactate ion. For lactic acid this rate constant is given by the following equation: ln k(1) = (23.85 +/- 0.19) - (1120 +/- 54)/T, corresponding to an activation energy of 9.31 +/- 0.45 kJ mol(-1) and a room temperature reaction rate constant of (5.24 +/- 0.35) x 10(8) M(-1) s(-1) (24.0 degrees C). For the lactate ion, the temperature-dependent rate constant is given by ln k(2) = (24.83 +/- 0.14) - (1295 +/- 42)/T, for an activation energy of 10.76 +/- 0.35 kJ mol(-1) and a room temperature value of (7.77 +/- 0.50) x 10(8) M(-1) s(-1) (22.2 degrees C). These kinetic data have been combined with autotitration measurements to determine the temperature-dependent behavior of the lactic acid pK(a) value, allowing thermodynamic parameters for the acid dissociation to be calculated as DeltaH(o) = -10.75 +/- 1.77 kJ mol(-1), DeltaS(o) = -103.9 +/- 6.0 J K(-1) mol(-1) and DeltaG(o) = 20.24 +/- 2.52 kJ mol(-1) at low ionic strength.

Catalytic processing of lactic acid over Pt/Nb(2)O(5).

PubMed

Serrano-Ruiz, Juan Carlos; Dumesic, James A

2009-01-01

Dilute aqueous solutions of lactic acid (30 %wt.) can be catalytically processed at 573 K and 57 bar over a low-metal-content Pt(0.1 %)/Nb(2)O(5) catalyst in a spontaneously separating organic phase rich in valuable products such as C(4)-C(7) ketones. An increase in the lactic acid concentration to 60 wt % allows conversion of approximately 50 % of the carbon feed in this organic layer, while maintaining good stability of the catalyst. Experiments at low conversion showed that lactic acid reacts first over Pt(0.1 %)/Nb(2)O(5) to produce acetaldehyde and propanoic acid (along with CO and CO(2) in the gas phase). These compounds (less oxygenated than lactic acid but still reactive) are the key intermediates in the overall process, and they react differently depending on the nature of the catalyst support. In particular, reaction kinetics studies with propanoic acid as feed showed that Pt(0.1 %)/Nb(2)O(5) favored the formation of pentanones by ketonization reactions, whereas a monofunctional Pt(0.1 %)/carbon catalyst produced ethane and CO(x) by decomposition reactions. In the same manner, acetaldehyde was preferentially hydrogenated to ethanol over Pt(0.1 %)/carbon, whereas the presence of niobia allowed this intermediate to react (by successive aldol condensations) to form C(4)-C(7) condensation products stored in the organic phase. Finally, reaction pathways are proposed to explain the catalytic processing of lactic acid over bifunctional Pt(0.1 %)/Nb(2)O(5). In this scheme, metal sites catalyze hydrogenation reactions and niobia promotes C--C coupling processes (ketonization and aldol condensation), in contrast to C--C cleavage reactions which take place preferentially over Pt(0.1 %)/carbon and lead to loss of carbon in the gas effluent as CO, CO(2), and methane.

Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives† †Electronic supplementary information (ESI) available: Experimental information, synthesis and characterization data, NMR spectra, solid state NMR data, X-ray data, ESR spectra, UV-Vis-NIR spectra, fluorescence spectra, kinetic experiments, theoretical calculations, Tables S1–S8, Scheme S1, Fig. S1–12, References. CCDC 1025063, 1038914, 1049677 and 1040722. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00946d

PubMed Central

Pandit, Palash; Yamamoto, Koji; Nakamura, Toshikazu; Nishimura, Katsuyuki; Kurashige, Yuki; Yanai, Takeshi; Nakamura, Go; Masaoka, Shigeyuki; Furukawa, Ko; Yakiyama, Yumi; Kawano, Masaki

2015-01-01

Regulation of electron transfer on organic substances by external stimuli is a fundamental issue in science and technology, which affects organic materials, chemical synthesis, and biological metabolism. Nevertheless, acid/base-responsive organic materials that exhibit reversible electron transfer have not been well studied and developed, owing to the difficulty in inventing a mechanism to associate acid/base stimuli and electron transfer. We discovered a new phenomenon in which N–N linked bicarbazole (BC) and tetramethylbiacridine (TBA) derivatives undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species. The reaction occurs through a biradical intermediate generated by the acid-triggered N–N bond cleavage reaction of BC or TBA, which acts as a two electron acceptor to undergo electron transfer reactions with two equivalents of BC or TBA. In addition, in the case of TBA the disproportionation reaction is highly reversible through neutralization with NEt3, which recovers TBA through back electron transfer and N–N bond formation reactions. This highly reversible electron transfer reaction is possible due to the association between the acid stimulus and electron transfer via the acid-regulated N–N bond cleavage/formation reactions which provide an efficient switching mechanism, the ability of the organic molecules to act as multi-electron donors and acceptors, the extraordinary stability of the radical species, the highly selective reactivity, and the balance of the redox potentials. This discovery provides new design concepts for acid/base-regulated organic electron transfer systems, chemical reagents, or organic materials. PMID:29218181

Kinetics of ozonation. 4. Reactions of ozone with. cap alpha. -tocopherol and oleate and linoleate esters in carbon tetrachloride and in aqueous micellar solvents

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

Giamalva, D.H.; Church, D.F.; Pryor, W.A.

1986-10-15

Vitamin E (..cap alpha..-tocopherol; ..cap alpha..-T) is known to protect animals against the deleterious effects of ozone in polluted air; one such effect is the ozone-initiated autooxidation of polyunsaturated fatty acids (PUFA) that occur in membranes. In order to assess the possibility of a direct reaction of ozone with ..cap alpha..-T competing with the very fast ozone-PUFA reaction, we have measured the rates of reaction of ozone with ..cap alpha..-T, oleic acid, and linoleic acid. I CCl/sub 4/ as solvent, ..cap alpha..-T reacts with ozone with a rate constant of about 5500 M/sup -1/ s/sup -1/; methyl oleate and methylmore » linoleate react 2 orders of magnitude faster. In aqueous micellar solutions the rate constants for ..cap alpha..-T and the fatty acids are more similar. The k for the ozone/..cap alpha..-T reaction is about 1 x 10/sup 6/ M/sup -1/ s/sup -1/ at pH 7, but decreases as the solution becomes more acidic; the k's for oleic acid and linoleic acid are ca. 1 x 10/sup 6/ M/sup -1/ s/sup -1/ and exhibit no significant pH dependence. Since the ratio of fatty acids to ..cap alpha..-T in membranes is typically at least 100-1000 to 1, we conclude that the direct reaction of ozone with ..cap alpha..-T is unlikely. Thus, the protection that vitamin E provides to animals breathing ozone-containing air must result from vitamin E acting as a free radical scavenger. We have also detected the ..cap alpha..-tocopheroxyl radical as an intermediate from the reaction of ozone with ..cap alpha..-T both in CCl/sub 4/ and aqueous micelles using electron spin resonance spectroscopy. The authors suggest that the observation of this intermediate is consistent with an initial electron transfer from ..cap alpha..-T to ozone.« less

42 CFR 493.1262 - Standard: Mycobacteriology.

Code of Federal Regulations, 2010 CFR

2010-10-01

... or test procedures used for mycobacteria identification with at least one acid-fast organism that produces a positive reaction and an acid-fast organism that produces a negative reaction. (b) For...

42 CFR 493.1262 - Standard: Mycobacteriology.

Code of Federal Regulations, 2011 CFR

2011-10-01

... or test procedures used for mycobacteria identification with at least one acid-fast organism that produces a positive reaction and an acid-fast organism that produces a negative reaction. (b) For...

42 CFR 493.1262 - Standard: Mycobacteriology.

Code of Federal Regulations, 2014 CFR

2014-10-01

... or test procedures used for mycobacteria identification with at least one acid-fast organism that produces a positive reaction and an acid-fast organism that produces a negative reaction. (b) For...

42 CFR 493.1262 - Standard: Mycobacteriology.

Code of Federal Regulations, 2013 CFR

2013-10-01

... or test procedures used for mycobacteria identification with at least one acid-fast organism that produces a positive reaction and an acid-fast organism that produces a negative reaction. (b) For...

42 CFR 493.1262 - Standard: Mycobacteriology.

Code of Federal Regulations, 2012 CFR

2012-10-01

... or test procedures used for mycobacteria identification with at least one acid-fast organism that produces a positive reaction and an acid-fast organism that produces a negative reaction. (b) For...

STUDIES ON ORGANIC ACID METABOLISM,

DTIC Science & Technology

Lipoic acid metabolism: The acetyl and succinyl thio esters of civinyl dimercapto were prepared by chemical and enzymatic means. The oxidation...reduction reactions of the disulfide-dimercapto groups in pyrimidine nucleotide-linked reactions were explored in the initial lipoic acid assay organiam...disulfide couple. The studies appeared to indicate a bound form of lipoic acid to be the coenzyme, and suggested that an amide or possibly another

Improved Understanding of In Situ Chemical Oxidation. Technical Objective 2: Soil Reactivity

DTIC Science & Technology

2009-05-01

each reaction tube. The reagents ( sulfuric acid /potassium dichromate/mercury sulfate ) were prepared following standard methods (APHA, 1998). When...reaction tubes. A volume (~20 mL) of potassium dichromate digestion solution (potassium dichromate (BDH Laboratories), sulfuric acid (EM Science...and mercury sulphate (EM Science)) and a sulfuric acid reagent solution ( sulfuric acid (EM Science) and silver sulphate (Alfa Aesar)) were added to

Acid–base bifunctional shell cross-linked micelle nanoreactor for one-pot tandem reaction

DOE PAGES

Lee, Li -Chen; Lu, Jie; Weck, Marcus; ...

2015-12-29

In shell cross-linked micelles (SCMs) containing acid sites in the shell and base sites in the core are prepared from amphiphilic poly(2-oxazoline) triblock copolymers. These materials are utilized as two-chamber nanoreactors for a prototypical acid-base bifunctional tandem deacetalization-nitroaldol reaction. Furthermore, the acid and base sites are localized in different regions of the micelle, allowing the two steps in the reaction sequence to largely proceed in separate compartments, akin to the compartmentalization that occurs in biological systems.

N-Triflylthiophosphoramide Catalyzed Enantioselective Mukaiyama Aldol Reaction of Aldehydes with Silyl Enol Ethers of Ketones

PubMed Central

Cheon, Cheol Hong; Yamamoto, Hisashi

2010-01-01

The first Brønsted acid catalyzed asymmetric Mukaiyama aldol reaction of aldehydes using silyl enol ethers of ketones as nucleophiles has been reported. A variety of aldehydes and silyl enol ethers of ketones afforded the aldol products in excellent yields and good to excellent enantioselectivities. Mechanistic studies revealed that the actual catalyst may be changed from the silylated Brønsted acid to Brønsted acid itself depending on the reaction temperature. PMID:20465277

N-triflylthiophosphoramide catalyzed enantioselective Mukaiyama aldol reaction of aldehydes with silyl enol ethers of ketones.

PubMed

Cheon, Cheol Hong; Yamamoto, Hisashi

2010-06-04

The first Brønsted acid catalyzed asymmetric Mukaiyama aldol reaction of aldehydes using silyl enol ethers of ketones as nucleophiles has been reported. A variety of aldehydes and silyl enol ethers of ketones afforded the aldol products in excellent yields and good to excellent enantioselectivities. Mechanistic studies revealed that the actual catalyst may be changed from the silylated Brønsted acid to the Brønsted acid itself depending on the reaction temperature.

Heterogeneous kinetics, products, and mechanisms of ferulic acid particles in the reaction with NO3 radicals

NASA Astrophysics Data System (ADS)

Liu, Changgeng; Zhang, Peng; Wen, Xiaoying; Wu, Bin

2017-03-01

Methoxyphenols, as an important component of wood burning, are produced by lignin pyrolysis and considered to be the potential tracers for wood smoke emissions. In this work, the heterogeneous reaction between ferulic acid particles and NO3 radicals was investigated. Six products including oxalic acid, 4-vinylguaiacol, vanillin, 5-nitrovanillin, 5-nitroferulic acid, and caffeic acid were confirmed by gas chromatography-mass spectrometry (GC-MS). In addition, the reaction mechanisms were proposed and the main pathways were NO3 electrophilic addition to olefin and the meta-position to the hydroxyl group. The uptake coefficient of NO3 radicals on ferulic acid particles was 0.17 ± 0.02 and the effective rate constant under experimental conditions was (1.71 ± 0.08) × 10-12 cm3 molecule-1 s-1. The results indicate that ferulic acid degradation by NO3 can be an important sink at night.

Cocondensation of urea with methylolphenols in acidic conditions

Treesearch

Bunchiro Tomita; Chung-Yun Hse

1992-01-01

The reactions of urea with methylolphenols under acidic conditions were investigated using 2- and 4-hydroxybenzyl alcohol and crude 2,4,6-trimethylophenol as model compounds. The reaction products were analyzed with 13C-NMR spectroscopy and GPC. From the reaction of urea with 4-hydroxybenzyl alcohol, the formations of 4-hydroxybenzylurea,

Miniature reaction chamber and devices incorporating same

DOEpatents

Mathies, Richard A.; Woolley, Adam T.

2000-10-17

The present invention generally relates to miniaturized devices for carrying out and controlling chemical reactions and analyses. In particular, the present invention provides devices which have miniature temperature controlled reaction chambers for carrying out a variety of synthetic and diagnostic applications, such as PCR amplification, nucleic acid hybridization, chemical labeling, nucleic acid fragmentation and the like.

ORGANIC REACTIONS IN THE SOLID STATE AND IN SOLID SOLUTIONS.

DTIC Science & Technology

on the reactions of phthalic acid and acetanilide , various acyl anilides, and ring-substituted acetanilides . Exploratory experiments were also...performed between ring-substituted acetanilides and succinic, glutaric, maleic and fumaric acids. The influence of imidazole as a catalyst of the...transacylation reaction of phthalic anhydride and acetanilide is also reported. (Author)

Possible mechanism of structural incorporation of Al into diatomite during the deposition process I. Via a condensation reaction of hydroxyl groups.

PubMed

Liu, Dong; Yu, Wenbin; Deng, Liangliang; Yuan, Weiwei; Ma, Lingya; Yuan, Peng; Du, Peixin; He, Hongping

2016-01-01

The structural incorporation of aluminium (Al) into diatomite is investigated by preparing several Al-diatomite composites by loading an Al precursor, hydroxyl aluminum polymer (Al13), onto the surface of diatomite and heating at various temperatures. The results indicate that Al was incorporated and implanted into the structure of diatomite by the condensation reaction of the hydroxyl groups of Al13 and diatomite, and the Si-O-Al(OH) groups were formed during the condensation reaction. Al incorporation by the condensation reaction of hydroxyl groups of Al13 with single silanols of diatomite occurred more readily than that with geminal silanols. The Al incorporation increased solid acidity of diatomite after Al incorporation. The acidity improvement was various for different types of acid sites, depending on the preparation temperature of the Al-incorporated diatomite. Both Brønsted and Lewis acid sites increased greatly after heating at 250 and 350 °C, but only L acid sites significantly improved after heating at 500 °C. These results demonstrate that the structural incorporation of Al(3+) ions into diatomite can occur by the condensation reaction of the hydroxyl groups of the Al precursors and diatomite. Moreover, the rich solid acid sites of Al-incorporated diatomite show its promising application as a solid acid catalyst. Copyright © 2015 Elsevier Inc. All rights reserved.

Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors

PubMed Central

Kawasaki, Shin-ichiro; Suzuki, Akira

2013-01-01

Summary The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd–Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid. PMID:23843908

Contactless, probeless and non-titrimetric determination of acid-base reactions using broadband acoustic resonance dissolution spectroscopy (BARDS).

PubMed

Ahmed, M Rizwan; McSweeney, Sean; Krüse, Jacob; Vos, Bastiaan; Fitzpatrick, Dara

2018-02-12

pH determination is a routine measurement in scientific laboratories worldwide. Most major advances in pH measurement were made in the 19th and early 20th century. pH measurements are critical for the determination of acid base reactions. This study demonstrates how an acid-base reaction can be monitored without the use of a pH probe, indicator and titres of reagent. The stoichiometric reaction between carbonate and HCl acid yields specific quantities of CO 2 , which causes reproducible changes to the compressibility of the solvent. This in turn slows down the speed of sound in solution which is induced by a magnetic follower gently tapping the inner wall of the vessel. As a consequence the frequencies of the acoustic resonances in the vessel are reduced. This approach is called Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS) which harnesses this phenomenon for many applications. The acid-carbonate experiments have also been validated using H 2 SO 4 acid and using both potassium and sodium counterions for the carbonate. This method can be used to interrogate strong acid-base reactions in a rapid and non-invasive manner using carbonate as the base. The data demonstrate the first example of a reactant also acting as an indicator. The applicability of the method to weak acids has yet to be determined. A novel conclusion from the study is that a person with a well-trained ear is capable of determining the concentration and pH of a strong acid just by listening. This brings pH measurement into the realm of human perception.

Comprehensive near infrared study of Jatropha oil esterification with ethanol for biodiesel production

NASA Astrophysics Data System (ADS)

Oliveira, Alianda Dantas de; Sá, Ananda Franco de; Pimentel, Maria Fernanda; Pacheco, José Geraldo A.; Pereira, Claudete Fernandes; Larrechi, Maria Soledad

2017-01-01

This work presents a comprehensive near infrared study for in-line monitoring of the esterification reaction of high acid oils, such as Jatropha curcas oil, using ethanol. Parallel reactions involved in the process were carried out to select a spectral region that characterizes the evolution of the esterification reaction. Using absorbance intensities at 5176 cm- 1, the conversion and kinetic behaviors of the esterification reaction were estimated. This method was applied to evaluate the influence of temperature and catalyst concentration on the estimates of initial reaction rate and ester conversion as responses to a 22 factorial experimental design. Employment of an alcohol/oil ratio of 16:1, catalyst concentration of 1.5% w/w, and temperatures at 65 °C or 75 °C, made it possible to reduce the initial acidity from 18% to 1.3% w/w, which is suitable for transesterification of high free fatty acid oils for biodiesel production. Using the proposed analytical method in the esterification reaction of raw materials with high free fatty acid content for biodiesel makes the monitoring process inexpensive, fast, simple, and practical.

Reactions of vitamin A with acceptors of electrons. Interactions with iodine and the formation of iodide

PubMed Central

Lucy, J. A.; Lichti, F. Ulrike

1969-01-01

1. The reactions of retinol and retinoic acid with iodine were investigated since knowledge of the chemical reactions of vitamin A with acceptors of electrons may shed light on its biochemical mode of action. 2. Colloidal retinol, but not retinoic acid, reacts with iodine to yield a blue–green complex that rapidly decomposes, giving iodide and an unknown species with λmax. at 870mμ. 3. In addition, both retinol and retinoic acid reduce iodine to iodide by a reaction that does not involve an intermediate coloured complex; this reaction appears to yield unstable carbonium ion derivatives of the vitamin. 4. The presence of water greatly facilitates the production of iodide from vitamin A and iodine. 5. Possible chemical pathways involved in these reactions are discussed. 6. It is suggested that the chemical properties of retinol and retinoic acid that underlie their biochemical behaviour might be apparent only when the molecules are at a lipid–water interface, and that vitamin A might be expected to react with a number of different electron acceptors in vivo. PMID:5801297

Detailed mechanistic investigation into the S-nitrosation of cysteamine.

PubMed

Morakinyo, Moshood K; Chipinda, Itai; Hettick, Justin; Siegel, Paul D; Abramson, Jonathan; Strongin, Robert; Martincigh, Bice S; Simoyi, Reuben H

The nitrosation of cysteamine (H 2 NCH 2 CH 2 SH) to produce cysteamine- S -nitrosothiol (CANO) was studied in slightly acidic medium by using nitrous acid prepared in situ. The stoichiometry of the reaction was H 2 NCH 2 CH 2 SH + HNO 2 → H 2 NCH 2 CH 2 SNO + H 2 O. On prolonged standing, the nitrosothiol decomposed quantitatively to yield the disulfide, cystamine: 2H 2 NCH 2 CH 2 SNO → H 2 NCH 2 CH 2 S-SCH 2 CH 2 NH 2 + 2NO. NO 2 and N 2 O 3 are not the primary nitrosating agents, since their precursor (NO) was not detected during the nitrosation process. The reaction is first order in nitrous acid, thus implicating it as the major nitrosating agent in mildly acidic pH conditions. Acid catalyzes nitrosation after nitrous acid has saturated, implicating the protonated nitrous acid species, the nitrosonium cation (NO + ) as a contributing nitrosating species in highly acidic environments. The acid catalysis at constant nitrous acid concentrations suggests that the nitrosonium cation nitrosates at a much higher rate than nitrous acid. Bimolecular rate constants for the nitrosation of cysteamine by nitrous acid and by the nitrosonium cation were deduced to be 17.9 ± 1.5 (mol/L) -1 s -1 and 6.7 × 10 4 (mol/L) -1 s -1 , respectively. Both Cu(I) and Cu(II) ions were effective catalysts for the formation and decomposition of the cysteamine nitrosothiol. Cu(II) ions could catalyze the nitrosation of cysteamine in neutral conditions, whereas Cu(I) could only catalyze in acidic conditions. Transnitrosation kinetics of CANO with glutathione showed the formation of cystamine and the mixed disulfide with no formation of oxidized glutathione (GSSG). The nitrosation reaction was satisfactorily simulated by a simple reaction scheme involving eight reactions.

Detailed mechanistic investigation into the S-nitrosation of cysteamine

PubMed Central

Morakinyo, Moshood K.; Chipinda, Itai; Hettick, Justin; Siegel, Paul D.; Abramson, Jonathan; Strongin, Robert; Martincigh, Bice S.; Simoyi, Reuben H.

2015-01-01

The nitrosation of cysteamine (H2NCH2CH2SH) to produce cysteamine-S-nitrosothiol (CANO) was studied in slightly acidic medium by using nitrous acid prepared in situ. The stoichiometry of the reaction was H2NCH2CH2SH + HNO2 → H2NCH2CH2SNO + H2O. On prolonged standing, the nitrosothiol decomposed quantitatively to yield the disulfide, cystamine: 2H2NCH2CH2SNO → H2NCH2CH2S–SCH2CH2NH2 + 2NO. NO2 and N2O3 are not the primary nitrosating agents, since their precursor (NO) was not detected during the nitrosation process. The reaction is first order in nitrous acid, thus implicating it as the major nitrosating agent in mildly acidic pH conditions. Acid catalyzes nitrosation after nitrous acid has saturated, implicating the protonated nitrous acid species, the nitrosonium cation (NO+) as a contributing nitrosating species in highly acidic environments. The acid catalysis at constant nitrous acid concentrations suggests that the nitrosonium cation nitrosates at a much higher rate than nitrous acid. Bimolecular rate constants for the nitrosation of cysteamine by nitrous acid and by the nitrosonium cation were deduced to be 17.9 ± 1.5 (mol/L)−1 s−1 and 6.7 × 104 (mol/L)−1 s−1, respectively. Both Cu(I) and Cu(II) ions were effective catalysts for the formation and decomposition of the cysteamine nitrosothiol. Cu(II) ions could catalyze the nitrosation of cysteamine in neutral conditions, whereas Cu(I) could only catalyze in acidic conditions. Transnitrosation kinetics of CANO with glutathione showed the formation of cystamine and the mixed disulfide with no formation of oxidized glutathione (GSSG). The nitrosation reaction was satisfactorily simulated by a simple reaction scheme involving eight reactions. PMID:26594054

Aldehyde-alcohol reactions catalyzed under mild conditions by chromium(III) terephthalate metal organic framework (MIL-101) and phosphotungstic acid composites.

PubMed

Bromberg, Lev; Hatton, T Alan

2011-12-01

Porous materials based on chromium(III) terephthalate metal organic frameworks (MIL-101) and their composites with phosphotungstic acid (PTA) were studied as heterogeneous acid catalysts in aldehyde-alcohol reactions exemplified by acetaldehyde-phenol (A-P) condensation and dimethylacetal formation from benzaldehyde and methanol (B-M reaction). The MIL-101 was synthesized solvothermically in water, and the MIL101/PTA composite materials were obtained by either impregnation of the already prepared MIL-101 porous matrix with phosphotungstic acid solution or by solvothermic treatment of aqueous mixtures of Cr(NO(3))(3), and terephthalic and phosphotungstic acids. The MIL101/PTA materials appeared to be effective catalysts for both A-P and B-M reactions occurring at room temperature, with half-lives ranging from 0.5 h (A-P) to 1.5-2 h (B-M) and turnover numbers over 600 for A-P and over 2900 for the B-M reaction, respectively. A synergistic effect of the strong acidic moieties (PTA) addition to mildly acidic Brønsted and Lewis acid cites of the MIL-101 was observed with the MIL101/PTA composites. The ability of the PTA and MIL101/PTA materials to strongly absorb and condense acetaldehyde vapors was discovered, with the MIL101/PTA absorbing over 10-fold its dry weight of acetaldehyde condensate at room temperature. The acetaldehyde was converted rapidly to crotonaldehyde and higher-molecular-weight compounds while in contact with MIL-101 and MIL101/PTA materials. The stability of the MIL-101 and MIL101/PTA catalysts was assessed within four cycles of the 1-day alcohol-aldehyde reactions in terms of the overall catalyst recovery, PTA or Cr content, and reaction rate constants in each cycle. The loss of the catalyst over 4 cycles was approximately 10 wt % for all tested catalysts due to the incomplete recovery and minute dissolution of the components. The reaction rates in all cycles remained unchanged and the catalyst losses stopped after the third cycle. The developed MIL101/PTA composites appear to be feasible for industrial catalytic applications. © 2011 American Chemical Society

Synthesis of fatty acid methyl ester from the transesterification of high- and low-acid-content crude palm oil (Elaeis guineensis) and karanj oil (Pongamia pinnata) over a calcium-lanthanum-aluminum mixed-oxides catalyst.

PubMed

Syamsuddin, Y; Murat, M N; Hameed, B H

2016-08-01

The synthesis of fatty acid methyl ester (FAME) from the high- and low-acid-content feedstock of crude palm oil (CPO) and karanj oil (KO) was conducted over CaO-La2O3-Al2O3 mixed-oxide catalyst. Various reaction parameters were investigated using a batch reactor to identify the best reaction condition that results in the highest FAME yield for each type of oil. The transesterification of CPO resulted in a 97.81% FAME yield with the process conditions of 170°C reaction temperature, 15:1 DMC-to-CPO molar ratio, 180min reaction time, and 10wt.% catalyst loading. The transesterification of KO resulted in a 96.77% FAME yield with the conditions of 150°C reaction temperature, 9:1 DMC-to-KO molar ratio, 180min reaction time, and 5wt.% catalyst loading. The properties of both products met the ASTM D6751 and EN 14214 standard requirements. The above results showed that the CaO-La2O3-Al2O3 mixed-oxide catalyst was suitable for high- and low-acid-content vegetable oil. Copyright © 2016 Elsevier Ltd. All rights reserved.

Coupling of hydrologic transport and chemical reactions in a stream affected by acid mine drainage

USGS Publications Warehouse

Kimball, B.A.; Broshears, R.E.; Bencala, K.E.; McKnight, Diane M.

1994-01-01

Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injection of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples of metal concentrations and the hydrologic characteristics of the stream. Transport of SO4 and Mn was generally conservative, but in the subreaches most affected by acidic inflows, transport was reactive. Both 0.1-??m filtered and particulate Fe were reactive over most of the stream reach. Filtered Al partitioned to the particulate phase in response to high instream concentrations. Simulations that accounted for the removal of SO4, Mn, Fe, and Al with first-order reactions reproduced the steady-state profiles. The calculated rate constants for net removal used in the simulations embody several processes that occur on a stream-reach scale. The comparison between rates of hydrologie transport and chemical reactions indicates that reactions are only important over short distances in the stream near the acidic inflows, where reactions occur on a comparable time scale with hydrologic transport and thus affect metal concentrations.

Sources and sinks of formic, acetic, and pyruvic acids over central Amazonia. II - Wet season

NASA Technical Reports Server (NTRS)

Talbot, R. W.; Andreae, M. O.; Berresheim, H.; Jacob, D. J.; Beecher, K. M.

1990-01-01

Potential sources and sinks of formic, acetic, and pyruvic acids over the Amazon forest were investigated using a photochemical model and data collected on gas phase concentrations of these acids in the forest canopy, boundary layer, and free troposphere over the central Amazon Basin during the 1987 wet season. It was found that the atmospheric reactions previously suggested in the literature as sources of carboxylic acids (i.e., the gas phase decomposition of isoprene, the reaction between CH3CO3 and a peroxide, and aqueous phase oxidation of CH2O) appear to be too slow to explain the observed concentrations, suggesting that other atmospheric reactions, so far unidentified, could make a major contribution to the carboxylic acid budgets.

Importance of Unimolecular HO 2 Elimination in the Heterogeneous OH Reaction of Highly Oxygenated Tartaric Acid Aerosol

DOE PAGES

Cheng, Chiu Tung; Chan, Man Nin; Wilson, Kevin R.

2016-07-09

Oxygenated organic molecules are abundant in atmospheric aerosols and are transformed by oxidation reactions near the aerosol surface by gas-phase oxidants such as hydroxyl (OH) radicals. To gain better insights into how the structure of an organic molecule, particularly in the presence of hydroxyl groups, controls the heterogeneous reaction mechanisms of oxygenated organic compounds, this paper investigates the OH-radical initiated oxidation of aqueous tartaric acid (C 4H 6O 6) droplets using an aerosol flow tube reactor. The molecular composition of the aerosols before and after reaction is characterized by a soft atmospheric pressure ionization source (Direct Analysis in Real Time)more » coupled with a high-resolution mass spectrometer. The aerosol mass spectra reveal that four major reaction products are formed: a single C 4 functionalization product (C 4H 4O 6) and three C 3 fragmentation products (C 3H 4O 4, C 3H 2O 4, and C 3H 2O 5). The C 4 functionalization product does not appear to originate from peroxy radical self-reactions but instead forms via an α-hydroxylperoxy radical produced by a hydrogen atom abstraction by OH at the tertiary carbon site. The proximity of a hydroxyl group to peroxy group enhances the unimolecular HO 2 elimination from the α-hydroxylperoxy intermediate. This alcohol-to-ketone conversion yields 2-hydroxy-3-oxosuccinic acid (C 4H 4O 6), the major reaction product. While in general, C–C bond scission reactions are expected to dominate the chemistry of organic compounds with high average carbon oxidation states (OS C), our results show that molecular structure can play a larger role in the heterogeneous transformation of tartaric acid (OS C = 1.5). Finally, these results are also compared with two structurally related dicarboxylic acids (succinic acid and 2,3-dimethylsuccinic acid) to elucidate how the identity and location of functional groups (methyl and hydroxyl groups) alter heterogeneous reaction mechanisms.« less

Closed cycle ion exchange method for regenerating acids, bases and salts

DOEpatents

Dreyfuss, Robert M.

1976-01-01

A method for conducting a chemical reaction in acidic, basic, or neutral solution as required and then regenerating the acid, base, or salt by means of ion exchange in a closed cycle reaction sequence which comprises contacting the spent acid, base, or salt with an ion exchanger, preferably a synthetic organic ion-exchange resin, so selected that the counter ions thereof are ions also produced as a by-product in the closed reaction cycle, and then regenerating the spent ion exchanger by contact with the by-product counter ions. The method is particularly applicable to closed cycle processes for the thermochemical production of hydrogen.

Cutaneous adverse reactions to amoxicillin-clavulanic acid suspension in children: the role of sodium benzoate.

PubMed

Mori, Francesca; Barni, Simona; Pucci, Neri; Rossi, Maria Elisabetta; de Martino, Maurizio; Novembre, Elio

2012-04-01

In Europe amoxicillin plus clavulanic acid is the most commonly prescribed antibiotic and sodium benzoate is contained in the suspension formulation as a preservative. We studied the relevance of sodium benzoate as the culprit agent. In a group of children with a history of adverse reactions to amoxicillin plus clavulanic acid suspension. A total of 89 children were enrolled over a period of 3 years (2006 - 2009). Single blind oral provocation tests (OPTs) with amoxicillin plus clavulanic acid, sodium benzoate and placebo were performed. 20 children with recurrent idiopathic urticaria were investigated as a control group. according to personal history: 70% of reactions were late in developing while 23% of reactions were immediate and for 5% of the cases it was not possible to define the timing. 8 children (8/89=9%) resulted positive to the provocation tests with amoxicillin plus clavulanic acid; ten children (10/89=11%) had positive results with sodium benzoate; 3% had a double positivity (i.e. excipient and active drug). The timing of reactions significantly differs between the Amoxicillin plus clavulanic acid and sodium benzoate groups (p=0.002). Sodium benzoate probably acts through a non-immunologic mechanism and care should be given to children allergic to sodium benzoate containing pharmaceutical formulations.

A combined experimental and computational study of the mechanism of fructose dehydration to 5-hydroxymethylfurfural in dimethylsulfoxide using Amberlyst 70, PO 4 3-/niobic acid, or sulfuric acid catalysts

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

Zhang, Jing; Das, Anirban; Assary, Rajeev S.

We report on a combined experimental and theoretical study of the acid catalyzed dehydration of d-fructose in dimethylsulfoxide (DMSO) using; Amberlyst 70, PO 4 3-/niobic acid, and sulfuric acid as catalysts. The reaction has been studied and intermediates characterized using; 13C, 1H, and 17O NMR, and high resolution electrospray ionization mass spectrometry (HR ESI–MS). High level G4MP2 theory calculations are used to understand the thermodynamic landscape for the reaction mechanism in DMSO. We have experimentally identified two key intermediates in the dehydration of fructose to form HMF that were also identified, using theory, as local minima on the potential surfacemore » for reaction. A third intermediate, a species capable of undergoing keto–enol tautomerism, was also experimentally detected. However, it was not possible to experimentally distinguish between the keto and the enol forms. These data with different catalysts are consistent with common intermediates along the reaction pathway from fructose to HMF in DMSO. The role of oxygen in producing acidic species in reactions carried out in DMSO in presence of air is also discussed.« less

Oxidative acylation using thioacids

NASA Technical Reports Server (NTRS)

Liu, R.; Orgel, L. E.

1997-01-01

Several important prebiotic reactions, including the coupling of amino acids into polypeptides by the formation of amide linkages, involve acylation. Theae reactions present a challenge to the understanding of prebiotic synthesis. Condensation reactions relying on dehydrating agents are either inefficient in aqueous solution or require strongly acidic conditions and high temperatures. Activated amino acids such as thioester derivatives have therefore been suggested as likely substrates for prebiotic peptide synthesis. Here we propose a closely related route to amide bond formation involving oxidative acylation by thioacids. We find that phenylalanine, leucine and phenylphosphate are acylated efficiently in aqueous solution by thioacetic acid and an oxidizing agent. From a prebiotic point of view, oxidative acylation has the advantage of proceeding efficiently in solution and under mild conditions. We anticipate that oxidative acylation should prove to be a general method for activating carboxylic acids, including amino acids.

[Study on the encapsulation technique of high purity gamma-linolenic acid, part 1--saponification reaction and saponification value].

PubMed

Liu, Feng-xia; Xue, Gang; Gao, Qiu-hua; Gao, Wei-xia; Zhang, Li-hua

2005-03-01

To measure the saponification value and fatty acid formation of evening primrose oil, to study the effects of pH value on production yield and fatty acid formation during the saponification reaction, and to provide rationales for the selection of raw material, the enhancement of production yield of saponification, and the encapsulation of gamma-linolenic acid with urea. To measure fatty acid's formation with gas chromatographic method and to measure the saponification value. The content of gamma-linolenic acid is 7%-10% in evening primrose oil. The content of gamma-linolenic acid is inversely correlated with that of unsaturated fatty acid. The saponification value, the amount of KOH for saponification of evening primrose oil, and the pH value for subsequent isolations of oils are determined. From the measurement of fatty acids of evening primrose oil in two different cultivation locations, the content of gamma-linolenic acid is determined to be 7%-10%, unsaturated oils account for 90%. The saponification value of evening primrose oil is between 180-200, pH value of isolated oil is 1.5-2.0 after saponification reaction. Fatty acids mainly include palmitic acid, stearic acid, oleic acid, linolic acid and gamma-linolenic acid.

The Roles of Acids and Bases in Enzyme Catalysis

ERIC Educational Resources Information Center

Weiss, Hilton M.

2007-01-01

Many organic reactions are catalyzed by strong acids or bases that protonate or deprotonate neutral reactants leading to reactive cations or anions that proceed to products. In enzyme reactions, only weak acids and bases are available to hydrogen bond to reactants and to transfer protons in response to developing charges. Understanding this…

Ketonization of Cuphea oil for the production of 2-undecanone

USDA-ARS?s Scientific Manuscript database

The objective of this work was to demonstrate the viability of the cross ketonization reaction with the triacylglycerol from Cuphea sp. and acetic acid in a fixed-bed plug-flow reactor. The seed oil from Cuphea sp. contains up to 71% decanoic acid and the reaction of this fatty acid residue with ac...

Role of basic and acidic centers of MgO and modified MgO in catalytic transfer hydrogenation of ketones studied by infrared spectroscopy

NASA Astrophysics Data System (ADS)

Szöllösi, György; Bartók, Mihály

1999-05-01

In this study our aim was to identify the active sites and the surface species responsible for deactivation of MgO during catalytic transfer hydrogenations (CTH) of ketones using alcohols as hydrogen donors. Our previous studies showed that deactivation of MgO could be prevented by previous treatment with chloromethanes. Therefore the surface species formed during the reaction were studied before and after treatment with chloroform or chloroform- d by in situ infrared spectroscopy (IR). As a result, it was concluded that the reaction requires the presence of surface basic and acidic centers. The presence of Lewis acid centers was not necessary, the reaction could proceed on weakly acidic surface Brönsted sites, as the alterations in intensity and position of the ν(OH) bands indicated. Modification with chloroform resulted also in the generation of surface OH groups with a proper acidity for the reaction. The shift in carbonyl vibrations led us to the conclusion that Lewis acid and base centers were responsible for the catalyst poisoning, so covering these acid sites by Cl - led to a stable catalyst.

Formation of Amino Acid Thioesters for Prebiotic Peptide Synthesis: Catalysis By Amino Acid Products

NASA Technical Reports Server (NTRS)

Weber, Arthur L.; DeVincenzi, Donald L. (Technical Monitor)

1999-01-01

The origin of life can be described as a series of events in which a prebiotic chemical process came increasingly under the control of its catalytic products. In our search for this prebiotic process that yielded catalytic takeover products (such as polypeptides), we have been investigating a reaction system that generates peptide-forming amino acid thioesters from formaldehyde, glycolaldehyde, and ammonia in the presence of thiols. As shown below, this model process begins by aldol condensation of formaldehyde and glycolaldehyde to give trioses and releases. These sugars then undergo beta-dehydration yielding their respective alpha-ketoaldehydes. Addition of ammonia to the alpha-ketoaldehydes yields imines which can either: (a) rearrange in the presence of thesis to give amino acid thioesters or (be react with another molecule of aldehyde to give imidazoles. This 'one-pot' reaction system operates under mild aqueous conditions, and like modem amino acid biosynthesis, uses sugar intermediates which are converted to products by energy-yielding redox reactions. Recently, we discovered that amino acids, such as the alanine reaction product, catalyze the first and second steps of the process. In the presence of ammonia the process also generates other synthetically useful products, like the important biochemical -- pyruvic acid.

Sulfuric acid-sulfur heat storage cycle

DOEpatents

Norman, John H.

1983-12-20

A method of storing heat is provided utilizing a chemical cycle which interconverts sulfuric acid and sulfur. The method can be used to levelize the energy obtained from intermittent heat sources, such as solar collectors. Dilute sulfuric acid is concentrated by evaporation of water, and the concentrated sulfuric acid is boiled and decomposed using intense heat from the heat source, forming sulfur dioxide and oxygen. The sulfur dioxide is reacted with water in a disproportionation reaction yielding dilute sulfuric acid, which is recycled, and elemental sulfur. The sulfur has substantial potential chemical energy and represents the storage of a significant portion of the energy obtained from the heat source. The sulfur is burned whenever required to release the stored energy. A particularly advantageous use of the heat storage method is in conjunction with a solar-powered facility which uses the Bunsen reaction in a water-splitting process. The energy storage method is used to levelize the availability of solar energy while some of the sulfur dioxide produced in the heat storage reactions is converted to sulfuric acid in the Bunsen reaction.

The Use of Gel Electrophoresis to Study the Reactions of Activated Amino Acids with Oligonucleotides

NASA Technical Reports Server (NTRS)

Zieboll, Gerhard; Orgel, Leslie E.

1994-01-01

We have used gel electrophoresis to study the primary covalent addition of amino acids to oligonu-cleotides or their analogs and the subsequent addition of further molecules of the amino acids to generate peptides covalently linked to the oligonucleotides. We have surveyed the reactions of a variety of amino acids with the phosphoramidates derived from oligonucleotide 5 inches phosphates and ethylenediamine. We find that arginine and amino acids can interact with oligonucleotidesl through stacking interactions react most efficiently. D- and L-amino acids give indistinguishable families of products.

Heavy metal recovery from electric arc furnace steel slag by using hydrochloric acid leaching

NASA Astrophysics Data System (ADS)

Wei, Lim Jin; Haan, Ong Teng; Shean Yaw, Thomas Choong; Chuah Abdullah, Luqman; Razak, Mus'ab Abdul; Cionita, Tezara; Toudehdehghan, Abdolreza

2018-03-01

Electric Arc Furnace steel slag (EAFS) is the waste produced in steelmaking industry. Environmental problem such as pollution will occur when dumping the steel slag waste into the landfill. These steel slags have properties that are suitable for various applications such as water treatment and wastewater. The objective of this study is to develop efficient and economical chlorination route for EAFS extraction by using leaching process. Various parameters such as concentration of hydrochloric acid, particle size of steel slag, reaction time and reaction temperature are investigated to determine the optimum conditions. As a result, the dissolution rate can be determined by changing the parameters, such as concentration of hydrochloric acid, particle size of steel slag, reaction time and reaction temperature. The optimum conditions for dissolution rates for the leaching process is at 3.0 M hydrochloric acid, particle size of 1.18 mm, reaction time of 2.5 hour and the temperature of 90°C.

Determination of total acid content in biomass hydrolysates by solvent-assisted and reaction based headspace gas chromatography.

PubMed

Huang, Liu-Lian; Hu, Hui-Chao; Chen, Li-Hui

2015-11-27

This work reports on a novel method for the determination of total acid (TA) in biomass hydrolysates by a solvent-assisted and reaction-based headspace gas chromatography (HS-GC). The neutralization reaction between the acids in hydrolysates and bicarbonate in an ethanol (50%) aqueous solution was performed in a closed headspace sample vial, from which the carbon dioxide generated from the reaction was detected by HS-GC. It was found that the addition of ethanol can effectively eliminate the precipitation of some organic acids in the biomass hydrolysates. The results showed that the reaction and headspace equilibration can be achieved within 45min at 70°C; the method has a good precision (RSD<3.27%) and accuracy (recovery of 97.4-105%); the limit of quantification is 1.36μmol. The present method is quite suitable to batch analysis of TA content in hydrolysate for the biorefinery related research. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation and Identification of Benzoic Acids and Benzamides: An Organic "Unknown" Lab

NASA Astrophysics Data System (ADS)

Taber, Douglass F.; Nelson, Jade D.; Northrop, John P.

1999-06-01

The reaction of an unknown substituted benzene derivative (illustrated by toluene) with oxalyl chloride and aluminum chloride gives the acid chloride. Hydrolysis of the acid chloride gives the acid, and reaction of the acid with concentrated aqueous ammonia gives the benzamide.

Biodiesel forming reactions using heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Liu, Yijun

Biodiesel synthesis from biomass provides a means for utilizing effectively renewable resources, a way to convert waste vegetable oils and animal fats to a useful product, a way to recycle carbon dioxide for a combustion fuel, and production of a fuel that is biodegradable, non-toxic, and has a lower emission profile than petroleum-diesel. Free fatty acid (FFA) esterification and triglyceride (TG) transesterification with low molecular weight alcohols constitute the synthetic routes to prepare biodiesel from lipid feedstocks. This project was aimed at developing a better understanding of important fundamental issues involved in heterogeneous catalyzed biodiesel forming reactions using mainly model compounds, representing part of on-going efforts to build up a rational base for assay, design, and performance optimization of solid acids/bases in biodiesel synthesis. As FFA esterification proceeds, water is continuously formed as a byproduct and affects reaction rates in a negative manner. Using sulfuric acid (as a catalyst) and acetic acid (as a model compound for FFA), the impact of increasing concentrations of water on acid catalysis was investigated. The order of the water effect on reaction rate was determined to be -0.83. Sulfuric acid lost up to 90% activity as the amount of water present increased. The nature of the negative effect of water on esterification was found to go beyond the scope of reverse hydrolysis and was associated with the diminished acid strength of sulfuric acid as a result of the preferential solvation by water molecules of its catalytic protons. The results indicate that as esterification progresses and byproduct water is produced, deactivation of a Bronsted acid catalyst like H2SO4 occurs. Using a solid composite acid (SAC-13) as an example of heterogeneous catalysts and sulfuric acid as a homogeneous reference, similar reaction inhibition by water was demonstrated for homogeneous and heterogeneous catalysis. This similarity together with other comparisons between the catalytic behaviors of liquid and solid acids suggests a common mode of operation of their Bronsted acid sites in carrying out esterification of a carboxylic acid with alcohol. The hypothesized Eley-Rideal type heterogeneous reaction mechanism involving a nucleophilic attack between adsorbed carboxylic acid and unadsorbed alcohol as the rate-limiting step was found to fit well the experimental observations and successfully predict the esterification rate obtained with SAC-13 as reaction progresses. The SAC-13 catalysis assay was also extended to carboxylic acids of higher molecular weights. A set of carboxylic acids with various alkyl chain lengths was used to investigate the structural effect of reacting carboxylic acids on heterogeneous catalyzed esterification. It was found that the reactivity of carboxylic acids was controlled by steric factors as the alkyl chain linearly lengthened. Despite their increased hydrophobicity, large carboxylic acids hardly impacted the deactivating effect of water on Bronsted acid sites. However, catalyst reusability and regeneration showed significant dependency on the size of the carboxylic acid used. With the use of larger reacting carboxylic acids, SAC-13 underwent more significant activity loss in consecutive reaction cycles due to stronger adsorption of the larger organics in the polymeric domains of the Nafion resin. In parallel to the research activity on acid catalyzed esterification, the use of strong solid bases with organic functionality (quarternary ammonium, QN+) was investigated from a fundamental perspective. Using triacetin as a model compound for TG molecules, the effectiveness of this Bronsted base functionality in transesterification was demonstrated even at mild reaction conditions. But its catalytic behavior including catalyst selectivity and deactivation was significantly affected by the nature of the adopted support. A purposive design of the immobilizing matrix is expected to optimize the activity, selectivity, and stability of the QN+ groups, thus enhancing their applicability in practical biodiesel synthesis from lipid feedstocks. As the solid organic base-matrix composite catalyst remains to be better designed to fit the need of TG methanolysis, inorganic solid bases composed of metal oxides appear to be a more feasible choice given that their thermal robustness generally allows the achievement of sufficient activity by increasing reaction temperature and potentially permits a convenient regeneration by recalcination. A study dealing with the methanolysis of real lipid feedstock (poultry fat) was carried out using Mg-Al hydrotalcite derived catalysts. From a practical standpoint, the impact of a variety of operational variables on reaction, such as catalyst pretreatments, temperature, reactants molar ratio, and usage of co-solvent were addressed. As a result, biodiesel synthesis from poultry fat was successfully conducted by appropriately adjusting these variables. However, many underlying aspects associated with catalyst performance remain unexamined and unexplained.

A Synthesis of "o"-Chlorocinnamic Acid Utilizing a Meerwein Reaction: An Undergraduate Organic Experiment.

ERIC Educational Resources Information Center

Cleland, George H.

1978-01-01

The Meerwein reaction is often omitted from undergraduate organic chemistry laboratory books. This experiment, the preparation of "o"-chlorocinnamic acid from "o"-chloroanaline, illustrates this section. (BB)

Negative influence of pKa on activation energy barrier: A case study for double proton transfer reaction in inorganic acid dimers.

PubMed

Parida, Rakesh; Giri, Santanab

2018-06-15

Strength of acid can be determined by means of pK a value. Attempts have been made to find a relationship between pK a and activation energy barrier for a double proton transfer (DPT) reaction in inorganic acid dimers. Negative influence of pK a is observed on activation energy (E a ) which is contrary to the general convention of pK a . Four different levels of theories with two different basis sets have been used to calculate the activation energy barrier of the DPT reaction in inorganic acid dimers. A model based on first and second order polynomial has been created to find the relationship between activation energy for DPT reaction. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Theoretical stusy of the reaction between 2,2',4' - trihydroxyazobenzene-5-sulfonic acid and zirconium

USGS Publications Warehouse

Fletcher, Mary H.

1960-01-01

Zirconium reacts with 2,2',4'-trihydroxyazobenzene-5-sulfonic acid in acid solutions to Form two complexes in which the ratios of dye to zirconium are 1 to 1 and 2 to 1. Both complexes are true chelates, with zirconium acting as a bridge between the two orthohydroxy dye groups. Apparent equilibrium constants for the reactions to form each of the complexes are determined. The reactions are used as a basis for the determination of the active component in the dye and a graphical method for the determination of reagent purity is described. Four absorption spectra covering the wave length region from 350 to 750 mu are given, which completely define the color system associated with the reactions in solutions where the hydrochloric acid concentration ranges from 0.0064N to about 7N.

Characterization of the reactivity of a silica derived from acid activation of sepiolite with silane by 29Si and 13C solid-state NMR.

PubMed

Valentín, J L; López-Manchado, M A; Posadas, P; Rodríguez, A; Marcos-Fernández, A; Ibarra, L

2006-06-15

The mechanism of the reaction between a silica sample coming from acid treatment of sepiolite (denominated Silsep) and an organosilane, namely bis(triethoxysilylpropyl)tetrasulfane (TESPT), has been evaluated by solid state NMR spectroscopy, being compared with the silanization reaction of a commercial silica. The effect of the silane concentration and temperature on the course of the reaction was considered. Experimental results indicate that the silanization reaction is more effective in the case of Silsep, favoring both the reaction of silane molecules with the filler surface and the reaction between neighboring silane molecules. This different behavior is attributed to structural factors, moisture, and number of acid centers on silica surface. Environmental scanning electron microscopy (ESEM) was used to deposit micrometric water drops on the surface of these samples and to evaluate the proportion and distribution of the organophylization process.

Catalytic Ring Hydrogenation of Benzoic Acid with Supported Transition Metal Catalysts in scCO2

PubMed Central

Wang, Hongjun; Zhao, Fengyu

2007-01-01

The ring hydrogenation of benzoic acid to cyclohexanecarboxylic acid over charcoal-supported transition metal catalysts in supercritical CO2 medium has been studied in the present work. The cyclohexanecarboxylic acid can be produced efficiently in supercritical CO2 at the low reaction temperature of 323 K. The presence of CO2 increases the reaction rate and several parameters have been discussed.

Synthesis of zwitterionic salts of pyridinium-Meldrum acid and barbiturate through unique four-component reactions.

PubMed

Wang, Qi-Fang; Hui, Li; Hou, Hong; Yan, Chao-Guo

2010-03-08

An efficient synthetic procedure for the preparation of the unusual charge-separated pyridinium-Meldrum acid and N,N-dimethylbarbiturate acid zwitterionic salts was developed though a unique one-pot four-component reaction involving pyridine, aromatic aldehyde, Meldrum acid or N,N-dimethylbarbituric acid, and p-nitrobenzyl bromide in acetonitrile. By varying combinations of four components involving nitrogen-containing heterocycles, we conveniently established reactive alpha-halomethylene compounds, aldehydes and beta-dicarbonyl compounds a library of zwitterionic salts.

A stimuli-responsive fluorescence platform for simultaneous determination of d-isoascorbic acid and Tartaric acid based on Maillard reaction product.

PubMed

Zhao, Yanmei; Yuan, Haiyan; Zhang, Xinling; Yang, Jidong

2018-05-05

An activatable fluorescence monitoring platform based on a novel Maillard reaction product from d-glucose and L-arginine was prepared through a facile one-pot approach and applied for simultaneous detection of d-isoascorbic acid and tartaric acid. In this work, the new Maillard reaction product GLA was first obtained, and its fluorescence intensity can be effectively quenched by KMnO 4 , resulting from a new complex (GLA-KMnO 4 ) formation between GLA and KMnO 4 . Upon addition of d-isoascorbic acid or tartaric acid, an enhanced fluorescence was observed under the optimumed experimental conditions, indicating a stimuli-responsive fluorescence turn on platform for d-isoascorbic acid or tartaric acid can be developed. The corresponding experimental results showed that this turn on fluorescence sensing platform has a high sensitivity for d-isoascorbic acid or tartaric acid, because the detection limits were 5.9μM and 21.5μM, respectively. Additionally, this proposed sensing platform was applied to simultaneously detection of d-isoascorbic acid and tartaric acid in real tap water samples with satisfactory results. Copyright © 2018 Elsevier B.V. All rights reserved.

Catalytic total hydrodeoxygenation of biomass-derived polyfunctionalized substrates to alkanes.

PubMed

Nakagawa, Yoshinao; Liu, Sibao; Tamura, Masazumi; Tomishige, Keiichi

2015-04-13

The total hydrodeoxygenation of carbohydrate-derived molecules to alkanes, a key reaction in the production of biofuel, was reviewed from the aspect of catalysis. Noble metals (or Ni) and acid are the main components of the catalysts, and group 6 or 7 metals such as Re are sometimes added as modifiers of the noble metal. The main reaction route is acid-catalyzed dehydration plus metal-catalyzed hydrogenation, and in some systems metal-catalyzed direct CO dissociation is involved. The appropriate active metal, acid strength, and reaction conditions depend strongly on the reactivity of the substrate. Reactions that use Pt or Pd catalysts supported on Nb-based acids or relatively weak acids are suitable for furanic substrates. Carbohydrates themselves and sugar alcohols undergo CC dissociation easily. The systems that use metal-catalyzed direct CO dissociations can give a higher yield of the corresponding alkane from carbohydrates and sugar alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Concordance of Collagen-Based Radiocarbon and Aspartic-Acid Racemization Ages

PubMed Central

Bada, Jeffrey L.; Schroeder, Roy A.; Protsch, Reiner; Berger, Rainer

1974-01-01

By determining the extent of racemization of aspartic acid in a well-dated bone, it is possible to calculate the in situ first-order rate constant for the interconversion of the L and D enantiomers of aspartic acid. Collagen-based radiocarbon-dated bones are shown to be suitable samples for use in “calibrating” the racemization reaction. Once the aspartic-acid racemization reaction has been “calibrated” for a site, the reaction can be used to date other bones from the deposit. Ages deduced by this method are in good agreement with radiocarbon ages. These results provide evidence that the aspartic-acid racemization reaction is an important chronological tool for dating bones either too old or too small for radiocarbon dating. As an example of the potential application of the technique for dating fossil man, a piece of Rhodesian Man from Broken Hill, Zambia, was analyzed and tentatively assigned an age of about 110,000 years. PMID:4522802

Recovery of acetic acid from dilute aqueous solutions using catalytic dehydrative esterification with ethanol.

PubMed

Yagyu, Daisuke; Ohishi, Tetsuo; Igarashi, Takeshi; Okumura, Yoshikuni; Nakajo, Tetsuo; Mori, Yuichiro; Kobayashi, Shū

2013-03-01

We have developed a direct esterification of aqueous acetic acid with ethanol (molar ratio=1:1) catalyzed by polystyrene-supported or homogeneous sulfonic acids toward the recovery of acetic acid from wastewater in chemical plants. The equilibrium yield was significantly increased by the addition of toluene, which had a high ability to extract ethyl acetate from the aqueous phase. It was shown that low-loading and alkylated polystyrene-supported sulfonic acid efficiently accelerated the reaction. These results suggest that the construction of hydrophobic reaction environments in water was critical in improving the chemical yield. Addition of inorganic salts was also effective for the reaction under not only biphasic conditions (toluene-water) but also toluene-free conditions, because the mutual solubility of ethyl acetate and water was suppressed by the salting-out effect. Among the tested salts, CaCl(2) was found to be the most suitable for this reaction system. Copyright © 2012 Elsevier Ltd. All rights reserved.

Catalytic actions of alkaline salts in reactions between 1,2,3,4-butanetetracarboxylic acid and cellulose: II. Esterification.

PubMed

Ji, Bolin; Tang, Peixin; Yan, Kelu; Sun, Gang

2015-11-05

1,2,3,4-Butanetetracarboxylic acid (BTCA) reacts with cellulose in two steps with catalysis of alkaline salts such as sodium hypophosphite: anhydride formation and esterification of anhydride with cellulose. The alkali metal ions were found effective in catalyzing formation of BTCA anhydride in a previous report. In this work, catalytic functions of the alkaline salts in the esterification reaction between BTCA anhydride and cellulose were investigated. Results revealed that acid anions play an important role in the esterification reaction by assisting removal of protons on intermediates and completion of the esterification between cellulose and BTCA. Besides, alkaline salts with lower pKa1 values of the corresponding acids are more effective ones for the reaction since addition of these salts could lead to lower pH values and higher acid anion concentrations in finishing baths. The mechanism explains the results of FTIR and wrinkle recovery angles of the fabrics cured under different temperatures and times. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solvent-Free Conversion of Alpha-Naphthaldehyde to 1-Naphthoic Acid and 1-Naphthalenemethanol: Application of the Cannizzaro Reaction

ERIC Educational Resources Information Center

Esteb, John J.; Gligorich, Keith M.; O'Reilly, Stacy A.; Richter, Jeremy M.

2004-01-01

A mixture of potassium hydroxide and alpha-naphthaldehyde (1) are heated under solvent-free conditions to produce 1-naphthoic acid (2) and 1-naphthalenemethanol (3). The experiment offers several advantages over many existing exercises including the ease of reaction workup, shorter reaction time, relative environmental friendliness of the…

40 CFR Appendix V to Part 265 - Examples of Potentially Incompatible Waste

Code of Federal Regulations, 2010 CFR

2010-07-01

... pressure, (2) fire or explosion, (3) violent reaction, (4) toxic dusts, mists, fumes, or gases, or (5... analyze his wastes so that he can avoid creating uncontrolled substances or reactions of the type listed... mixed in a way that precludes a reaction (e.g., adding acid to water rather than water to acid) or that...

40 CFR Appendix V to Part 265 - Examples of Potentially Incompatible Waste

Code of Federal Regulations, 2011 CFR

2011-07-01

... pressure, (2) fire or explosion, (3) violent reaction, (4) toxic dusts, mists, fumes, or gases, or (5... analyze his wastes so that he can avoid creating uncontrolled substances or reactions of the type listed... mixed in a way that precludes a reaction (e.g., adding acid to water rather than water to acid) or that...

40 CFR Appendix V to Part 264 - Examples of Potentially Incompatible Waste

Code of Federal Regulations, 2011 CFR

2011-07-01

... explosion, (3) violent reaction, (4) toxic dusts, mists, fumes, or gases, or (5) flammable fumes or gases... can avoid creating uncontrolled substances or reactions of the type listed below, whether they are... precludes a reaction (e.g., adding acid to water rather than water to acid) or that neutralizes them (e.g...

Reaction pH of urea-formaldehyde resins as related to strength properties of southern pine particleboard

Treesearch

C. -Y. Hse

1974-01-01

Twelve urea-formaldehyde resins were prepared with factorial combinations of 4 alkaline and 3 acidic reaction phases; i. e., the reaction mixture was adjusted to pH 7, 8, 9, or 10 for the first hour and then made weakly acid to pH 5.8, 4.8, or 3.8.

Reaction of atomic hydrogen with formic acid.

PubMed

Cao, Qian; Berski, Slawomir; Latajka, Zdzislaw; Räsänen, Markku; Khriachtchev, Leonid

2014-04-07

We study the reaction of atomic hydrogen with formic acid and characterize the radical products using IR spectroscopy in a Kr matrix and quantum chemical calculations. The reaction first leads to the formation of an intermediate radical trans-H2COOH, which converts to the more stable radical trans-cis-HC(OH)2via hydrogen atom tunneling on a timescale of hours at 4.3 K. These open-shell species are observed for the first time as well as a reaction between atomic hydrogen and formic acid. The structural assignment is aided by extensive deuteration experiments and ab initio calculations at the UMP2 and UCCSD(T) levels of theory. The simplest geminal diol radical trans-cis-HC(OH)2 identified in the present work as the final product of the reaction should be very reactive, and further reaction channels are of particular interest. These reactions and species may constitute new channels for the initiation and propagation of more complex organic species in the interstellar clouds.

Study on Al2O3 extraction from activated coal gangue under different calcination atmospheres

NASA Astrophysics Data System (ADS)

Dong, Ling; Liang, Xinxing; Song, Qiang; Gao, Gewu; Song, Lihua; Shu, Yuanfeng; Shu, Xinqian

2017-12-01

Coal gangue was calcinated under air, nitrogen, carbon dioxide, air-hydrogen, and hydrogen atmospheres. The effects of different calcination temperatures and atmospheres on the mineral composition of activated coal gangue were investigated by X-ray diffraction. Moreover, the acid leaching kinetics of aluminum oxide from coal gangue was investigated with sulfuric acid. It showed that the air atmosphere promoted kaolinite decomposition during coal gangue calcination. The hydrogen atmosphere promoted the activation and decomposition of kaolinite at reaction temperatures exceeding 650°C. The carbon dioxide atmosphere eliminated the influence of residual carbon on coal gangue. When the ratio of acid/coal gangue was 1.5 and reaction temperature was 650°C, the sulfuric acid leaching rate under air, air-hydrogen, carbon dioxide, hydrogen and nitrogen atmospheres were 93.66%, 90.90%, 84.06%, 81.91% and 77.54% respectively. The acid leaching reaction process conformed to unreacted shrinking core model of particle unchanged, and was controlled by the interfacial chemical reaction. The reaction kinetic equation for the leaching process was 1-(1-x)1/3=kt with an apparent activation energy of 48.97 kJ/mol.

Methods for preparation of cyclopentadienyliron (II) arenes

DOEpatents

Keipert, Steven J.

1991-01-01

Two improved methods for preparation of compounds with the structure shown in equation X [(Cp)--Fe--(Ar)].sup.+.sub.b X.sup.b- (X) where Cp is an eta.sup.5 complexed, substituted or unsubstituted, cyclopentadienyl or indenyl anion, Ar is an eta.sup.6 complexed substituted or unsubstituted, pi-arene ligand anad X is a b-valent anion where b is an integer between 1 and 3. The two methods, which differ in the source of the cyclopentadienyl anion - Lewis acid complex, utilize a Lewis acid assisted ligand transfer reaction. The cyclopentadienyl anion ligand, assisted by a Lewis acid is transferred to ferrous ion in the presence of an arene. In the first method, the cyclopentadienyl anion is derived from ferrocene and ferrous chloride. In this reaction, the cyclopentadienyliron (II) arene product is derived partially from ferrocene and partially from the ferrous salt. In the second method, the cyclopentadienyl anion - Lewis acid complex is formed by direct reaction of the Lewis acid with an inorganic cyclopentadienide salt. The cyclopentadienyliron (II) arene product of this reaction is derived entirely from the ferrous salt. Cyclopentadienyliron (II) arene cations are of great interest due to their utility as photoactivatable catalysts for a variety of polymerization reactions.

Ethanesulfonic acid-based esterification of industrial acidic crude palm oil for biodiesel production.

PubMed

Hayyan, Adeeb; Mjalli, Farouq S; Hashim, Mohd Ali; Hayyan, Maan; AlNashef, Inas M; Al-Zahrani, Saeed M; Al-Saadi, Mohammed A

2011-10-01

An industrial grade acidic crude palm oil (ACPO) pre-treatment process was carried out using ethanesulfonic acid (ESA) as a catalyst in the esterification reaction. ESA was used in different dosages to reduce free fatty acid (FFA) to a minimum level for the second stage of biodiesel production via alkaline transesterification reaction. Different process operating conditions were optimized such as ESA dosage (0.25-3.5% wt/wt), methanol to ACPO molar ratio (1:1-20:1), reaction temperature (40-70 °C), and reaction time (3-150 min). This study revealed the potential use of abundant quantities of ACPO from oil palm mills for biodiesel production. The lab scale results showed the effectiveness of the pre-treatment process using ESA catalyst. Three consecutive catalyst recycling runs were achieved without significant degradation in its performance. Second and third reuse runs needed more reaction time to achieve the target level of FFA content. Esterification and transesterification using ESA and KOH respectively is proposed for biodiesel industrial scale production. The produced biodiesel meets the international standards specifications for biodiesel fuel (EN 14214 and ASTM D6751). Copyright © 2011 Elsevier Ltd. All rights reserved.

A Successful Replacement of Phenols with Isocyanides in the Bargellini Reaction: Synthesis of 3-Carboxamido-Isobutyric Acids.

PubMed

Giustiniano, Mariateresa; Pelliccia, Sveva; Galli, Ubaldina; Amato, Jussara; Travagin, Fabio; Novellino, Ettore; Tron, Gian Cesare

2016-11-18

Old multicomponent reactions are still a source of inspiration for discovering novel combinations of three or more reactants. A simple idea is to replace one of the educts of a known multicomponent reaction with another functional group and still be able to mimic the same reactivity. Following this line of thought, we report a three-component reaction in which isocyanides are able to open the epoxide intermediate of the Bargellini reaction affording 3-carboxamido-isobutyric acids in yields of 47-95%.

Recombinant human glutathione S-transferases catalyse enzymic isomerization of 13-cis-retinoic acid to all-trans-retinoic acid in vitro.

PubMed Central

Chen, H; Juchau, M R

1998-01-01

The steric conversion of 13-cis-retinoic acid (13-cRA) to all-trans-retinoic acid (t-RA) has been proposed as an activation mechanism for the observed therapeutic and teratogenic activities of 13-cRA. Here we have investigated the catalysis of isomerization of 13-cRA to t-RA by recombinant human glutathione S-transferases (GSTs). Substrate was incubated with GST in 0.1 M sodium phosphate buffer, pH 7.5, at 37 degrees C in total darkness. The t-RA generated was measured quantitatively by HPLC. Under the reaction conditions used, GSTP1-1 was far more effective than human GSTM1-1 or human GSTA1-1 in catalysing the isomerization reaction. The reaction catalysed by GSTP1-1 showed substrate saturation and the Km and Vmax values for the reaction were approx. 7 microM and 650 pmol/min per nmol respectively. The reaction rate increased linearly with increasing enzyme concentration. The reaction was inhibited both by heat treatment and by S-decylglutathione (a potent inhibitor of transferase activity associated with GST). Additions of polyclonal rabbit antiserum for human GSTP1-1 to the reaction resulted in a significant decrease in generation of t-RA (70-80%). In addition, ethacrynic acid, a selective substrate for Pi isoforms of GST, also inhibited the isomerization of 13-cRA to t-RA catalysed by GSTP1-1. Under the same reaction conditions, GSTP1-1 was much less effective in catalysing the steric conversion of 9-cis-retinoic acid to t-RA, indicating that the enzyme was stereospecific for the conversion of 13-cRA to t-RA. These observations suggest that enzymic catalysis was the primary mechanism for the GSTP1-1-dependent conversion of 13-cRA to t-RA. Reactions catalysed by a purified rat hepatic GST Pi isoenzyme proceeded more slowly than reactions catalysed by human GSTP1-1. Comparative studies also showed that there were marked species differences in catalytic activities between various purified mammalian hepatic GST mixtures. PMID:9806904

Recombinant human glutathione S-transferases catalyse enzymic isomerization of 13-cis-retinoic acid to all-trans-retinoic acid in vitro.

PubMed

Chen, H; Juchau, M R

1998-11-15

The steric conversion of 13-cis-retinoic acid (13-cRA) to all-trans-retinoic acid (t-RA) has been proposed as an activation mechanism for the observed therapeutic and teratogenic activities of 13-cRA. Here we have investigated the catalysis of isomerization of 13-cRA to t-RA by recombinant human glutathione S-transferases (GSTs). Substrate was incubated with GST in 0.1 M sodium phosphate buffer, pH 7.5, at 37 degrees C in total darkness. The t-RA generated was measured quantitatively by HPLC. Under the reaction conditions used, GSTP1-1 was far more effective than human GSTM1-1 or human GSTA1-1 in catalysing the isomerization reaction. The reaction catalysed by GSTP1-1 showed substrate saturation and the Km and Vmax values for the reaction were approx. 7 microM and 650 pmol/min per nmol respectively. The reaction rate increased linearly with increasing enzyme concentration. The reaction was inhibited both by heat treatment and by S-decylglutathione (a potent inhibitor of transferase activity associated with GST). Additions of polyclonal rabbit antiserum for human GSTP1-1 to the reaction resulted in a significant decrease in generation of t-RA (70-80%). In addition, ethacrynic acid, a selective substrate for Pi isoforms of GST, also inhibited the isomerization of 13-cRA to t-RA catalysed by GSTP1-1. Under the same reaction conditions, GSTP1-1 was much less effective in catalysing the steric conversion of 9-cis-retinoic acid to t-RA, indicating that the enzyme was stereospecific for the conversion of 13-cRA to t-RA. These observations suggest that enzymic catalysis was the primary mechanism for the GSTP1-1-dependent conversion of 13-cRA to t-RA. Reactions catalysed by a purified rat hepatic GST Pi isoenzyme proceeded more slowly than reactions catalysed by human GSTP1-1. Comparative studies also showed that there were marked species differences in catalytic activities between various purified mammalian hepatic GST mixtures.

Catalytic effects of glycine on prebiotic divaline and diproline formation.

PubMed

Plankensteiner, Kristof; Reiner, Hannes; Rode, Bernd M

2005-07-01

The catalytic effects of the simple amino acid glycine on the formation of diproline and divaline in the prebiotically relevant salt-induced peptide formation (SIPF) reaction was investigated in systems of different amino acid starting concentrations and using the two enantiomeric forms of the respective amino acid. Results show an improved applicability of the SIPF reaction to prebiotic conditions, especially at low amino acid concentrations, as presumably present in a primordial scenario, and indicate excellent conditions and resources for chemical evolution of peptides and proteins on the early earth. For valine, furthermore differences in catalytic yield increase are found indicating a chiral selectivity of the active copper complex of the reaction and showing a connection to previously found enantiomeric differences in complex formation constants with amino acids.

Enzymatic production of infant milk fat analogs containing palmitic acid: optimization of reactions by response surface methodology.

PubMed

Maduko, C O; Akoh, C C; Park, Y W

2007-05-01

Infant milk fat analogs resembling human milk fat were synthesized by an enzymatic interesterification between tripalmitin, coconut oil, safflower oil, and soybean oil in hexane. A commercially immobilized 1,3-specific lipase, Lipozyme RM IM, obtained from Rhizomucor miehei was used as a biocatalyst. The effects of substrate molar ratio, reaction time, and incubation temperature on the incorporation of palmitic acid at the sn-2 position of the triacylglycerols were investigated. A central composite design with 5 levels and 3 factors consisting of substrate ratio, reaction temperature, and incubation time was used to model and optimize the reaction conditions using response surface methodology. A quadratic model using multiple regressions was then obtained for the incorporation of palmitic acid at the sn-2 positions of glycerols as the response. The coefficient of determination (R2) value for the model was 0.845. The incorporation of palmitic acid appeared to increase with the decrease in substrate molar ratio and increase in reaction temperature, and optimum incubation time occurred at 18 h. The optimal conditions generated from the model for the targeted 40% palmitic acid incorporation at the sn-2 position were 3 mol/mol, 14.4 h, and 55 degrees C; and 2.8 mol/mol, 19.6 h, and 55 degrees C for substrate ratio (moles of total fatty acid/moles of tripalmitin), time, and temperature, respectively. Infant milk fat containing fatty acid composition and sn-2 fatty acid profile similar to human milk fat was successfully produced. The fat analogs produced under optimal conditions had total and sn-2 positional palmitic acid levels comparable to that of human milk fat.

The major components of particles emitted during recycling of waste printed circuit boards in a typical e-waste workshop of South China

NASA Astrophysics Data System (ADS)

Bi, Xinhui; Simoneit, Bernd R. T.; Wang, ZhenZhen; Wang, Xinming; Sheng, Guoying; Fu, Jiamo

2010-11-01

Electronic waste from across the world is dismantled and disposed of in China. The low-tech recycling methods have caused severe air pollution. Air particle samples from a typical workshop of South China engaged in recycling waste printed circuit boards have been analyzed with respect to chemical constituents. This is the first report on the chemical composition of particulate matter (PM) emitted in an e-waste recycling workshop of South China. The results show that the composition of PM from this recycling process was totally different from other emission sources. Organic matter comprised 46.7-51.6% of the PM. The major organic constituents were organophosphates consisting mainly of triphenyl phosphate (TPP) and its methyl substituted compounds, methyl esters of hexadecanoic and octadecanoic acids, levoglucosan and bisphenol A. TPP and bisphenol A were present at 1-5 orders of magnitude higher than in other indoor and outdoor environments throughout the world, which implies that they might be used as potential markers for e-waste recycling. The elemental carbon, inorganic elements and ions had a minor contribution to the PM (<5% each). The inorganic elements were dominated by phosphorus and followed by crustal elements and metal elements Pb, Zn, Sn, and lesser Cu, Sb, Mn, Ni, Ba and Cd. The recycling of printed circuit boards was demonstrated as an important contributor of heavy metal contamination, particularly Cd, Pb and Ni, to the local environment. These findings suggest that this recycling method represents a strong source of PM associated with pollutants to the ambient atmosphere of an e-waste recycling locale.

A concise synthesis of benzimidazoles via the microwave-assisted one-pot batch reaction of amino acids up to a 10-g scale.

PubMed

Peng, Pai; Xiong, Jin-Feng; Mo, Guang-Zhen; Zheng, Jia-Li; Chen, Ren-Hong; Chen, Xiao-Yun; Wang, Zhao-Yang

2014-10-01

An efficient method for the synthesis of aminomethyl benzimidazoles is developed by using a one-pot batch reaction between amino acids and o-phenylenediamines. This reaction proceeds smoothly in an unmodified household microwave oven, even though scale-up is to 10 g. A desirable method for the quick synthesis of benzimidazoles, which are used as a kind of important intermediates in drug synthesis, is provided by the scale-up utilization of amino acid resource.

Organocatalyzed, Visible-Light Photoredox-Mediated, One-Pot Minisci Reaction Using Carboxylic Acids via N-(Acyloxy)phthalimides.

PubMed

Sherwood, Trevor C; Li, Ning; Yazdani, Aliza N; Dhar, T G Murali

2018-03-02

An improved, one-pot Minisci reaction has been developed using visible light, an organic photocatalyst, and carboxylic acids as radical precursors via the intermediacy of in situ-generated N-(acyloxy)phthalimides. The conditions employed are mild, demonstrate a high degree of functional group tolerance, and do not require a large excess of the carboxylic acid reactant. As a result, this reaction can be applied to drug-like scaffolds and molecules with sensitive functional groups, enabling late-stage functionalization, which is of high interest to medicinal chemistry.

N-N bond formation in Ugi processes: from nitric acid to libraries of nitramines.

PubMed

Mercalli, Valentina; Nyadanu, Aude; Cordier, Marie; Tron, Gian Cesare; Grimaud, Laurence; El Kaim, Laurent

2017-02-09

The Ugi reaction has drawn considerable attention over the years leading to numerous libraries of heterocycles and various extensions changing the nature of the components of the coupling. We report here the use of nitric acid as carboxylic acids surrogates, displaying the first aminative Ugi-type reaction leading to nitramines.

The H[subscript 3]PO[subscript 4] Acid Ionization Reactions: A Capstone Multiconcept Thermodynamics General Chemistry Laboratory Exercise

ERIC Educational Resources Information Center

Nyasulu, Frazier; Barlag, Rebecca; Wise, Lindy; McMills, Lauren

2013-01-01

The thermodynamic properties of weak acid ionization reactions are determined. The thermodynamic properties are corresponding values of the absolute temperature (T), the weak acid equilibrium constant (K[subscript a]), the enthalpy of ionization (delta[subscript i]H[degrees]), and the entropy of ionization (delta[subscript i]S[degrees]). The…

Diastereoselective radical addition to γ-alkyl-α-methylene-γ-butyrolactams and the synthesis of a chiral pyroglutamic acid derivative.

PubMed

Yajima, Tomoko; Yoshida, Eriko; Hamano, Masako

2013-01-01

The cis- and trans-stereoselective radical additions to α-methylene-γ-alkyl- γ-lactams were investigated and the scope and limitation of the reaction were also revealed. This stereoselective radical reaction was used for synthesis of chiral pyroglutamic acid derivatives starting from a commercially available chiral amino acid.

Tandem catalysis for the production of alkyl lactates from ketohexoses at moderate temperatures

DOE PAGES

Orazov, Marat; Davis, Mark E.

2015-09-08

Retro-aldol reactions have been implicated as the limiting steps in catalytic routes to convert biomass-derived hexoses and pentoses into valuable C2, C3, and C4 products such as glycolic acid, lactic acid, 2-hydroxy-3-butenoic acid, 2,4-dihydroxybutanoic acid, and alkyl esters thereof. Due to a lack of efficient retro-aldol catalysts, most previous investigations of catalytic pathways involving these reactions were conducted at high temperatures (≥160 °C). Here, we report moderate-temperature (around 100 °C) retro-aldol reactions of various hexoses in aqueous and alcoholic media with catalysts traditionally known for their capacity to catalyze 1,2-intramolecular carbon shift (1,2-CS) reactions of aldoses, i.e., various molybdenum oxidemore » and molybdate species, nickel(II) diamine complexes, alkali-exchanged stannosilicate molecular sieves, and amorphous TiO2–SiO2 coprecipitates. Solid Lewis acid cocatalysts that are known to catalyze 1,2-intramolecular hydride shift (1,2-HS) reactions that enable the formation of α-hydroxy carboxylic acids from tetroses, trioses, and glycolaldehyde, but cannot readily catalyze retro-aldol reactions of hexoses and pentoses at these moderate temperatures, are shown to be compatible with the aforementioned retro-aldol catalysts. The combination of a distinct retro-aldol catalyst with a 1,2-HS catalyst enables lactic acid and alkyl lactate formation from ketohexoses at moderate temperatures (around 100 °C), with yields comparable to best-reported chemocatalytic examples at high temperature conditions (≥160 °C). The use of moderate temperatures enables numerous desirable features such as lower pressure and significantly less catalyst deactivation.« less

Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid.

PubMed

Sustaita-Rodríguez, Alejandro; Ramos-Sánchez, Víctor H; Camacho-Dávila, Alejandro A; Zaragoza-Galán, Gerardo; Espinoza-Hicks, José C; Chávez-Flores, David

2018-04-11

Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1 H NMR, 13 C NMR and GC-MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

Two-stage acid saccharification of fractionated Gelidium amansii minimizing the sugar decomposition.

PubMed

Jeong, Tae Su; Kim, Young Soo; Oh, Kyeong Keun

2011-11-01

Two-stage acid hydrolysis was conducted on easy reacting cellulose and resistant reacting cellulose of fractionated Gelidium amansii (f-GA). Acid hydrolysis of f-GA was performed at between 170 and 200 °C for a period of 0-5 min, and an acid concentration of 2-5% (w/v, H2SO4) to determine the optimal conditions for acid hydrolysis. In the first stage of the acid hydrolysis, an optimum glucose yield of 33.7% was obtained at a reaction temperature of 190 °C, an acid concentration of 3.0%, and a reaction time of 3 min. In the second stage, a glucose yield of 34.2%, on the basis the amount of residual cellulose from the f-GA, was obtained at a temperature of 190 °C, a sulfuric acid concentration of 4.0%, and a reaction time 3.7 min. Finally, 68.58% of the cellulose derived from f-GA was converted into glucose through two-stage acid saccharification under aforementioned conditions. Copyright © 2011 Elsevier Ltd. All rights reserved.

Recent Selected Ion Flow Tube (SIFT) Studies Concerning the Formation of Amino Acids in the Gas Phase

NASA Technical Reports Server (NTRS)

Jackson, Douglas M.; Adams, Nigel G.; Babcock, Lucia M.

2006-01-01

Recently the simplest amino acid, glycine, has been detected in interstellar clouds, ISC, although this has since been contested. In order to substantiate either of these claims, plausible routes to amino acids need to be investigated. For gas phase synthesis, the SIFT technique has been employed to study simple amino acids via ion-molecule reactions of several ions of interstellar interest with methylamine, ethylamine, formic acid, acetic acid, and methyl formate. Carboxylic acid type ions were considered in the reactions involving the amines. In reactions where the carboxylic acid and methyl formate neutrals were studied, the reactant ions were primarily amine ion fragments. It was observed that the amines and acids preferentially fragment or accept a proton whenever energetically possible. NH3(+), however, uniquely reacted with the neutrals via atom abstraction to form NH4(+). These studies yielded a body of data relevant to astrochemistry, supplementing the available literature. However, the search for gas phase routes to amino acids using conventional molecules has been frustrated. Our most recent research investigates the fragmentation patterns of several amino acids and several possible routes have been suggested for future study.

Amino acid-based dithiazines: synthesis and photofragmentation of their benzaldehyde adducts.

PubMed

Kurchan, Alexei N; Kutateladze, Andrei G

2002-11-14

Alpha-amino acids and GABA are functionalized with dithiazine rings via reaction with sodium hydrosulfide in aqueous formaldehyde. The resulting dithiazines are lithiated at -78 degrees C and reacted with benzaldehyde furnishing amino acid-based 2,5-bis-substituted dithiazines. These adducts undergo externally sensitized photofragmentation with quantum efficiency comparable to that of the parent dithiane adducts, thus offering a novel approach to amino acid-based photolabile tethers. [reaction: see text

The mechanism of hydrothermal hydrolysis for glycyrrhizic acid into glycyrrhetinic acid and glycyrrhetinic acid 3-O-mono-β-D-glucuronide in subcritical water.

PubMed

Fan, Rui; Li, Nan; Xu, Honggao; Xiang, Jun; Wang, Lei; Gao, Yanxiang

2016-01-01

To improve the bioactivity and sweetness properties of glycyrrhizic acid (GL), the hydrothermal hydrolysis of GL into glycyrrhetinic acid (GA) and glycyrrhetinic acid 3-O-mono-β-D-glucuronide (GAMG) in subcritical water was investigated. The effects of temperature, time and their interaction on the conversion ratios were analyzed and the reactions were elaborated with kinetics and thermodynamics. The results showed that GL hydrothermal hydrolysis was significantly (P < 0.05) affected by reaction time and temperature, as well as their interaction, and could be fitted into first-order kinetics. The thermodynamic analysis indicated that the hydrolysis of GL was endergonic and non-spontaneous. The hydrolytic pathways were composed of complex consecutive and parallel reactions. It was concluded that subcritical water may be a potential medium for producing GAMG and GA. Copyright © 2015 Elsevier Ltd. All rights reserved.

n-hydrocarbons conversions over metal-modified solid acid catalysts

NASA Astrophysics Data System (ADS)

Zarubica, A.; Ranđelović, M.; Momčilović, M.; Radulović, N.; Putanov, P.

2013-12-01

The quality of a straight-run fuel oil can be improved if saturated n-hydrocarbons of low octane number are converted to their branched counterparts. Poor reactivity of traditional catalysts in isomerization reactions imposed the need for the development of new catalysts among which noble metal promoted acid catalysts, liquid and/or solid acid catalysts take a prominent place. Sulfated zirconia and metal promoted sulfated zirconia exhibit high activity for the isomerization of light alkanes at low temperatures. The present paper highlights the original results which indicate that the modification of sulfated zirconia by incorporation of metals (platinum and rhenium) significantly affects catalytic performances in n-hydrocarbon conversion reactions. Favourable activity/selectivity of the promoted sulfated zirconia depends on the crystal phase composition, critical crystallites sizes, platinum dispersion, total acidity and type of acidity. Attention is also paid to the recently developed solid acid catalysts used in other conversion reactions of hydrocarbons.

Synthesis of glycerol mono-laurate from lauric acid and glycerol for food antibacterial additive

NASA Astrophysics Data System (ADS)

Setianto, W. B.; Wibowo, T. Y.; Yohanes, H.; Illaningtyas, F.; Anggoro, D. D.

2017-05-01

Synthesis of glycerol mono-laurate (GML) has been performed using esterification reaction of glycerol and lauric acid. The reaction was performed at the condition of temperature of 120-140 °C within 7 hour, variation of molar ratio of glycerol - lauric acid, and was using heterogeneous catalyst of zeolist Y. Without catalyst dealumination the maximum acid conversion was 78%, with GML contained in the sample was 38.6%, and it was obtained at the reaction condition of 140 oC, 15wt% catalyst, and 8:1 molar ratio of glycerol - lauric acid. At the same condition, using dealuminated catalyst, the maximum acid conversion was increased up to 98%, with GML contained in the sample was 50.4%. The GML antibacterial activity was examined. It was observed that the GML has antibacterial activity against gram positive bacterial such as B. cereus and S. aureus.

Optimization of the Synthesis of Structured Phosphatidylcholine with Medium Chain Fatty Acid.

PubMed

Ochoa-Flores, Angélica A; Hernández-Becerra, Josafat A; Cavazos-Garduño, Adriana; Vernon-Carter, Eduardo J; García, Hugo S

2017-11-01

Structured phosphatidylcholine was successfully produced by acidolysis between phosphatidylcholine and free medium chain fatty acid, using phospholipase A 1 immobilized on Duolite A568. Response surface methodology was applied to optimize the reaction system using three process parameters: molar ratio of substrates (phosphatidylcholine to free medium chain fatty acid), enzyme loading, and reaction temperature. All parameters evaluated showed linear and quadratic significant effects on the production of modified phosphatidylcholine; molar ratio of substrates contributed positively, but temperature influenced negatively. Increased enzyme loading also led to increased production of modified phosphatidylcholine but only during the first 9 hours of the acidolysis reaction. Optimal conditions obtained from the model were a ratio of phosphatidylcholine to free medium chain fatty acid of 1:15, an enzyme loading of 12%, and a temperature of 45°C. Under these conditions a production of modified phosphatidylcholine of 52.98 % were obtained after 24 h of reaction. The prediction was confirmed from the verification experiments; the production of modified phosphatidylcholine was 53.02%, the total yield of phosphatidylcholine 64.28% and the molar incorporation of medium chain fatty acid was 42.31%. The acidolysis reaction was scaled-up in a batch reactor with a similar production of modified phosphatidylcholine, total yield of phosphatidylcholine and molar incorporation of medium chain fatty acid. Purification by column chromatography of the structured phosphatidylcholine yielded 62.53% of phosphatidylcholine enriched with 42.52% of medium chain fatty acid.

Theoretical chemical kinetic study of the H-atom abstraction reactions from aldehydes and acids by Ḣ atoms and ȮH, HȮ2, and ĊH3 radicals.

PubMed

Mendes, Jorge; Zhou, Chong-Wen; Curran, Henry J

2014-12-26

We have performed a systematic, theoretical chemical kinetic investigation of H atom abstraction by Ḣ atoms and ȮH, HȮ2, and ĊH3 radicals from aldehydes (methanal, ethanal, propanal, and isobutanal) and acids (methanoic acid, ethanoic acid, propanoic acid, and isobutanoic acid). The geometry optimizations and frequencies of all of the species in the reaction mechanisms of the title reactions were calculated using the MP2 method and the 6-311G(d,p) basis set. The one-dimensional hindered rotor treatment for reactants and transition states and the intrinsic reaction coordinate calculations were also determined at the MP2/6-311G(d,p) level of theory. For the reactions of methanal and methanoic acid with Ḣ atoms and ȮH, HȮ2, and ĊH3 radicals, the calculated relative electronic energies were obtained with the CCSD(T)/cc-pVXZ (where X = D, T, and Q) method and were extrapolated to the complete basis set limit. The electronic energies obtained with the CCSD(T)/cc-pVTZ method were benchmarked against the CCSD(T)/CBS energies and were found to be within 1 kcal mol(-1) of one another. Thus, the energies calculated using the less expensive CCSD(T)/cc-pVTZ method were used in all of the reaction mechanisms and in calculating our high-pressure limit rate constants for the title reactions. Rate constants were calculated using conventional transition state theory with an asymmetric Eckart tunneling correction, as implemented in Variflex. Herein, we report the individual and average rate constants, on a per H atom basis, and total rate constants in the temperature range 500-2000 K. We have compared some of our rate constant results to available experimental and theoretical data, and our results are generally in good agreement.

Stereospecific synthesis of syn-α-oximinoamides by a three-component reaction of isocyanides, syn-chlorooximes, and carboxylic acids.

PubMed

Pirali, Tracey; Mossetti, Riccardo; Galli, Simona; Tron, Gian Cesare

2011-07-15

A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acids provides an efficient synthesis of biologically relevant syn-α-oximinoamides. © 2011 American Chemical Society

21 CFR 175.260 - Partial phosphoric acid esters of polyester resins.

Code of Federal Regulations, 2010 CFR

2010-04-01

... resins are prepared by the reaction of trimellitic anhydride with 2,2-dimethyl-1,3-propanediol followed by reaction of the resin thus produced with phosphoric acid anhydride to produce a resin having an...

An experimental study of tissue reaction to hyaluronic acid (Restylane) and polymethylmethacrylate (Metacrill) in the mouse.

PubMed

Rosa, Simone C; Macedo, Jefferson L S; Magalhães, Albino V

2012-10-01

The aging skin is a challenge for medical science. Plastic surgeons and dermatologists are called every day to solve problems like filling wrinkles or folds. The material used must be biocompatible because abnormal reactions may cause catastrophic results. This study analyzes the biological behavior of polymethylmethacrylate (Metacrill) and hyaluronic acid (Restylane), using a histopathologic study in mice. A prospective study was performed using 40 mice for each substance: polymethylmethacrylate or hyaluronic acid was injected into the right ear, the left ear been used as a control. Histopathologic analyses of the right ear, liver, and kidney were performed at intervals during the study and revealed the development of a granulomatous reaction with fibrosis and absorption of spheres and signs of liver and kidney sistematization for polymethylmethacrylate. A discrete cellular reaction, with less formation of fibrosis, and no giant cells were seen in the mice injected with hyaluronic acid.

How the folding rates of two- and multistate proteins depend on the amino acid properties.

PubMed

Huang, Jitao T; Huang, Wei; Huang, Shanran R; Li, Xin

2014-10-01

Proteins fold by either two-state or multistate kinetic mechanism. We observe that amino acids play different roles in different mechanism. Many residues that are easy to form regular secondary structures (α helices, β sheets and turns) can promote the two-state folding reactions of small proteins. Most of hydrophilic residues can speed up the multistate folding reactions of large proteins. Folding rates of large proteins are equally responsive to the flexibility of partial amino acids. Other properties of amino acids (including volume, polarity, accessible surface, exposure degree, isoelectric point, and phase transfer energy) have contributed little to folding kinetics of the proteins. Cysteine is a special residue, it triggers two-state folding reaction and but inhibits multistate folding reaction. These findings not only provide a new insight into protein structure prediction, but also could be used to direct the point mutations that can change folding rate. © 2014 Wiley Periodicals, Inc.

Efficient Synthesis and Antimicrobial Evaluation of Pyrazolopyranopyrimidines in the Presence of SBA-Pr-SO3H as a Nanoporous Acid Catalyst

PubMed Central

Mohammadi Ziarani, Ghodsi; Aleali, Faezeh; Lashgari, Negar; Badiei, Alireza; Abolhasani Soorki, Ali

2018-01-01

A simple, efficient, and environmentally friendly method has been developed for the synthesis of a series of tricyclic fused pyrazolopyranopyrimidines via a one-pot three-component reaction of barbituric acids, aromatic aldehydes, and 3-methyl-5-pyrazolone in the presence of SBA-Pr-SO3H. SBA-15 mesoporous silica material functionalized with propyl sulfonic acid groups was used as a heterogeneous Brønsted acid catalyst with hexagonal structure, high surface area, thick walls, and large uniform pores. All reactions were performed under reflux conditions in water in the presence of a catalytic amount of SBA-Pr-SO3H. High yields, mild reaction conditions, short reaction times, and simple work-up procedures are some advantages of this method. The antimicrobial activities of the synthesized compounds were also evaluated and some products exhibited significant antibacterial activities at low concentrations. PMID:29881410

Acid-Base Chemistry According to Robert Boyle: Chemical Reactions in Words as well as Symbols

ERIC Educational Resources Information Center

Goodney, David E.

2006-01-01

Examples of acid-base reactions from Robert Boyle's "The Sceptical Chemist" are used to illustrate the rich information content of chemical equations. Boyle required lengthy passages of florid language to describe the same reaction that can be done quite simply with a chemical equation. Reading or hearing the words, however, enriches the student's…

Esterification Reaction Utilizing Sense of Smell and Eyesight for Conversion and Catalyst Recovery Monitoring

ERIC Educational Resources Information Center

Janssens, Nikki; Wee, Lik H.; Martens, Johan A.

2014-01-01

The esterification reaction of salicylic acid with ethanol is performed in presence of dissolved 12-tungstophosphoric Brønsted-Lowry acid catalyst, a Keggin-type polyoxometalate (POM). The monitoring of the reaction with smell and the recovery of the catalyst with sight is presented. Formation of the sweet-scented ester is apparent from the smell.…

Regioselective SN2' Mitsunobu reaction of Morita-Baylis-Hillman alcohols: A facile and stereoselective synthesis of α-alkylidene-β-hydrazino acid derivatives.

PubMed

Xu, Silong; Shang, Jian; Zhang, Junjie; Tang, Yuhai

2014-01-01

A highly regioselective SN2' Mitsunobu reaction between Morita-Baylis-Hillman (MBH) alcohols, azodicarboxylates, and triphenylphosphine is developed, which provides an easy access to α-alkylidene-β-hydrazino acid derivatives in high yields and good stereoselectivity. This reaction represents the first direct transformation of MBH alcohols into hydrazines.

An efficient synthesis of tetramic acid derivatives with extended conjugation from L-Ascorbic Acid

PubMed Central

Singh, Biswajit K; Bisht, Surendra S; Tripathi, Rama P

2006-01-01

Background Tetramic acids with polyenyl substituents are an important class of compounds in medicinal chemistry. Both solid and solution phase syntheses of such molecules have been reported recently. Thiolactomycin, a clinical candidate for treatment of tuberculosis has led to further explorations in this class. We have recently developed an efficient synthesis of tetramic acids derivatives from L- ascorbic acid. In continuation of this work, we have synthesised dienyl tetramic acid derivatives. Results 5,6-O-Isopropylidene-ascorbic acid on reaction with DBU led to the formation of tetronolactonyl allyl alcohol, which on oxidation with pyridinium chlorochromate gave the respective tetranolactonyl allylic aldehydes. Wittig olefination followed by reaction of the resulting tetranolactonyl dienyl esters with different amines resulted in the respective 5-hydroxy lactams. Subsequent dehydration of the hydroxy lactams with p-toluene sulphonic acid afforded the dienyl tetramic acid derivatives. All reactions were performed at ambient temperature and the yields are good. Conclusion An efficient and practical method for the synthesis of dienyl tetramic acid derivatives from inexpensive and easily accessible ascorbic acid has been developed. The compounds bear structural similarities to the tetramic acid based polyenic antibiotics and thus this method offers a new and short route for the synthesis of tetramic acid derivatives of biological significance. PMID:17147830

An efficient synthesis of tetramic acid derivatives with extended conjugation from L-ascorbic acid.

PubMed

Singh, Biswajit K; Bisht, Surendra S; Tripathi, Rama P

2006-12-06

Tetramic acids with polyenyl substituents are an important class of compounds in medicinal chemistry. Both solid and solution phase syntheses of such molecules have been reported recently. Thiolactomycin, a clinical candidate for treatment of tuberculosis has led to further explorations in this class. We have recently developed an efficient synthesis of tetramic acids derivatives from L-ascorbic acid. In continuation of this work, we have synthesised dienyl tetramic acid derivatives. 5,6-O-isopropylidene-ascorbic acid on reaction with DBU led to the formation of tetronolactonyl allyl alcohol, which on oxidation with pyridinium chlorochromate gave the respective tetranolactonyl allylic aldehydes. Wittig olefination followed by reaction of the resulting tetranolactonyl dienyl esters with different amines resulted in the respective 5-hydroxy lactams. Subsequent dehydration of the hydroxy lactams with p-toluene sulphonic acid afforded the dienyl tetramic acid derivatives. All reactions were performed at ambient temperature and the yields are good. An efficient and practical method for the synthesis of dienyl tetramic acid derivatives from inexpensive and easily accessible ascorbic acid has been developed. The compounds bear structural similarities to the tetramic acid based polyenic antibiotics and thus this method offers a new and short route for the synthesis of tetramic acid derivatives of biological significance.

A New Synthetic Route to N-Benzyl Carboxamides through the Reverse Reaction of N-Substituted Formamide Deformylase

PubMed Central

Hashimoto, Yoshiteru; Sakashita, Toshihide; Fukatsu, Hiroshi; Sato, Hiroyoshi

2014-01-01

Previously, we isolated a new enzyme, N-substituted formamide deformylase, that catalyzes the hydrolysis of N-substituted formamide to the corresponding amine and formate (H. Fukatsu, Y. Hashimoto, M. Goda, H. Higashibata, and M. Kobayashi, Proc. Natl. Acad. Sci. U. S. A. 101:13726–13731, 2004, doi:10.1073/pnas.0405082101). Here, we discovered that this enzyme catalyzed the reverse reaction, synthesizing N-benzylformamide (NBFA) from benzylamine and formate. The reverse reaction proceeded only in the presence of high substrate concentrations. The effects of pH and inhibitors on the reverse reaction were almost the same as those on the forward reaction, suggesting that the forward and reverse reactions are both catalyzed at the same catalytic site. Bisubstrate kinetic analysis using formate and benzylamine and dead-end inhibition studies using a benzylamine analogue, aniline, revealed that the reverse reaction of this enzyme proceeds via an ordered two-substrate, two-product (bi-bi) mechanism in which formate binds first to the enzyme active site, followed by benzylamine binding and the subsequent release of NBFA. To our knowledge, this is the first report of the reverse reaction of an amine-forming deformylase. Surprisingly, analysis of the substrate specificity for acids demonstrated that not only formate, but also acetate and propionate (namely, acids with numbers of carbon atoms ranging from C1 to C3), were active as acid substrates for the reverse reaction. Through this reaction, N-substituted carboxamides, such as NBFA, N-benzylacetamide, and N-benzylpropionamide, were synthesized from benzylamine and the corresponding acid substrates. PMID:24123742

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

Cheng, Chiu Tung; Chan, Man Nin; Wilson, Kevin R.

Oxygenated organic molecules are abundant in atmospheric aerosols and are transformed by oxidation reactions near the aerosol surface by gas-phase oxidants such as hydroxyl (OH) radicals. To gain better insights into how the structure of an organic molecule, particularly in the presence of hydroxyl groups, controls the heterogeneous reaction mechanisms of oxygenated organic compounds, this study investigates the OH-radical initiated oxidation of aqueous tartaric acid (C 4 H 6 O 6 ) droplets using an aerosol flow tube reactor. The molecular composition of the aerosols before and after reaction is characterized by a soft atmospheric pressure ionization source (Direct Analysismore » in Real Time) coupled with a high-resolution mass spectrometer. The aerosol mass spectra reveal that four major reaction products are formed: a single C 4 functionalization product (C 4 H 4 O 6 ) and three C 3 fragmentation products (C 3 H 4 O 4 , C 3 H 2 O 4 , and C 3 H 2 O 5 ). The C 4 functionalization product does not appear to originate from peroxy radical self-reactions but instead forms via an α-hydroxylperoxy radical produced by a hydrogen atom abstraction by OH at the tertiary carbon site. The proximity of a hydroxyl group to peroxy group enhances the unimolecular HO 2 elimination from the α-hydroxylperoxy intermediate. This alcohol-to-ketone conversion yields 2-hydroxy-3-oxosuccinic acid (C 4 H 4 O 6 ), the major reaction product. While in general, C-C bond scission reactions are expected to dominate the chemistry of organic compounds with high average carbon oxidation states (OS C ), our results show that molecular structure can play a larger role in the heterogeneous transformation of tartaric acid (OS C = 1.5). These results are also compared with two structurally related dicarboxylic acids (succinic acid and 2,3-dimethylsuccinic acid) to elucidate how the identity and location of functional groups (methyl and hydroxyl groups) alter heterogeneous reaction mechanisms.« less

Catalytic effects of histidine enantiomers and glycine on the formation of dileucine and dimethionine in the salt-induced peptide formation reaction.

PubMed

Li, Feng; Fitz, Daniel; Fraser, Donald G; Rode, Bernd M

2010-01-01

The salt-induced peptide formation (SIPF) reaction takes place readily under mild reaction conditions and proceeds via a copper complex. Its ease of reaction and the universality for prebiotic scenarios add weights to the arguments in favour of the importance of peptide and proteins in the tug of war with the RNA world hypothesis. In addition, the SIPF reaction has a preference for L-form amino acids in dipeptide formation, casting light on the puzzle of biohomochirality, especially for the amino acids with aliphatic side chains. A detailed investigation on the behaviour of aliphatic leucine in the SIPF reaction is presented in this paper, including the catalytic effects of glycine, L- and D-histidine as well as the stereoselectivity under all the reaction conditions above. The results show a relatively low reactivity and stereoselectivity of leucine in the SIPF reaction, while both glycine and histidine enantiomers remarkably increase the yields of dileucine by factors up to 40. Moreover, a comparative study of the effectiveness of L- and D-histidine in catalysing the formation of dimethionine was also carried out and extends the scope of mutual catalysis by amino acid enantiomers in the SIPF reaction.

The Role of Citric Acid in Perfecting Platinum Monolayer on Palladium Nanoparticles during the Surface Limited Redox Replacement Reaction

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

Zhu, Shangqian; Yue, Jeffrey; Qin, Xueping

Cu-mediated-Pt-displacement method that involves the displacement of an underpotentially deposited (UPD) Cu monolayer by Pt has been extensively studied to prepare core-shell catalysts. It has been found that Pt clusters instead of a uniform Pt monolayer were formed in the gram batch synthesis. With a suitable surfactant, such as citric acid, the Pt shell could be much more uniform. In this study, the role of citric acid in controlling the Cu-Pt displacement reaction kinetics was studied by electrochemical techniques and theoretical approaches. It was found that citric acid strongly adsorbed on Pd, Pt, Cu/Pd, and Pt/Pd surfaces, especially in themore » double layer region in acid solutions. The strong adsorption of citric acid slowed down the Cu-Pt displacement reaction. The main characteristics of such strong interaction most likely arises from the OH groups in the citric acid molecule according to the molecular dynamics simulation results.« less

The Role of Citric Acid in Perfecting Platinum Monolayer on Palladium Nanoparticles during the Surface Limited Redox Replacement Reaction

DOE PAGES

Zhu, Shangqian; Yue, Jeffrey; Qin, Xueping; ...

2016-07-28

Cu-mediated-Pt-displacement method that involves the displacement of an underpotentially deposited (UPD) Cu monolayer by Pt has been extensively studied to prepare core-shell catalysts. It has been found that Pt clusters instead of a uniform Pt monolayer were formed in the gram batch synthesis. With a suitable surfactant, such as citric acid, the Pt shell could be much more uniform. In this study, the role of citric acid in controlling the Cu-Pt displacement reaction kinetics was studied by electrochemical techniques and theoretical approaches. It was found that citric acid strongly adsorbed on Pd, Pt, Cu/Pd, and Pt/Pd surfaces, especially in themore » double layer region in acid solutions. The strong adsorption of citric acid slowed down the Cu-Pt displacement reaction. The main characteristics of such strong interaction most likely arises from the OH groups in the citric acid molecule according to the molecular dynamics simulation results.« less

Interaction of the acid soap of triethanolamine stearate and stearic acid with water.

PubMed

Zhu, S; Pudney, P D A; Heppenstall-Butler, M; Butler, M F; Ferdinando, D; Kirkland, M

2007-02-08

Stearic acid and triethanolamine (TEA) in a molar ratio of 2:1 were mixed in aqueous solution at 80 degrees C and subsequently cooled to ambient temperature. The structural evolution of the resultant sample during storage was characterized by using light microscopy, Cryo-SEM, differential scanning calorimetery, pH, infrared spectroscopy, elemental analysis, and simultaneous small and wide-angle X-ray diffraction. It was found that a lamellar liquid crystalline phase was formed when stearic acid and TEA solution were mixed at 80 degrees C and multilamellar spheres of a few microns diameter were formed initially after cooling. A hydrolysis reaction (i.e., the reverse reaction of neutralization between stearic acid and TEA) occurred thereafter that caused the breakdown of the lamellar gel phase and the formation of platelet stearic acid crystals. Three polymorphs of stearic acid (defined following previous work as the A, C, and E forms) were formed as the result of hydrolysis reaction, which gave rise to a strong optically pearlescent appearance.

Comparison of sulfuric and hydrochloric acids as catalysts in hydrolysis of Kappaphycus alvarezii (cottonii).

PubMed

Meinita, Maria Dyah Nur; Hong, Yong-Ki; Jeong, Gwi-Taek

2012-01-01

In this study, hydrolysis of marine algal biomass Kappaphhycus alvarezii using two different acid catalysts was examined with the goal of identifying optimal reaction conditions for the formation of sugars and by-products. K. alvarezii were hydrolyzed by autoclave using sulfuric acid or hydrochloric acid as catalyst with different acid concentrations (0.1-1.0 M), substrate concentrations (1.0-13.5%), hydrolysis time (10-90 min) and hydrolysis temperatures (100-130 (°)C). A difference in galactose, glucose, reducing sugar and total sugar content was observed under the different hydrolysis conditions. Different by-product compounds such as 5-hydroxymethylfurfural and levulinic acid were also observed under the different reaction conditions. The optimal conditions for hydrolysis were achieved at a sulfuric acid concentration, temperature and reaction time of 0.2 M, 130 °C and 15 min, respectively. These results may provide useful information for the development of more efficient systems for biofuel production from marine biomass.

Progress on Zeolite-membrane-aided Organic Acid Esterification

NASA Astrophysics Data System (ADS)

Makertiharta, I. G. B. N.; Dharmawijaya, P. T.

2017-07-01

Esterification is a common route to produce carboxylic acid esters as important intermediates in chemical and pharmaceutical industries. However, the reaction is equilibrium limited and needs to be driven forward by selective removal one of the products. There have been some efforts to selectively remove water from reaction mixture via several separation processes (such as pervaporation and reactive distillation). Integrated pervaporation and esterification has gained increasing attention towards. Inorganic zeolite is the most popular material for pervaporation due to its high chemical resistant and separation performance towards water. Zeolite also has proven to be an effective material in removing water from organic compound. Zeolite can act not only as selective layer but also simultaneously act as a catalyst on promoting the reaction. Hence, there are many configurations in integrating zeolite membrane for esterification reaction. As a selective layer to remove water from reaction mixture, high Si/Al zeolite is preferred to enhance its hydrophilicity. However, low Si/Al zeolite is unstable in acid condition due to dealumination thus eliminate its advantages. As a catalyst, acid zeolites (e.g. H-ZSM-5) provide protons for autoprotolysis of the carboxylic acid similar to other catalyst for esterification (e.g. inorganic acid, and ion exchange resins). There are many studies related to zeolite membrane aided esterification. This paper will give brief information related to zeolite membrane role in esterification and also research trend towards it.

Theoretical investigation of the mechanism of the baeyer-villiger reaction in nonpolar solvents.

PubMed

Okuno, Y

1997-02-01

The Baeyer-Villiger reaction of p-anisaldehyde with peroxyacetic acid in nonpolar solvents to give p-anisylformate was examined on the basis of ab initio molecular orbital calculations. To explain the experimental observations, the free-energy change was evaluated for each case in the absence and in the presence of an acid catalyst. It was found that, without catalysts, the rate-determining step corresponds to the carbonyl addition of peroxyacetic acid to p-anisaldehyde and the reaction hardly occurs. Acetic acid was found to catalyze the carbonyl addition and change the rate-determining step from the carbonyl addition to the migration of the carbonyl-adduct intermediate. Trifluoroacetic acid was observed to catalyze both the carbonyl addition and migration, and the carbonyl addition was demonstrated to be a rate-determining step. The results provided a convincing explanation of the complex kinetics seen experimentally. Further calculations were performed for the reaction of benzaldehyde with peroxyacetic acid to give phenylformate. Migratory aptitude was found to depend on the catalyst. Isotope effects were also investigated, and the exceptional isotope effect observed experimentally was shown to be due to the rate-determining carbonyl addition caused by autocatalysis. It is concluded that the mechanism of the reaction varies with catalysis or substituent effects. Copyright © 1997 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ceramic oxide reactions with V2O5 and SO3

NASA Technical Reports Server (NTRS)

Jones, R. L.; Williams, C. E.

1985-01-01

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Effect of amino acids on the interaction between cobalamin(II) and dehydroascorbic acid

NASA Astrophysics Data System (ADS)

Dereven'kov, I. A.; Thi, Thu Thuy Bui; Salnikov, D. S.; Makarov, S. V.

2016-03-01

The kinetics of the reaction between one-electron-reduced cobalamin (cobalamin(II), Cb(II)) and the two-electron-oxidized form of vitamin C (dehydroascorbic acid, DHA) with amino acids in an acidic medium is studied by conventional UV-Vis spectroscopy. It is shown that the oxidation of Cbl(II) by dehydroascorbic acid proceeds only in the presence of sulfur-containing amino acids (cysteine, acetylcysteine). A proposed reaction mechanism includes the step of amino acid coordination on the Co(II)-center through the sulfur atom, along with that of the interaction between this complex and DHA molecules, which results in the formation of ascorbyl radical and the corresponding Co(III) thiolate complex.

Metabolism of exogenous fatty acids, fatty acid-mediated cholesterol efflux, PKA and PKC pathways in boar sperm acrosome reaction.

PubMed

Hossain, Md Sharoare; Afrose, Sadia; Sawada, Tomio; Hamano, Koh-Ichi; Tsujii, Hirotada

2010-03-01

For understanding the roles of fatty acids on the induction of acrosome reaction which occurs under association of cholesterol efflux and PKA or PKC pathways in boar spermatozoa, metabolic fate of alone and combined radiolabeled 14 C-oleic acid and 3 H-linoleic acid incorporated in the sperm was compared, and behavior of cholesterol and effects of PKA and PKC inhibitors upon fatty acid-induced acrosome reaction were examined. Semen was collected from a Duroc boar, and the metabolic activities of fatty acids in the spermatozoa were measured using radioactive compounds and thin layer chromatography. Cholesterol efflux was measured with a cholesterol determination assay kit. Participation of fatty acids on the AR through PKA and PKC pathways was evaluated using a specific inhibitor of these enzymes. Incorporation rate of 14 C-oleic acid into the sperm lipids was significantly higher than that of 3 H-linoleic acid ( P < 0.05). The oxidation of 14 C-oleic acid was higher in combined radiolabeling rather than in one. The highest amounts of 3 H-linoleic acid and 14 C-oleic acid were recovered mainly in the triglycerides and phospholipids fraction, and 14 C-oleic acid distribution was higher than the 3 H-linoleic acid in both labeled ( P < 0.05) sperm lipids. In the 3 H-linoleic and 14 C-oleic acid combined radiolabeling, the incorporation rate of the radioactive fatty acids in all the lipid fractions increased 15 times more than the alone radiolabeling. Boar sperm utilize oleic acid to generate energy for hyperactivation ( P < 0.05). Supplementation of arachidonic acid significantly increased ( P < 0.05) cholesterol efflux in sperm. When spermatozoa were incubated with PKA or PKC inhibitors, there was a significant reduction of arachidonic acid-induced acrosome reaction (AR) ( P < 0.05), and inhibition by PKA inhibitor is stronger than that by PKC inhibitor. Incorporation of unsaturated fatty acids, especially oleic acid, into triglycerides and phospholipids provides prerequisite energy for AR. Cholesterol efflux by arachidonic acid triggers AR. Arachidonic acid activated PKA and PKC pathway participate in induction of the AR.

Electrocatalysis of fuel cell reactions: Investigation of alternate electrolytes

NASA Technical Reports Server (NTRS)

Chin, D. T.; Hsueh, K. L.; Chang, H. H.

1984-01-01

Oxygen reduction and transport properties of the electrolyte in the phosphoric acid fuel cell are studied. The areas covered were: (1) development of a theoretical expression for the rotating ring disk electrode technique; (2) determination of the intermediate reaction rate constants for oxygen reduction on platinum in phosphoric acid electrolyte; (3) determination of oxygen reduction mechanism in trifluoreomethanesulfonic acid (TFMSA) which was considered as an alternate electrolyte for the acid fuel cells; and (4) the measurement of transport properties of the phosphoric acid electrolyte at high concentrations and temperatures.

Protecting‐Group‐Free Amidation of Amino Acids using Lewis Acid Catalysts

PubMed Central

Sabatini, Marco T.; Karaluka, Valerija; Lanigan, Rachel M.; Boulton, Lee T.; Badland, Matthew

2018-01-01

Abstract Amidation of unprotected amino acids has been investigated using a variety of ‘classical“ coupling reagents, stoichiometric or catalytic group(IV) metal salts, and boron Lewis acids. The scope of the reaction was explored through the attempted synthesis of amides derived from twenty natural, and several unnatural, amino acids, as well as a wide selection of primary and secondary amines. The study also examines the synthesis of medicinally relevant compounds, and the scalability of this direct amidation approach. Finally, we provide insight into the chemoselectivity observed in these reactions. PMID:29505683

Five- and six-membered ring opening of pyroglutamic diketopiperazine.

PubMed

Parrish, Dennis A; Mathias, Lon J

2002-03-22

A variety of ring-opening reactions of pyroglutamic diketopiperazine at both the five-membered and six-membered rings is described. Mild, basic conditions facilitate nucleophilic attack by amines at the diketopiperazine carbonyls giving pyroglutamides in excellent yield. Reaction with nucleophiles under acidic conditions give bis-glutamate derivatives of 2,5-diketopiperazine (DKP). These reactions provide simple, two-step sequences to pyroglutamides and symmetrical diketopiperazines from commercial pyroglutamic acid with control of product dictated by reaction conditions, catalyst, and nucleophile.

Chiral phosphoric acid catalysis: from numbers to insights.

PubMed

Maji, Rajat; Mallojjala, Sharath Chandra; Wheeler, Steven E

2018-02-19

Chiral phosphoric acids (CPAs) have emerged as powerful organocatalysts for asymmetric reactions, and applications of computational quantum chemistry have revealed important insights into the activity and selectivity of these catalysts. In this tutorial review, we provide an overview of computational tools at the disposal of computational organic chemists and demonstrate their application to a wide array of CPA catalysed reactions. Predictive models of the stereochemical outcome of these reactions are discussed along with specific examples of representative reactions and an outlook on remaining challenges in this area.

Determination of Arrhenius and Thermodynamic Parameters for the Aqueous Reaction of the Hydroxyl Radical with Lactic Acid

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

Leigh R. Martin; Stephen P. Mezyk; Bruce J. Mincher

2009-01-01

Lactic acid is a major component of the TALSPEAK process planned for use in the separation of trivalent lanthanide and actinide elements. This acid acts both as a buffer, and also to protect the actinide complexant from radiolytic damage. However, there is little kinetic information on the reaction of water radiolysis species with lactic acid, particularly under the anticipated process conditions of aerated aqueous solution at pH~3, where oxidizing reactions are expected to dominate. Here we have determined temperature-dependent reaction rate constants for the reactions of the hydroxyl radical with lactic acid and the lactate ion. For lactic acid thismore » rate constant is given by the equation: ln k1 = (23.85 ± 0.19) – (1120 ± 54) / T, corresponding to an activation energy of 9.31 ± 0.45 kJ mol-1 and a room temperature reaction rate constant of (5.24 ± 0.09) x 108 M-1 s-1 (24.0oC). For the lactate ion, the temperature-dependent rate constant is given by: ln k2 = (24.83 ± 0.14) – (1295 ± 42) / T, for an activation energy of 10.76 ± 0.35 kJ mol-1 and a room temperature value of (7.77 ± 0.11) x 108 M-1 s-1 (22.2oC). These kinetic data have been combined with autotitration measurements to determine the temperature-dependent behavior of the lactic acid pKa value, allowing thermodynamic parameters for the acid dissociation to be calculated as ?Hº = -10.75 ± 1.77 kJ mol-1, ?Sº = -103.9 ± 6.0 J K-1 mol-1 and ?Gº = 20.24 ± 2.52 kJ mol-1 at low ionic strength.« less

Selective Ring Opening of 1-Methylnaphthalene Over NiW-Supported Catalyst Using Dealuminated Beta Zeolite.

PubMed

Kim, Eun-Sang; Lee, You-Jin; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

2016-02-01

Nanoporous Beta zeolite was dealuminated by weak acid treatment for reducing the acidity. Bi-functional catalysts were prepared using commercial Beta zeolites and the dealuminated zeolites for acidic function, NiW for metallic function. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction has been investigated using the prepared bi-functional catalysts with different acidity in fixed bed reaction system. The dealuminated Beta zeolites, which crystal structure and nanoporosity were maintained, showed the higher SiO2/Al2O3 ratio and smaller acidity than their original zeolite. NiW-supported catalyst using the dealuminated Beta zeolite with SiO2/Al203 mole ratio of 55 showed the highest performance for the selective ring opening. The acidity of catalyst seemed to play an important role as active sites for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. The acidity of Beta zeolite could be controlled by the acid treatment and the catalyst with the optimum acidity for the selective ring opening could be prepared.

Diastereoselective radical addition to γ-alkyl-α-methylene-γ-butyrolactams and the synthesis of a chiral pyroglutamic acid derivative

PubMed Central

Yoshida, Eriko; Hamano, Masako

2013-01-01

Summary The cis- and trans-stereoselective radical additions to α-methylene-γ-alkyl- γ-lactams were investigated and the scope and limitation of the reaction were also revealed. This stereoselective radical reaction was used for synthesis of chiral pyroglutamic acid derivatives starting from a commercially available chiral amino acid. PMID:23946839

A Comparative Study of French and Turkish Students' Ideas on Acid-Base Reactions

ERIC Educational Resources Information Center

Cokelez, Aytekin

2010-01-01

The goal of this comparative study was to determine the knowledge that French and Turkish upper secondary-school students (grades 11 and 12) acquire on the concept of acid-base reactions. Following an examination of the relevant curricula and textbooks in the two countries, 528 students answered six written questions about the acid-base concept.…

Characterization and quantification of endogenous fatty acid nitroalkene metabolites in human urine[S

PubMed Central

Salvatore, Sonia R.; Vitturi, Dario A.; Baker, Paul R. S.; Bonacci, Gustavo; Koenitzer, Jeffrey R.; Woodcock, Steven R.; Freeman, Bruce A.; Schopfer, Francisco J.

2013-01-01

The oxidation and nitration of unsaturated fatty acids transforms cell membrane and lipoprotein constituents into mediators that regulate signal transduction. The formation of 9-NO2-octadeca-9,11-dienoic acid and 12-NO2-octadeca-9,11-dienoic acid stems from peroxynitrite- and myeloperoxidase-derived nitrogen dioxide reactions as well as secondary to nitrite disproportionation under the acidic conditions of digestion. Broad anti-inflammatory and tissue-protective responses are mediated by nitro-fatty acids. It is now shown that electrophilic fatty acid nitroalkenes are present in the urine of healthy human volunteers (9.9 ± 4.0 pmol/mg creatinine); along with electrophilic 16- and 14-carbon nitroalkenyl β-oxidation metabolites. High resolution mass determinations and coelution with isotopically-labeled metabolites support renal excretion of cysteine-nitroalkene conjugates. These products of Michael addition are in equilibrium with the free nitroalkene pool in urine and are displaced by thiol reaction with mercury chloride. This reaction increases the level of free nitroalkene fraction >10-fold and displays a KD of 7.5 × 10−6 M. In aggregate, the data indicates that formation of Michael adducts by electrophilic fatty acids is favored under biological conditions and that reversal of these addition reactions is critical for detecting both parent nitroalkenes and their metabolites. The measurement of this class of mediators can constitute a sensitive noninvasive index of metabolic and inflammatory status. PMID:23620137

Kinetics and Quantitative Structure—Activity Relationship Study on the Degradation Reaction from Perfluorooctanoic Acid to Trifluoroacetic Acid

PubMed Central

Gong, Chen; Sun, Xiaomin; Zhang, Chenxi; Zhang, Xue; Niu, Junfeng

2014-01-01

Investigation of the degradation kinetics of perfluorooctanoic acid (PFOA) has been carried out to calculate rate constants of the main elementary reactions using the multichannel Rice-Ramsperger-Kassel-Marcus theory and canonical variational transition state theory with small-curvature tunneling correction over a temperature range of 200~500 K. The Arrhenius equations of rate constants of elementary reactions are fitted. The decarboxylation is role step in the degradation mechanism of PFOA. For the perfluorinated carboxylic acids from perfluorooctanoic acid to trifluoroacetic acid, the quantitative structure–activity relationship of the decarboxylation was analyzed with the genetic function approximation method and the structure–activity model was constructed. The main parameters governing rate constants of the decarboxylation reaction from the eight-carbon chain to the two-carbon chain were obtained. As the structure–activity model shows, the bond length and energy of C1–C2 (RC1–C2 and EC1–C2) are positively correlated to rate constants, while the volume (V), the energy difference between EHOMO and ELUMO (ΔE), and the net atomic charges on atom C2 (QC2) are negatively correlated. PMID:25196516

Sunlight-initiated chemistry of aqueous pyruvic acid: building complexity in the origin of life.

PubMed

Griffith, Elizabeth C; Shoemaker, Richard K; Vaida, Veronica

2013-10-01

Coupling chemical reactions to an energy source is a necessary step in the origin of life. Here, we utilize UV photons provided by a simulated sun to activate aqueous pyruvic acid and subsequently prompt chemical reactions mimicking some of the functions of modern metabolism. Pyruvic acid is interesting in a prebiotic context due to its prevalence in modern metabolism and its abiotic availability on early Earth. Here, pyruvic acid (CH3COCOOH, a C3 molecule) photochemically reacts to produce more complex molecules containing four or more carbon atoms. Acetoin (CH3CHOHCOCH3), a C4 molecule and a modern bacterial metabolite, is produced in this chemistry as well as lactic acid (CH3CHOHCOOH), a molecule which, when coupled with other abiotic chemical reaction pathways, can provide a regeneration pathway for pyruvic acid. This chemistry is discussed in the context of plausible environments on early Earth such as near the ocean surface and atmospheric aerosol particles. These environments allow for combination and exchange of reactants and products of other reaction environments (such as shallow hydrothermal vents). The result could be a contribution to the steady increase in chemical complexity requisite in the origin of life.

DNAPL remediation with in situ chemical oxidation using potassium permanganate - Part I. Mineralogy of Mn oxide and its dissolution in organic acids

NASA Astrophysics Data System (ADS)

Li, X. David; Schwartz, Franklin W.

2004-01-01

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 Å. The chemical formula is K 0.854Mn 1.786O 4·1.55H 2O. It has a relatively small specific surface area at 23.6±0.82 m 2/g. Its point of zero charge (pzc) was measured as 3.7±0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m 2/h for citric acid, 1.35 mM/m 2/h for oxalic acid, and 5.176 mM/m 2/h for EDTA. These rates compare with 0.0025 mM/m 2/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant potential in using these organic acids to remove precipitates formed during the oxidation reaction.

[The hyperiricosuria as an indicator of derangement of biologic functions of endoecology and adaptation, biologic reactions of excretion, inflammation and arterial tension].

PubMed

Titov, V N; Oshchepkova, E V; Dmitriev, V A; Gushchina, O V; Shiriaeva, Iu K; Iashin, A Ia

2012-04-01

During millions years in all animals allantoine (oxidized by uricase uric acid) was catabolite of purines and ascorbic acid was an acceptor of active forms of oxygen. The proximal tubules of nephron reabsorbed the trace amounts of uric acid Then during phylogenesis the primates had a mutation of ascorbic acid gen minus. Later on occurred a second spontaneous mutation and uricase gen minus and uric acid became catabolites of purines. In absence of ascorbic acid synthesis ions of urates became a major capturers of active forms of oxygen and all uric acid as before underwent the reabsorption. Later the carriers were formed which began in epithelium of proximal tubules to secrete all uric acid into urine. At every incident of "littering" of intercellular medium with endogenic flogogens (impairment of biologic function of endoecology) under compensatory development of biologic reaction of inflammation the need in inactivation of active forms of oxygen increases. Hence later on in phylogenesis one more stage was formed--post secretory reabsorption of uric acid In the biologic reaction of inflammation epithelium of proximal tubules initiates retentional hyperiricosuria. The general antioxidant activity of human blood plasma in 60% is presented by urates' ions. The excretion of uric acid includes 4 stages: filtration, full reabsorption, secretion and post secretory reabsorption. In phylogenesis these stages formed in sequence. The mild hyperiricosuria is most frequently considered as a non-specific indicator of activation of biologic reaction of inflammation. The productive hyperiricosuria develops more infrequently under surplus of meat food and cytolysis syndrome (intensification of cell loss in vivo). Under concentration of uric acid more than 400 mkmol/l part of urates circulates in intercellular medium in the form of crystals. The microcrystals of uric acid (biologic "litter") initiate the syndrome of systemic inflammatory response as an endogenic flogogen--initiator of inflammation. The uric acid in the form of ion-capturers of active forms of oxygen is involved into in the formation of syndrome of compensatory anti-inflammatory defense. It may be assumed that simultaneously with post-secretory reabsorption of ions of urates in proximal tubules of nephron occurs intensification of philogenetically late post-secretory reabsorption of ions of sodium and activation of of biologic reaction of hydrodynamic and hydraulic pressure in local pool of intravascular medium i.e. arterial tension. The uric acid simultaneously participates in realization of biologic function of endoecology and adaptation, biologic reactions of excretion, inflammation and arterial tension.

Sustainable synthesis of aldehydes, ketones or acids from neat alcohols using nitrogen dioxide gas, and related reactions.

PubMed

Naimi-Jamal, M Reza; Hamzeali, Hamideh; Mokhtari, Javad; Boy, Jürgen; Kaupp, Gerd

2009-01-01

Benzylic alcohols are quantitatively oxidized by gaseous nitrogen dioxide to give pure aromatic aldehydes. The reaction gas mixtures are transformed to nitric acid, which renders the processes free of waste. The exothermic gas-liquid or gas-solid reactions profit from the solubility of nitrogen dioxide in the neat benzylic alcohols. The acid formed impedes further oxidation of the benzaldehydes. The neat isolated benzaldehydes and nitrogen dioxide quantitatively give the benzoic acids. Solid long-chain primary alcohols are directly and quantitatively oxidized with nitrogen dioxide gas to give the fatty acids in the solid state. The oxidations with ubiquitous nitrogen dioxide are extended to solid heterocyclic thioamides, which gives disulfides, and to diphenylamine, which gives tetraphenylhydrazine. These sustainable (green) specific oxidation procedures produce no dangerous residues from the oxidizing agent or from auxiliaries.

Influence of vegetable oils fatty acid composition on reaction temperature and glycerides conversion to biodiesel during transesterification.

PubMed

Pinzi, S; Gandía, L M; Arzamendi, G; Ruiz, J J; Dorado, M P

2011-01-01

Presence of unreacted glycerides in biodiesel may reduce drastically its quality. This is why conversion of raw material in biodiesel through transesterification needs to readjust reaction parameter values to complete. In the present work, monitoring of glycerides transformation in biodiesel during the transesterification of vegetable oils was carried out. To check the influence of the chemical composition on glycerides conversion, selected vegetable oils covered a wide range of fatty acid composition. Reactions were carried out under alkali-transesterification in the presence of methanol. In addition, a multiple regression model was proposed. Results showed that kinetics depends on chemical and physical properties of the oils. It was found that the optimal reaction temperature depends on both length and unsaturation degree of vegetable oils fatty acid chains. Vegetable oils with higher degree of unsaturation exhibit faster monoglycerides conversion to biodiesel. It can be concluded that fatty acid composition influences reaction parameters and glycerides conversion, hence biodiesel yield and economic viability. Copyright © 2010 Elsevier Ltd. All rights reserved.

Sequential Aldol Condensation – Transition Metal-Catalyzed Addition Reactions of Aldehydes, Methyl Ketones and Arylboronic Acids

PubMed Central

Liao, Yuan-Xi; Xing, Chun-Hui; Israel, Matthew; Hu, Qiao-Sheng

2011-01-01

Sequential aldol condensation of aldehydes with methyl ketones followed by transition metal-catalyzed addition reactions of arylboronic acids to form β-substituted ketones is described. By using the 1,1′-spirobiindane-7,7′-diol (SPINOL)-based phosphite, an asymmetric version of this type of sequential reaction, with up to 92% ee, was also realized. Our study provided an efficient method to access β-substituted ketones and might lead to the development of other sequential/tandem reactions with transition metal-catalyzed addition reactions as the key step. PMID:21417359

Sequential aldol condensation-transition metal-catalyzed addition reactions of aldehydes, methyl ketones, and arylboronic acids.

PubMed

Liao, Yuan-Xi; Xing, Chun-Hui; Israel, Matthew; Hu, Qiao-Sheng

2011-04-15

Sequential aldol condensation of aldehydes with methyl ketones followed by transition metal-catalyzed addition reactions of arylboronic acids to form β-substituted ketones is described. By using the 1,1'-spirobiindane-7,7'-diol (SPINOL)-based phosphite, an asymmetric version of this type of sequential reaction, with up to 92% ee, was also realized. Our study provided an efficient method to access β-substituted ketones and might lead to the development of other sequential/tandem reactions with transition metal-catalyzed addition reactions as the key step. © 2011 American Chemical Society

Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

NASA Astrophysics Data System (ADS)

Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

2016-05-01

Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition.

Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

PubMed Central

Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

2016-01-01

Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition. PMID:27222322

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.

Aryl Ketone Synthesis via Tandem Orthoplatinated Triarylphosphite-Catalyzed Addition Reactions of Arylboronic Acids with Aldehydes Followed by Oxidation

PubMed Central

Liao, Yuan-Xi; Hu, Qiao-Sheng

2010-01-01

Tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%. PMID:20849092

Enantioselective Bronsted Acid Catalysis with Chiral Pentacarboxycyclopentadienes

NASA Astrophysics Data System (ADS)

Gheewala, Chirag

This thesis details the design and development of pentacarboxycyclopentadienes (PCCPs) as a new platform for enantioselective Bronsted acid catalysis. Prior to this research, enantioselective Bronsted acid catalysis was limited to the BINOL (and variations thereof) framework. While this catalyst platform has paved the way for a myriad of novel asymmetric chemical transformations, the utility of this catalyst scaffold has suffered from its lengthy and expensive preparations. As an alternative, starting from readily available 1,2,3,4,5-pentacarbomethoxycyclopentadiene and various chiral alcohols and amines, the synthesis of a library of strongly acidic chiral catalysts is described. The utility of these novel acid catalysts is explored in various transformations. As a prelude to the heart of this work, Chapter 1 focuses on the advancements made in asymmetric Bronsted acid catalysis through BINOL-phosphate derived catalysts, focusing on the major accomplishments made by researchers since 2004. The provided review highlights the utility of these chiral acid catalysts but also reveals the need for a new scaffold that is more affordable and accessible. Chapter 2 discusses the background of PCCPs, including its initial discovery and subsequent applications. Our work in developing novel transesterified and amidated derivatives is discussed with accompanying crystal structures of achiral and chiral PCCPs. pKa measurements demonstrate the capacity of PCCPs to be used as strong Bronsted acid catalysts and are compared to literature values of known Bronsted acid catalysts. Chapter 3 focuses on the utility of PCCPs as enantioselective Bronsted acid catalysts in a variety of chemical transformations including the Mukaiyama-Mannich reaction, transfer hydrogenation, Pictet-Spengler reaction, diaryl alcohol substitution, Mukayaiama oxocarbenium aldol reaction, and [4+2]-cycloaddition. Catalyst loadings down to 0.01 mol% and reaction scale up to 25 grams in the Mukaiyama-Mannich reaction demonstrate the practical utility and robustness of PCCPs. Substrate scopes of these transformations show the breadth of accessible molecules that can be synthesized via PCCPs. Mechanistic rationales and transition state analyses are discussed in each of the transformations.

Total amino acid stabilization during cell-free protein synthesis reactions.

PubMed

Calhoun, Kara A; Swartz, James R

2006-05-17

Limitations in amino acid supply have been recognized as a substantial problem in cell-free protein synthesis reactions. Although enzymatic inhibitors and fed-batch techniques have been beneficial, the most robust way to stabilize amino acids is to remove the responsible enzymatic activities by genetically modifying the source strain used for cell extract preparation. Previous work showed this was possible for arginine, serine, and tryptophan, but cysteine degradation remained a major limitation in obtaining high protein synthesis yields. Through radiolabel techniques, we confirmed that cysteine degradation was caused by the activity of glutamate-cysteine ligase (gene gshA) in the cell extract. Next, we created Escherichia coli strain KC6 that combines a gshA deletion with previously described deletions for arginine, serine, and tryptophan stabilization. Strain KC6 grows well, and active cell extract can be produced from it for cell-free protein synthesis reactions. The extract from strain KC6 maintains stable amino acid concentrations of all 20 amino acids in a 3-h batch reaction. Yields for three different proteins improved 75-250% relative to cell-free expression using the control extract.

Anionic Four Electron Donor-Based Palladacycles as Catalysts for Addition Reactions of Arylboronic Acids with α,β-Unsaturated Ketones, Aldehydes and α-Ketoesters

PubMed Central

He, Ping; Lu, Yong; Dong, Cheng-Guo; Hu, Qiao-Sheng

2008-01-01

Anionic four electron donor-based palladacycle-catalyzed 1,4-additions of arylboronic acids with α,β-unsaturated ketones and 1,2-additions of arylboronic acids with aldehydes and α-ketoesters are described. Our study demonstrated that palladacycles were highly efficient, practical catalysts for these addition reactions. The work described here not only opened a new paradigm for the application of palladacycles, but may also pave the road for other metalacycles as practically useful catalysts for such addition reactions including asymmetric ones. PMID:17217300

Impacts of dyebath auxiliaries on the reductive discoloration of Acid Orange 7 dye by high-carbon iron filings.

PubMed

Kumar, Raja; Sinha, Alok

This study proposed that the physicochemical effects of common dyebath auxiliaries on the bulk dye solution as well as on the iron surface can influence the reductive discoloration of effluent containing Acid Orange 7 (AO7) dye using high-carbon iron filings. Sodium chloride increased the discoloration rate because of the pitting corrosion on the iron surface, triggered by chloride anion. 'Salting out' effect of ammonium sulfate improved the reaction rate up to a certain concentration, beyond which it could compete with dye molecules for the reactive sites, as revealed by formed sulfite and sulfide. Urea drastically reduced the discoloration rates by its chaotropic effect on the bulk solution and by wrapping around the iron surface. Organic acids, namely acetic acid and citric acid, stimulated iron corrosion to improve the discoloration rates. The discoloration reaction was biphasic with an initial fast reaction phase, where in every case more than 70% discoloration was observed within 5 min of reaction, preceding a slow reaction phase. The experimental data could be well described using biphasic kinetics equation (R(2)> 0.997 in all cases) and a biphasic equation was developed considering the individual impact of co-existing auxiliaries on AO7 discoloration.

Hydrodechlorination of Tetrachloromethane over Palladium Catalysts Supported on Mixed MgF₂-MgO Carriers.

PubMed

Bonarowska, Magdalena; Wojciechowska, Maria; Zieliński, Maciej; Kiderys, Angelika; Zieliński, Michał; Winiarek, Piotr; Karpiński, Zbigniew

2016-11-25

Pd/MgO, Pd/MgF₂ and Pd/MgO-MgF₂ catalysts were investigated in the reaction of CCl₄ hydrodechlorination. All the catalysts deactivated in time on stream, but the degree of deactivation varied from catalyst to catalyst. The MgF₂-supported palladium with relatively large metal particles appeared the best catalyst, characterized by good activity and selectivity to C₂-C₅ hydrocarbons. Investigation of post-reaction catalyst samples allowed to find several details associated with the working state of hydrodechlorination catalysts. The role of support acidity was quite complex. On the one hand, a definite, although not very high Lewis acidity of MgF₂ is beneficial for shaping high activity of palladium catalysts. The MgO-MgF₂ support characterized by stronger Lewis acidity than MgF₂ contributes to very good catalytic activity for a relatively long reaction period (~5 h) but subsequent neutralization of stronger acid centers (by coking) eliminates them from the catalyst. On the other hand, the role of acidity evolution, which takes place when basic supports (like MgO) are chlorided during HdCl reactions, is difficult to assess because different events associated with distribution of chlorided support species, leading to partial or even full blocking of the surface of palladium, which plays the role of active component in HdCl reactions.

Temperature-programmed deoxygenation of acetic acid on molybdenum carbide catalysts

DOE PAGES

Nash, Connor P.; Farberow, Carrie A.; Hensley, Jesse E.

2017-02-07

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system includes a reactor, furnace, gas and vapor sources, flow control, instrumentation to quantify reaction products (e.g., gas chromatograph), and instrumentation to monitor the reaction in real time (e.g., mass spectrometer). Here, we apply the TPRxn methodology to study molybdenum carbide catalysts for the deoxygenation of acetic acid, an important reaction among many in the upgrading/stabilization of biomass pyrolysis vapors. TPRxn is used to evaluate catalyst activity and selectivity and to test hypothetical reaction pathways (e.g., decarbonylation, ketonization,more » and hydrogenation). Furthermore, the results of the TPRxn study of acetic acid deoxygenation show that molybdenum carbide is an active catalyst for this reaction at temperatures above ca. 300 °C and that the reaction favors deoxygenation (i.e., C-O bond-breaking) products at temperatures below ca. 400 °C and decarbonylation (i.e., C-C bond-breaking) products at temperatures above ca. 400 °C.« less

Jasmonic acid-amino acid conjugation enzyme assays.

PubMed

Rowe, Martha L; Staswick, Paul E

2013-01-01

Jasmonic acid (JA) is activated for signaling by its conjugation to isoleucine (Ile) through an amide linkage. The Arabidopsis thaliana JASMONIC ACID RESISTANT1 (JAR1) enzyme carries out this Mg-ATP-dependent reaction in two steps, adenylation of the free carboxyl of JA, followed by condensation of the activated group to Ile. This chapter details the protocols used to detect and quantify the enzymatic activity obtained from a glutathione-S-transferase:JAR1 fusion protein produced in Escherichia coli, including an isotope exchange assay for the adenylation step and assays for the complete reaction that involve the high-performance liquid chromatography quantitation of adenosine monophosphate, a stoichiometric by-product of the reaction, and detection of the conjugation product by thin-layer chromatography or gas -chromatography/mass spectrometry.

Hydrolysis reaction of 2,4-dichlorophenoxyacetic acid. A kinetic and computational study

NASA Astrophysics Data System (ADS)

Romero, Jorge Marcelo; Jorge, Nelly Lidia; Grand, André; Hernández-Laguna, Alfonso

2015-10-01

The degradation of the 2,4-dichlorophenoxyacetic acid in aqueous solution is an hydrolysis reaction. Two products are identified: 2,4-dichlorophenol and glycolic acid. Reaction is investigated as a function of pH and temperature, and it is first-order kinetics and pH-dependent. Reaction is modeled in gas phase, where a proton catalyses the reaction. Critical points of PES are calculated at B3LYP/6-311++G(3df,2p), and aug-cc-pvqz//6-311++G(3df,2p) levels plus ZPE at 6-311++G(3df,2p) level. The activation barrier is 21.2 kcal/mol. Theoretical results agree with the experimental results. A second mechanism related with a Cl2Phsbnd Osbnd CH2sbnd COOH⋯H2O complex is found, but with a rate limiting step of 38.4 kcal/mol.

Copper(II)-Catalyzed Conversion of Aryl/Heteroaryl Boronic Acids, Boronates, and Trifluoroborates into the Corresponding Azides: Substrate Scope and Limitations.

PubMed

Grimes, Kimberly D; Gupte, Amol; Aldrich, Courtney C

2010-05-01

We report the copper(II)-catalyzed conversion of organoboron compounds into the corresponding azide derivatives. A systematic series of phenylboronic acid derivatives is evaluated to examine the importance of steric and electronic effects of the substituents on reaction yield as well as functional group compatibility. Heterocyclic substrates are also shown to participate in this mild reaction while compounds incorporating B-C(sp(3)) bonds are unreactive under the reaction conditions. The copper(II)-catalyzed boronic acid-azide coupling reaction is further extended to both boronate esters and potassium organotrifluoroborate salts. The method described herein complements existing procedures for the preparation of aryl azides from the respective amino, triazene, and halide derivatives and we expect that it will greatly facilitate copper- and ruthenium-catalyzed azide-alkyne cycloaddition reactions for the preparation of diversely functionalized 1-aryl- or 1-heteroaryl-1,2,3-triazoles derivatives.

Facile Formation of Acetic Sulfuric Anhydride in a Supersonic Jet: Characterization by Microwave Spectroscopy and Computational Chemistry

NASA Astrophysics Data System (ADS)

Huff, Anna; Smith, CJ; Mackenzie, Becca; Leopold, Ken

2017-06-01

Sulfur trioxide and acetic acid are shown to react under supersonic jet conditions to form acetic sulfuric anhydride, CH_{3}COOSO_{2}OH. Rotational spectra of the parent, ^{34}S, methyl ^{13}C, and fully deuterated isotopologues have been observed by chirped-pulse and conventional cavity microwave spectroscopy. A and E internal rotation states have been observed for each isotopologue studied and the methyl group internal rotation barriers have been determined (241.043(65) \\wn for the parent species). The reaction is analogous to that of our previous report on the reaction of sulfur trioxide and formic acid. DFT and CCSD calculations are also presented which indicate that the reaction proceeds via a π_{2} + π_{2} + σ_{2} cycloaddition reaction. These results support our previous conjecture that the reaction of SO_{3} with carboxylic acids is both facile and general. Possible implications for atmospheric aerosol formation are discussed.

Acid-catalyzed oxidation of 2,4-dichlorophenoxyacetic acid by ammonium nitrate in aqueous solution

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

Leavitt, D.D.; Abraham, M.A.

1990-04-01

2,4-Dichlorophenoxyacetic acid (2,4-D) was oxidized to CO{sub 2} and water by homogeneous, liquid-phase reaction with ammonium nitrate at temperatures between 250 and 450{degree}F and pressures below 100 psi. N{sub 2} and N{sub 2}O were produced from the thermal decomposition of the ammonium nitrate oxidant. An unexpected maximum in conversion was observed at an intermediate reaction temperature, which was consistent with rapid thermal decomposition of the NH{sub 4}NO{sub 3} oxidant. Postulated reaction pathways consisting of simultaneous oxidation of 2,4-D and decomposition of the oxidant allowed estimation of kinetic constants from best-fit analysis of the data. The proposed reaction model provided amore » mathematical description of 2,4-D conversion, which allowed extrapolation of the results to reaction conditions and reactor configurations that were not experimentally investigated.« less

Boehmite-An Efficient and Recyclable Acid-Base Bifunctional Catalyst for Aldol Condensation Reaction.

PubMed

Reshma, P C Rajan; Vikneshvaran, Sekar; Velmathi, Sivan

2018-06-01

In this work boehmite was used as an acid-base bifunctional catalyst for aldol condensation reactions of aromatic aldehydes and ketones. The catalyst was prepared by simple sol-gel method using Al(NO3)3·9H2O and NH4OH as precursors. The catalyst has been characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), UV-visible spectroscopy (DRS), BET surface area analyses. Boehmite is successfully applied as catalyst for the condensation reaction between 4-nitrobenzaldehyde and acetone as a model substrate giving α, β-unsaturated ketones without any side product. The scope of the reaction is extended for various substituted aldehydes. A probable mechanism has been suggested to explain the cooperative behavior of the acidic and basic sites. The catalyst is environmentally friendly and easily recovered from the reaction mixture. Also the catalyst is reusable up to 3 catalytic cycles.

Acid-$beta$-glycerophosphatase reaction products in the central nervous system mitochondria following x-ray irradiation

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

Roizin, L.; Orlovskaja, D.; Liu, J.C.

A survey of the literature to date on the enzyme histochemistry of intracellular organelles has not yielded any reference to the presence of acid phosphatase reaction products in the mammalian mitochondria of the central nervous system. A combination of Gomori's acid phosphatase method, however, with standard electron microscopy has disclosed the presence of enzyme reaction products in the mitochondria of the central nervous system of rats from 2 hr to 22 weeks after x-ray irradiation, as well as in a cerebral biopsy performed on a patient affected by Huntington's chorea. No enzyme reaction products, on the other hand, were observedmore » in serial sections that had been incubated in substrates either containing sodium fluoride or lacking in $beta$- glycerophosphate. The abnormal mitochondrial enzyme reaction (chemical lesion) is considered to be the consequence of the pathologic process affecting the ultrastructural-chemical organization of the organelle. (auth)« less

Simultaneous production of oil enriched in ω-3 polyunsaturated fatty acids and biodiesel from fish wastes.

PubMed

Enascuta, Cristina Emanuela; Stepan, Emil; Bolocan, Ion; Bombos, Dorin; Calin, Catalina; Oprescu, Elena-Emilia; Lavric, Vasile

2018-05-01

The waste resulted from fish processing industries are discarded into the environment around the world, causing environmental pollution. The main problem of fish oil extracted from waste is the high content in free fatty acids (FFA) which decrease the yield in fatty acids esters during transesterification reactions. Therefore, to correct the fish-oil properties, a new environmentally friendly heterogeneous superacid catalyst (SO 4 2- /SnO 2 -ZrO 2 ) was tested in the esterification reaction of FFA with ethanol. The catalyst was characterized by different techniques (XRD, FT-IR, FT-IR of adsorbed pyridine, BET, SEM-EDX, TGA and acidity measurements). The reaction was found to follow a Langmuir-Hinshelwood (L-H) dual-site mechanism with the novelty that both Brönsted and Lewis acid centers participate equally in the esterification reaction. The pre-treated oil was subjected to transesterification reaction with ethanol over a heterogeneous base catalyst and then, the saturated and unsaturated fractions of fatty acid ethyl esters (FAEE) were separated using a vacuum rectification unit with falling film. The saturated content can be used as biofuel, while the unsaturated FAEE are further transesterified with glycerol in order to obtain oil with high content in polyunsaturated fatty acids (PUFA). A detailed study of the intrinsic kinetic process at the surface of the superacid catalyst and a thorough mathematical model of the fixed bed reactor were written and validated by an experimental program, designed according to the D-optimal methodology. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sulfur Radical-Induced Redox Modifications in Proteins: Analysis and Mechanistic Aspects.

PubMed

Schöneich, Christian

2017-03-10

The sulfur-containing amino acids cysteine (Cys) and methionine (Met) are prominent protein targets of redox modification during conditions of oxidative stress. Here, two-electron pathways have received widespread attention, in part due to their role in signaling processes. However, Cys and Met are equally prone to one-electron pathways, generating intermediary radicals and/or radial ions. These radicals/radical ions can generate various reaction products that are not commonly monitored in redox proteomic studies, but they may be relevant for the fate of proteins during oxidative stress. Recent Advances: Time-resolved kinetic studies and product analysis have expanded our mechanistic understanding of radical reaction pathways of sulfur-containing amino acids. These reactions are now studied in some detail for Met and Cys in proteins, and homocysteine (Hcy) chemically linked to proteins, and the role of protein radical reactions in physiological processes is evolving. Radical-derived products from Cys, Hcy, and Met can react with additional amino acids in proteins, leading to secondary protein modifications, which are potentially remote from initial points of radical attack. These products may contain intra- and intermolecular cross-links, which may lead to protein aggregation. Protein sequence and conformation will have a significant impact on the formation of such products, and a thorough understanding of reaction mechanisms and specifically how protein structure influences reaction pathways will be critical for identification and characterization of novel reaction products. Future studies must evaluate the biological significance of novel reaction products that are derived from radical reactions of sulfur-containing amino acids. Antioxid. Redox Signal. 26, 388-405.

Methods for suppressing isomerization of olefin metathesis products

DOEpatents

Firth, Bruce E.; Kirk, Sharon E.; Gavaskar, Vasudeo S.

2015-09-22

A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. The isomerization suppression agent is phosphorous acid, a phosphorous acid ester, phosphinic acid, a phosphinic acid ester or combinations thereof. Methods of refining natural oils are described.

Production of aviation fuel via catalytic hydrothermal decarboxylation of fatty acids in microalgae oil.

PubMed

Yang, Cuiyue; Nie, Renfeng; Fu, Jie; Hou, Zhaoyin; Lu, Xiuyang

2013-10-01

A series of fatty acids in microalgae oil, such as stearic acid, palmitic acid, lauric acid, myristic acid, arachidic acid and behenic acid, were selected as the raw materials to produce aviation fuel via hydrothermal decarboxylation over a multi-wall carbon nanotube supported Pt catalyst (Pt/MWCNTs). It was found that Pt/MWCNTs catalysts exhibited higher activity for the hydrothermal decarboxylation of stearic acid with a 97% selectivity toward heptadecane compared to Pt/C and Ru/C under the same conditions. And Pt/MWCNTs is also capable for the decarboxylation of different fatty acids in microalgae oil. The reaction conditions, such as Pt/MWCNTs loading amount, reaction temperature and time were optimized. The activation energy of stearic acid decarboxylation over Pt/MWCNTs was calculated (114 kJ/mol). Copyright © 2013 Elsevier Ltd. All rights reserved.

Modeling and optimization of phospholipase A₁-catalyzed hydrolysis of phosphatidylcholine using response surface methodology for lysophosphatidylcholine production.

PubMed

Lim, Chang Wan; Kim, Byung Hee; Kim, In-Hwan; Lee, Moon-Won

2015-01-01

Modeling the phospholipase A1 (PLA1 )-catalyzed partial hydrolysis of soy phosphatidylcholine (PC) in hexane for the production of lysophosphatidylcholine (LPC) and optimizing the reaction conditions using response surface methodology were described. The reaction was performed with 4 g of PC in a stirred batch reactor using a commercial PLA1 (Lecitase Ultra) as the biocatalyst. The effects of temperature, reaction time, water content, and enzyme loading on LPC and glycerylphosphorylcholine (GPC) content in the reaction products were elucidated using the models established. Optimal reaction conditions for maximizing the LPC content while suppressing acyl migration, which causes GPC formation, were as follows: temperature, 60°C; reaction time, 3 h; water content, 10% of PC; and enzyme loading, 1% of PC. When the reaction was conducted with 40 g of PC under these conditions, the reaction products contained 83.7 mol % LPC and were free of GPC. LPC had a higher total unsaturated fatty acid content than original PC had and was mainly composed of linoleic acid (78.0 mol % of the total fatty acids). © 2014 American Institute of Chemical Engineers.

Synthesis of Hydrophobic, Crosslinkable Resins.

DTIC Science & Technology

1984-12-01

insoluble products, in reactions analogous to the preparation of polyimides from polyamic acids . Examples fron7 the recent literature are provided by the...Vilsmeyer formylation,using a secondary amine with formic acid and phosphorous oxychloride [471. d. Probably the most convenient method utilises...such as styrene react with Lewis acids and so the scope for Friedel Crafts reactions is limited. Stilbene and its derivatives may be employed in such

Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

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

Jiang, Tingshun, E-mail: tshjiang@mail.ujs.edu.cn; Cheng, Jinlian; Liu, Wangping

2014-10-15

Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH{sub 3}-TPD and N{sub 2} physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 still have good mesoporous structure and long rangemore » ordering. Compared with the Zr (or Al)–MCM-48 samples, SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO{sub 4}{sup 2−}/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h{sup −1} and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO{sub 4}{sup 2−}/Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO{sub 4}{sup 2−}/Zr-MCM-48-25.« less

Synthesis of new β-amidodehydroaminobutyric acid derivatives and of new tyrosine derivatives using copper catalyzed C-N and C-O coupling reactions.

PubMed

Pereira, G; Vilaça, H; Ferreira, P M T

2013-02-01

Several β-amidodehydroaminobutyric acid derivatives were prepared from N,C-diprotected β-bromodehydroaminobutyric acids and amides by a copper catalyzed C-N coupling reaction. The best reaction conditions include the use of a catalytic amount of CuI, N,N'-dimethylethylenediamine as ligand and K(2)CO(3) as base in toluene at 110 °C. The stereochemistry of the products was determined using NOE difference experiments and the results obtained are in agreement with an E-stereochemistry. Thus, the stereochemistry is maintained in the case of the E-isomers of β-bromodehydroaminobutyric acid derivatives, but when the Z-isomers were used as substrates the reaction proceeds with inversion of configuration. The use of β-bromodehydrodipeptides as substrates was also tested. It was found that the reaction outcome depend on the stereochemistry of the β-bromodehydrodipeptide and on the nature of the first amino acid residue. The products isolated were the β-amidodehydrodipeptide derivatives and/or the corresponding dihydropyrazines. The same catalytic system (CuI/N,N'-dimethylethylene diamine) was used in the C-O coupling reactions between a tyrosine derivative and aryl bromides. The new O-aryltyrosine derivatives were isolated in moderate to good yields. The photophysical properties of two of these compounds were studied in four solvents of different polarity. The results show that these compounds after deprotection can be used as fluorescence markers.

Reaction pathways for the deoxygenation of vegetable oils and related model compounds.

PubMed

Gosselink, Robert W; Hollak, Stefan A W; Chang, Shu-Wei; van Haveren, Jacco; de Jong, Krijn P; Bitter, Johannes H; van Es, Daan S

2013-09-01

Vegetable oil-based feeds are regarded as an alternative source for the production of fuels and chemicals. Paraffins and olefins can be produced from these feeds through catalytic deoxygenation. The fundamentals of this process are mostly studied by using model compounds such as fatty acids, fatty acid esters, and specific triglycerides because of their structural similarity to vegetable oils. In this Review we discuss the impact of feedstock, reaction conditions, and nature of the catalyst on the reaction pathways of the deoxygenation of vegetable oils and its derivatives. As such, we conclude on the suitability of model compounds for this reaction. It is shown that the type of catalyst has a significant effect on the deoxygenation pathway, that is, group 10 metal catalysts are active in decarbonylation/decarboxylation whereas metal sulfide catalysts are more selective to hydrodeoxygenation. Deoxygenation studies performed under H2 showed similar pathways for fatty acids, fatty acid esters, triglycerides, and vegetable oils, as mostly deoxygenation occurs indirectly via the formation of fatty acids. Deoxygenation in the absence of H2 results in significant differences in reaction pathways and selectivities depending on the feedstock. Additionally, using unsaturated feedstocks under inert gas results in a high selectivity to undesired reactions such as cracking and the formation of heavies. Therefore, addition of H2 is proposed to be essential for the catalytic deoxygenation of vegetable oil feeds. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactions of Thiocyanate Ions with Acid: A Laboratory Experiment.

ERIC Educational Resources Information Center

Glidewell, Christopher; And Others

1984-01-01

Background information, procedures, and typical results are provided for a three-part experiment involving reactions of potassium thiocynate (KNCS) with sulfuric acid. The experiment represents the final stage of structured work prior to students' research projects during their final year. (JM)

Interactions between Therapeutic Proteins and Acrylic Acid Leachable.

PubMed

Liu, Dengfeng; Nashed-Samuel, Yasser; Bondarenko, Pavel V; Brems, David N; Ren, Da

2012-01-01

Leachables are chemical compounds that migrate from manufacturing equipment, primary containers and closure systems, and packaging components into biopharmaceutical and pharmaceutical products. Acrylic acid (at concentration around 5 μg/mL) was detected as leachable in syringes from one of the potential vendors (X syringes). In order to evaluate the potential impact of acrylic acid on therapeutic proteins, an IgG 2 molecule was filled into a sterilized X syringe and then incubated at 45 °C for 45 days in a pH 5 acetate buffer. We discovered that acrylic acid can interact with proteins at three different sites: (1) the lysine side chain, (2) the N-terminus, and (3) the histidine side chain, by the Michael reaction. In this report, the direct interactions between acrylic acid leachable and a biopharmaceutical product were demonstrated and the reaction mechanism was proposed. Even thought a small amount (from 0.02% to 0.3%) of protein was found to be modified by acrylic acid, the modified protein can potentially be harmful due to the toxicity of acrylic acid. After being modified by acrylic acid, the properties of the therapeutic protein may change due to charge and hydrophobicity variations. Acrylic acid was detected to migrate from syringes (Vendor X) into a therapeutic protein solution (at a concentration around 5 μg/mL). In this study, we discovered that acrylic acid can modify proteins at three different sites: (1) the lysine side chain, 2) the N-terminus, and 3) the histidine side chain, by the Michael reaction. In this report, the direct interactions between acrylic acid leachable and a biopharmaceutical product were demonstrated and the reaction mechanism was proposed.

The fluorimetric microdetermination of glyoxylic acid in blood, urine and bacterial extracts

PubMed Central

Zarembski, P. M.; Hodgkinson, A.

1965-01-01

1. A spectrophotofluorimetric method for the determination of glyoxylic acid in biological materials is described. 2. The method is based on the reaction between glyoxylic acid and resorcinol in acid solution, a fluorescent complex being obtained on the subsequent addition of alkali. 3. The reaction was found to be sensitive and highly specific, the minimum detectable amount of glyoxylic acid being 1·35×10−8 mole. 4. The urinary excretion of glyoxylic acid by ten normal adults ranged from 1·4 to 4·7mg./24hr. Small but measurable amounts of glyoxylic acid were found in cell-free extracts of Pseudomonas oxalaticus OX1 grown on oxalic acid as a source of carbon. No glyoxylic acid was detected in human serum. PMID:14343135

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

PubMed Central

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

2013-01-01

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

The kinetics of lanthanide complexation by EDTA and DTPA in lactate media.

PubMed

Nash, K L; Brigham, D; Shehee, T C; Martin, A

2012-12-28

The interaction of trivalent lanthanide and actinide cations with polyaminopolycarboxylic acid complexing agents in lactic acid buffer systems is an important feature of the chemistry of the TALSPEAK process for the separation of trivalent actinides from lanthanides. To improve understanding of metal ion coordination chemistry in this process, the results of an investigation of the kinetics of lanthanide complexation by ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA) and diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA) in 0.3 M lactic acid/0.3 M ionic strength solution are reported. Progress of the reaction was monitored using the distinctive visible spectral changes attendant to lanthanide complexation by the colorimetric indicator ligand Arsenazo III, which enables the experiment but plays no mechanistic role. Under the conditions of these experiments, the reactions occur in a time regime suitable for study by stopped-flow spectrophotometric techniques. Experiments have been conducted as a function of EDTA/DTPA ligand concentration, total lactic acid concentration, and pH. The equilibrium perturbation reaction proceeds as a first order approach to equilibrium over a wide range of conditions, allowing the simultaneous determination of complex formation and dissociation rate constants. The rate of the complexation reaction has been determined for the entire lanthanide series (except Pm(3+)). The predominant pathway for lanthanide-EDTA and lanthanide-DTPA dissociation is inversely dependent on the total lactate concentration; the complex formation reaction demonstrates a direct dependence on [H(+)]. Unexpectedly, the rate of the complex formation reaction is seen in both ligand systems to be fastest for Gd(3+). Correlation of these results indicates that in 0.3 M lactate solutions the exchange of lanthanide ions between lactate complexes and the polyaminopolycarboxylate govern the process.

Permanganate oxidation of α-amino acids: kinetic correlations for the nonautocatalytic and autocatalytic reaction pathways.

PubMed

Perez-Benito, Joaquin F

2011-09-08

The reactions of permanganate ion with seven α-amino acids in aqueous KH(2)PO(4)/K(2)HPO(4) buffers have been followed spectrophotometrically at two different wavelengths: 526 nm (decay of MnO(4)(-)) and 418 nm (formation of colloidal MnO(2)). All of the reactions studied were autocatalyzed by colloidal MnO(2), with the contribution of the autocatalytic reaction pathway decreasing in the order glycine > l-threonine > l-alanine > l-glutamic acid > l-leucine > l-isoleucine > l-valine. The rate constants corresponding to the nonautocatalytic and autocatalytic pathways were obtained by means of either a differential rate law or an integrated one, the latter requiring the use of an iterative method for its implementation. The activation parameters for the two pathways were determined and analyzed to obtain statistically significant correlations for the series of reactions studied. The activation enthalpy of the nonautocatalytic pathway showed a strong, positive dependence on the standard Gibbs energy for the dissociation of the protonated amino group of the α-amino acid. Linear enthalpy-entropy correlations were found for both pathways, leading to isokinetic temperatures of 370 ± 21 K (nonautocatalytic) and 364 ± 28 K (autocatalytic). Mechanisms in agreement with the experimental data are proposed for the two reaction pathways.

Study of quinones reactions with wine nucleophiles by cyclic voltammetry.

PubMed

Oliveira, Carla M; Barros, António S; Ferreira, António C S; Silva, Artur M S

2016-11-15

Quinones are electrophilic species which can react with various nucleophiles, like wine antioxidants, such as sulfur dioxide or ascorbic acid, thiols, amino acids, and numerous polyphenols. These reactions are very important in wine aging because they mediate oxygen reactions during both production and bottle aging phases. In this work, the major challenge was to determine the interaction between ortho-quinones and wine nucleophiles (amino acids, thiols, and the antioxidants SO2 and ascorbic acid), by cyclic voltammetry. Wine-model solutions with gallic acid, caffeic acid, or (+)-catechin and nucleophilic compounds were used. To understand the effect of nucleophilic addition in wine, a white wine with the same added nucleophiles was also analysed. Cyclic voltammograms were taken with glassy carbon electrode or screen-printed carbon electrodes, respectively, for wine-model and white wines solutions, in the absence and in the presence of nucleophiles. A nucleophilic order profile related to the cathodic current intensity decrease was observed. Copyright © 2016 Elsevier Ltd. All rights reserved.

How are the Concepts and Theories of Acid Base Reactions Presented? Chemistry in Textbooks and as Presented by Teachers

NASA Astrophysics Data System (ADS)

Furió-Más, Carlos; Calatayud, María Luisa; Guisasola, Jenaro; Furió-Gómez, Cristina

2005-09-01

This paper investigates the views of science and scientific activity that can be found in chemistry textbooks and heard from teachers when acid base reactions are introduced to grade 12 and university chemistry students. First, the main macroscopic and microscopic conceptual models are developed. Second, we attempt to show how the existence of views of science in textbooks and of chemistry teachers contributes to an impoverished image of chemistry. A varied design has been elaborated to analyse some epistemological deficiencies in teaching acid base reactions. Textbooks have been analysed and teachers have been interviewed. The results obtained show that the teaching process does not emphasize the macroscopic presentation of acids and bases. Macroscopic and microscopic conceptual models involved in the explanation of acid base processes are mixed in textbooks and by teachers. Furthermore, the non-problematic introduction of concepts, such as the hydrolysis concept, and the linear, cumulative view of acid base theories (Arrhenius and Brönsted) were detected.

Synthesis of biodiesel from a model waste oil feedstock using a carbon-based solid acid catalyst: reaction and separation.

PubMed

Shu, Qing; Nawaz, Zeeshan; Gao, Jixian; Liao, Yuhui; Zhang, Qiang; Wang, Dezheng; Wang, Jinfu

2010-07-01

A solid acid catalyst that can keep high activity and stability is necessary when low cost feedstocks are utilized for biodiesel synthesis because the reaction medium contains a large amount of water. Three solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt. The structure of these catalysts was characterized by a variety of techniques. A new process that used the coupling of the reaction and separation was employed, which greatly improved the conversion of cottonseed oil (triglyceride) and free fatty acids (FFA) when a model waste oil feedstock was used. The vegetable oil asphalt-based catalyst showed the highest catalytic activity. This was due to the high density and stability of its acid sites, its loose irregular network, its hydrophobicity that prevented the hydration of -OH species, and large pores that provided more acid sites for the reactants. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Interactive effects of cadmium and acid rain on photosynthetic light reaction in soybean seedlings.

PubMed

Sun, Zhaoguo; Wang, Lihong; Chen, Minmin; Wang, Lei; Liang, Chanjuan; Zhou, Qing; Huang, Xiaohua

2012-05-01

Interactive effects of cadmium (Cd(2+)) and acid rain on photosynthetic light reaction in soybean seedlings were investigated under hydroponic conditions. Single treatment with Cd(2+) or acid rain and the combined treatment decreased the content of chlorophyll, Hill reaction rate, the activity of Mg(2+)-ATPase, maximal photochemical efficiency and maximal quantum yield, increased initial fluorescence and damaged the chloroplast structure in soybean seedlings. In the combined treatment, the change in the photosynthetic parameters and the damage of chloroplast structure were stronger than those of any single pollution. Meanwhile, Cd(2+) and acid rain had the interactive effects on the test indices in soybean seedlings. The results indicated that the combined pollution of Cd(2+) and acid rain aggravated the toxic effect of the single pollution of Cd(2+) or acid rain on the photosynthetic parameters due to the serious damage to the chloroplast structure. Copyright © 2011 Elsevier Inc. All rights reserved.

Versatile Synthesis of Amino Acid Functional Polymers without Protection Group Chemistry.

PubMed

Brisson, Emma R L; Xiao, Zeyun; Franks, George V; Connal, Luke A

2017-01-09

The copolymerization of N-isopropylacrylamide (NiPAm) with aldehyde functional monomers facilitates postpolymerization functionalization with amino acids via reductive amination, negating the need for protecting groups. In reductive amination, the imine formed from the condensation reaction between an amine and an aldehyde is reduced to an amine. In this work, we categorize amino acids into four classes based on the functionality of their side chains (acidic, polar neutral, neutral, and basic) and use their amine groups in condensation reactions with aldehyde functional polymers. The dynamic nature of the imine as well as the versatility of reductive amination to functionalize a polymer with a range of amino acids is highlighted. In this manner, amino acid functional polymers are synthesized without the use of protecting groups with high yields, demonstrating the high functional group tolerance of carbonyl condensation chemistry and the subsequent reduction of the imine. Prior to the reduction of the imine bond, transimination reactions are used to demonstrate dynamic polymers that shuffle from a glycine- to a histidine-functional polymer.

Mutual amino acid catalysis in salt-induced peptide formation supports this mechanism's role in prebiotic peptide evolution.

PubMed

Suwannachot, Y; Rode, B M

1999-10-01

The presence of some amino acids and dipeptides under the conditions of the salt-induced peptide formation reaction (aqueous solution at 85 degrees C, Cu(II) and NaCl) has been found to catalyze the formation of homopeptides of other amino acids, which are otherwise produced only in traces or not at all by this reaction. The condensation of Val, Leu and Lys to form their homodipeptides can occur to a considerable extent due to catalytic effects of other amino acids and related compounds, among which glycine, histidine, diglycine and diketopiperazine exhibit the most remarkable activity. These findings also lead to a modification of the table of amino acid sequences preferentially formed by the salt-induced peptide formation (SIPF) reaction, previously used for a comparison with the sequence preferences in membrane proteins of primitive organisms.

Mutual Amino Acid Catalysis in Salt-Induced Peptide Formation Supports this Mechanism's Role in Prebiotic Peptide Evolution

NASA Astrophysics Data System (ADS)

Suwannachot, Yuttana; Rode, Bernd M.

1999-10-01

The presence of some amino acids and dipeptides under the conditions of the salt-induced peptide formation reaction (aqueous solution at 85 °C, Cu(II) and NaCl) has been found to catalyze the formation of homopeptides of other amino acids, which are otherwise produced only in traces or not at all by this reaction. The condensation of Val, Leu and Lys to form their homodipeptides can occur to a considerable extent due to catalytic effects of other amino acids and related compounds, among which glycine, histidine, diglycine and diketopiperazine exhibit the most remarkable activity. These findings also lead to a modification of the table of amino acid sequences preferentially formed by the salt-induced peptide formation (SIPF) reaction, previously used for a comparison with the sequence preferences in membrane proteins of primitive organisms

Differential diffusion effects on buoyancy-driven instabilities of acid-base fronts: the case of a color indicator.

PubMed

Kuster, S; Riolfo, L A; Zalts, A; El Hasi, C; Almarcha, C; Trevelyan, P M J; De Wit, A; D'Onofrio, A

2011-10-14

Buoyancy-driven hydrodynamic instabilities of acid-base fronts are studied both experimentally and theoretically in the case where an aqueous solution of a strong acid is put above a denser aqueous solution of a color indicator in the gravity field. The neutralization reaction between the acid and the color indicator as well as their differential diffusion modifies the initially stable density profile in the system and can trigger convective motions both above and below the initial contact line. The type of patterns observed as well as their wavelength and the speed of the reaction front are shown to depend on the value of the initial concentrations of the acid and of the color indicator and on their ratio. A reaction-diffusion model based on charge balances and ion pair mobility explains how the instability scenarios change when the concentration of the reactants are varied.

Estolides Synthesis Catalyzed by Immobilized Lipases

PubMed Central

Aguieiras, Erika C. G.; Veloso, Cláudia O.; Bevilaqua, Juliana V.; Rosas, Danielle O.; da Silva, Mônica A. P.; Langone, Marta A. P.

2011-01-01

Estolides are vegetable-oil-based lubricants obtained from oleic acid or any source of hydroxy fatty acids. In this work, the estolides synthesis from oleic acid and methyl ricinoleate (biodiesel from castor oil), using immobilized commercial lipases (Novozym 435, Lipozyme RM-IM, and Lipozyme TL-IM) in a solvent-free medium was investigated. Acid value was used to monitor the reaction progress by determining the consumption of acid present in the medium. Novozym 435 showed the best performance. Water removal improved the conversion. Novozym 435 was more active at atmospheric pressure. Novozym 435 was reused four times with conversion reaching 15% after the fourth reaction at 80°C. Estolides produced under the reaction conditions used in this work presented good properties, such as, low temperature properties as pour point (−24°C), viscosity (23.9 cSt at 40°C and 5.2 cSt at 100°C), and viscosity index (153). PMID:21755040

Stereodivergent Mannich reaction of bis(trimethylsilyl)ketene acetals with N-tert-butanesulfinyl imines by Lewis acid or Lewis base activation, a one-pot protocol to obtain chiral β-amino acids.

PubMed

Cantú-Reyes, Margarita; Alvarado-Beltrán, Isabel; Ballinas-Indilí, Ricardo; Álvarez-Toledano, Cecilio; Hernández-Rodríguez, Marcos

2017-09-20

We report a one-pot synthesis of chiral β 2,2,3 -amino acids by the Mannich addition of bistrimethylsilyl ketene acetals to N-tert-butanesulfinyl imines followed by the removal of the chiral auxiliary. The synthesis and isolation of pure β-amino acid hydrochlorides were conducted under mild conditions, without strong bases and this method is operationally simple. The stereoselective reaction was promoted by two different activation methods that lead to different stereoisomers: (1) Lewis Acid (LA) catalysis with boron trifluoride diethyl etherate and (2) Lewis Base (LB) catalysis with tetrabutylammonium difluorotriphenylsilicate. The reaction presented good diastereoselectivity with LB activation and moderate to good dr with LA catalysis. The exceptions in both protocols were imines with electron donating groups in the aromatic ring.

Photo-kinetics of photoinduced transformation reaction of methylene green with titanium trichloride in different solvents

NASA Astrophysics Data System (ADS)

Nadeem, Syed Muhammad Saqib; Saeed, Rehana

2017-08-01

The photo-kinetics of photoinduced transformation reaction of methylene green and titanium trichloride was investigated in water and different aqueous-alcoholic solvents. The reaction is pseudo-first order, dependent only on the concentration of titanium trichloride at fixed concentration of methylene green. The effect of water and aqueous-alcoholic solvents was studied in the acidic range from 4 to 7. It was observed that the quantum yield (φ) of reaction increased with increase in polarity of the solvent. The quantum yield (φ) was high in acidic condition and decreased with further increase in acidity. The quantum yield (φ) increased sharply with increase in concentration of titanium trichloride while it almost remained unaffected by change in concentration of methylene green. The addition of ions increased the quantum yield (φ) of reaction. The increase in temperature decreased the rate and quantum yield (φ) of reaction. An electron transfer mechanism for the reaction has been proposed in accordance with the kinetics of reaction. The absence of any reaction intermediate was confirmed by spectroscopic investigations. Activation energy ( E a) was calculated by Arrhenius relation. Thermodynamic parameters such as activation energy ( E a), enthalpy change (Δ H), free energy change (Δ G) and entropy change (Δ S) were also evaluated.

Experimental and Quantum Mechanics Investigations of Early Reactions of Monomethylhydrazine with Mixtures of NO2 and N2O4

DTIC Science & Technology

2013-02-15

red fuming nitric acid (RFNA), which is composed of nitric acid (HNO3, 85 wt%) and NO2 (8–15 wt%). Recently the impinging stream vortex engine (ISVE... nitric acid [51]. As a result, growth of the particles is favored over H-abstraction reactions at the low temperatures of our experiments. As the...followed by the proton transfer from NAH bond to NO3 to form nitric acid , as shown in Scheme 3. Although it is very easy to form nitric acid (enthalpic

Effect of silicate and phosphate additives on the kinetics of the oxygen evolution reaction in valve-regulated lead/acid batteries

NASA Astrophysics Data System (ADS)

Vinod, M. P.; Vijayamohanan, K.; Joshi, S. N.

Effect of sodium silicate and phosphoric acid additives on the kinetics of oxygen evolution on PbO 2 electrodes in sulfuric acid has been studied in gelled and flooded electrolytes with relevance to valve-regulated lead/acid batteries. A comparison of the open-circuit potential versus time transients, with and without these additives, indicates that the additives suppress self-discharge of the electrodes. Tafel polarization studies also suggest that the addition of phosphoric acid attenuates the rate of oxygen evolution reaction. These findings have been supported with cyclic voltammetric data.

Recovery of organic acids

DOEpatents

Verser, Dan W.; Eggeman, Timothy J.

2009-10-13

A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO.sub.2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.

Recovery of organic acids

DOEpatents

Verser, Dan W [Menlo Park, CA; Eggeman, Timothy J [Lakewood, CO

2011-11-01

A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO.sub.2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.

Thermometric titrimetry Studies of the cerium(IV) oxidation of alpha-mercaptocarboxylic acids.

PubMed

Alexander, W A; Mash, C J; McAuley, A

1969-04-01

The cerium(IV) oxidation of thioglycollic, thiolactic and thiomalic acids has been examined by thermometric titration. The titration curves indicate stoichiometries of more than 1 mole of cerium(IV) per mole of alpha-thiol, suggesting possible side-reactions. In the presence of methyl acrylate, however, the expected ratio is observed. The overall heat of each reaction has been derived. Only with a titration method of this kind where allowance can be made for side-reactions can the heats of reaction for these systems be measured.

The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

1982-01-01

The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

Stereochemical analysis of the elimination reaction catalyzed by D-amino-acid oxidase.

PubMed

Cheung, Y F; Walsh, C

1976-06-01

The stereochemistry of the intramolecular proton transfer catalyzed by the flavoenzyme, D-amino-acid oxidase, during the elimination reaction of beta-chloro-alpha-amino acid substrates (Walsh et al. (1973), J. Biol. Chem. 248, 1964) has been established. Both D-erythro- and D-threo-2-amino-3-chloro(2-3H) butyrate have been shown to yield (3R)-2-keto (3-3H)-2- butyrate predominantly. Tritium kinetic isotope effects on the rate of the reaction (4.7 for the D-erythro, and 3.8 for the D-threo compound) and percentages of intramolecular triton transfer (7.2% for the D-erythro- and 2.6% for the D-threo compound) have been measured. Their implications on the mechanism of this unusual elimination reaction are discussed.

Esterification Reaction of Glycerol and Palm Oil Oleic Acid Using Methyl Ester Sulfonate Acid Catalyst as Drilling Fluid Formulation

NASA Astrophysics Data System (ADS)

Sari, V. I.; Hambali, E.; Suryani, A.; Permadi, P.

2017-02-01

Esterification reaction between glycerol with palm oil oleic acid to produce glycerol ester and one of the utilization of glycerol esters is as ingredients of drilling fluids formula for oil drilling needs. The purpose of this research is to get the best conditions of the esterification process. The esterification reaction does with the reactants is glycerol with purity of 97.6%, palm oil oleic acid with the molar ratio is 1:1, Methyl Ester Sulfonate Acid (MESA) catalyst 0.5%, and stirring speed 400 rpm. The temperature range of 180°C to 240°C and the processing time between 120 to 180 minutes. The results showed that the best conditions of the esterification reaction at the temperature 240°C and time process are 180 minute. The increasing temperature resulted that the acid number decreases and causing the conversion increased. The maximum conversion is 99.24%, density 0.93 g/cm3, flash point 241°C, pour point -3°C, the boiling point of 244 °C, the acid value of 1.90 mg KOH/g sample, kinematic viscosity 31.51 cSt (40°C), surface tension 37.0526 dyne/cm and GCMS identification, glycerol ester at 22,256 retention time (minutes) and wide area 73.75 (%). From the research results obtained glycerol ester with characteristics suitable for drilling fluid formulations.

Radiation chemistry of salicylic and methyl substituted salicylic acids: Models for the radiation chemistry of pharmaceutical compounds

NASA Astrophysics Data System (ADS)

Ayatollahi, Shakiba; Kalnina, Daina; Song, Weihua; Turks, Maris; Cooper, William J.

2013-11-01

Salicylic acid and its derivatives are components of many medications and moieties found in numerous pharmaceutical compounds. They have been used as models for various pharmaceutical compounds in pharmacological studies, for the treatment of pharmaceuticals and personal care products (PPCPs), and, reactions with natural organic matter (NOM). In this study, the radiation chemistry of benzoic acid, salicylic acid and four methyl substituted salicylic acids (MSA) is reported. The absolute bimolecular reaction rate constants for hydroxyl radical reaction with benzoic and salicylic acids as well as 3-methyl-, 4-methyl-, 5-methyl-, and 6-methyl-salicylic acid were determined (5.86±0.54)×109, (1.07±0.07)×1010, (7.48±0.17)×109, (7.31±0.29)×109, (5.47±0.25)×109, (6.94±0.10)×109 (M-1 s-1), respectively. The hydrated electron reaction rate constants were measured (3.02±0.10)×109, (8.98±0.27)×109, (5.39±0.21)×109, (4.33±0.17)×109, (4.72±0.15)×109, (1.42±0.02)×109 (M-1 s-1), respectively. The transient absorption spectra for the six model compounds were examined and their role as model compounds for the radiation chemistry of pharmaceuticals investigated.

Production of Biodiesel by Esterification of Free Fatty Acid over Solid Catalyst from Biomass Waste

NASA Astrophysics Data System (ADS)

Mukti, N. I. F.; Sutrisno, B.; Hidayat, A.

2018-05-01

Recently, low cost feedstocks have been utilized to replace vegetable oils in order to improve the economic feasibility of biodiesel. The esterification of free fatty acid (FFA) on Palm Fatty Acid Distillate (PFAD) with methanol using solid catalyst generated from bagasse fly ash is a promising method to convert FFA into biodiesel. In this research, the esterification of FFA on PFAD using the sulfonated bagasse fly ash catalyst was studied. The performances of the catalysts were evaluated in terms of the reaction temperatures, the molar ratios of methanol to PFAD, and the catalyst loading. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimum conditions were methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%wt. of PFAD, and reaction temperature of 6°C. The reusability of the solid acid carbon catalysts was also studied in this work. The catalytic activity decreased up to 38% after third cycle. The significant decline in catalyst esterification activity was due to acid site leaching. The physico-characteristics and acid site densities were analyzed by Nitrogen gas adsorption, surface functional groups by Fourier transform infrared spectroscopy (FT-IR), elemental analysis using X-ray fluorescent (XRF), and acid-base back titration methods for determination of acid density.

Kinetics and Optimization of Lipophilic Kojic Acid Derivative Synthesis in Polar Aprotic Solvent Using Lipozyme RMIM and Its Rheological Study.

PubMed

Ishak, Nurazwa; Lajis, Ahmad Firdaus B; Mohamad, Rosfarizan; Ariff, Arbakariya B; Mohamed, Mohd Shamzi; Halim, Murni; Wasoh, Helmi

2018-02-24

The synthesis of kojic acid derivative (KAD) from kojic and palmitic acid (C16:0) in the presence of immobilized lipase from Rhizomucor miehei (commercially known as Lipozyme RMIM), was studied using a shake flask system. Kojic acid is a polyfunctional heterocycles that acts as a source of nucleophile in this reaction allowing the formation of a lipophilic KAD. In this study, the source of biocatalyst, Lipozyme RMIM, was derived from the lipase of Rhizomucor miehei immobilized on weak anion exchange macro-porous Duolite ES 562 by the adsorption technique. The effects of solvents, enzyme loading, reaction temperature, and substrate molar ratio on the reaction rate were investigated. In one-factor-at-a-time (OFAT) experiments, a high reaction rate (30.6 × 10 -3 M·min -1 ) of KAD synthesis was recorded using acetone, enzyme loading of 1.25% ( w / v ), reaction time of 12 h, temperature of 50 °C and substrate molar ratio of 5:1. Thereafter, a yield of KAD synthesis was optimized via the response surface methodology (RSM) whereby the optimized molar ratio (fatty acid: kojic acid), enzyme loading, reaction temperature and reaction time were 6.74, 1.97% ( w / v ), 45.9 °C, and 20 h respectively, giving a high yield of KAD (64.47%). This condition was reevaluated in a 0.5 L stirred tank reactor (STR) where the agitation effects of two impellers; Rushton turbine (RT) and pitch-blade turbine (PBT), were investigated. In the STR, a very high yield of KAD synthesis (84.12%) was achieved using RT at 250 rpm, which was higher than the shake flask, thus indicating better mixing quality in STR. In a rheological study, a pseudoplastic behavior of KAD mixture was proposed for potential application in lotion formulation.

Digital isothermal quantification of nucleic acids via simultaneous chemical initiation of recombinase polymerase amplification reactions on SlipChip.

PubMed

Shen, Feng; Davydova, Elena K; Du, Wenbin; Kreutz, Jason E; Piepenburg, Olaf; Ismagilov, Rustem F

2011-05-01

In this paper, digital quantitative detection of nucleic acids was achieved at the single-molecule level by chemical initiation of over one thousand sequence-specific, nanoliter isothermal amplification reactions in parallel. Digital polymerase chain reaction (digital PCR), a method used for quantification of nucleic acids, counts the presence or absence of amplification of individual molecules. However, it still requires temperature cycling, which is undesirable under resource-limited conditions. This makes isothermal methods for nucleic acid amplification, such as recombinase polymerase amplification (RPA), more attractive. A microfluidic digital RPA SlipChip is described here for simultaneous initiation of over one thousand nL-scale RPA reactions by adding a chemical initiator to each reaction compartment with a simple slipping step after instrument-free pipet loading. Two designs of the SlipChip, two-step slipping and one-step slipping, were validated using digital RPA. By using the digital RPA SlipChip, false-positive results from preinitiation of the RPA amplification reaction before incubation were eliminated. End point fluorescence readout was used for "yes or no" digital quantification. The performance of digital RPA in a SlipChip was validated by amplifying and counting single molecules of the target nucleic acid, methicillin-resistant Staphylococcus aureus (MRSA) genomic DNA. The digital RPA on SlipChip was also tolerant to fluctuations of the incubation temperature (37-42 °C), and its performance was comparable to digital PCR on the same SlipChip design. The digital RPA SlipChip provides a simple method to quantify nucleic acids without requiring thermal cycling or kinetic measurements, with potential applications in diagnostics and environmental monitoring under resource-limited settings. The ability to initiate thousands of chemical reactions in parallel on the nanoliter scale using solvent-resistant glass devices is likely to be useful for a broader range of applications.

Digital Isothermal Quantification of Nucleic Acids via Simultaneous Chemical Initiation of Recombinase Polymerase Amplification Reactions on SlipChip

PubMed Central

Shen, Feng; Davydova, Elena K.; Du, Wenbin; Kreutz, Jason E.; Piepenburg, Olaf; Ismagilov, Rustem F.

2011-01-01

In this paper, digital quantitative detection of nucleic acids was achieved at the single-molecule level by chemical initiation of over one thousand sequence-specific, nanoliter, isothermal amplification reactions in parallel. Digital polymerase chain reaction (digital PCR), a method used for quantification of nucleic acids, counts the presence or absence of amplification of individual molecules. However it still requires temperature cycling, which is undesirable under resource-limited conditions. This makes isothermal methods for nucleic acid amplification, such as recombinase polymerase amplification (RPA), more attractive. A microfluidic digital RPA SlipChip is described here for simultaneous initiation of over one thousand nL-scale RPA reactions by adding a chemical initiator to each reaction compartment with a simple slipping step after instrument-free pipette loading. Two designs of the SlipChip, two-step slipping and one-step slipping, were validated using digital RPA. By using the digital RPA SlipChip, false positive results from pre-initiation of the RPA amplification reaction before incubation were eliminated. End-point fluorescence readout was used for “yes or no” digital quantification. The performance of digital RPA in a SlipChip was validated by amplifying and counting single molecules of the target nucleic acid, Methicillin-resistant Staphylococcus aureus (MRSA) genomic DNA. The digital RPA on SlipChip was also tolerant to fluctuations of the incubation temperature (37–42 °C), and its performance was comparable to digital PCR on the same SlipChip design. The digital RPA SlipChip provides a simple method to quantify nucleic acids without requiring thermal cycling or kinetic measurements, with potential applications in diagnostics and environmental monitoring under resource-limited settings. The ability to initiate thousands of chemical reactions in parallel on the nanoliter scale using solvent-resistant glass devices is likely to be useful for a broader range of applications. PMID:21476587

Accelerated isothermal nucleic acid amplification in betaine-free reaction.

PubMed

Ma, Cuiping; Wang, Yifan; Zhang, Pansong; Shi, Chao

2017-08-01

Betaine was used as a common additive to isothermal nucleic acid amplification reactions because of lowering the melting temperature (Tm) of DNA. Herein, we reported a novel finding that betaine was inhibiting the reaction efficiency of isothermal amplification reactions. In this work, we have verified this finding by classical loop-mediated isothermal amplification that the addition of 0.8 M betaine inhibited the efficiency of reaction dropping to approximately 1%. Additionally, we clarified the mechanism of betaine hindering isothermal amplification reactions with a molecular barrier to lower associate rate constant K1 for intermolecular hybridization. This finding would be very significant for studies on the interaction between small molecule substance and DNA, and the development of point-of-care testing because of simplifying reaction system and increasing reaction efficiency. Copyright © 2017 Elsevier Inc. All rights reserved.

New bis(alkythio) fatty acid methyl esters

USDA-ARS?s Scientific Manuscript database

The addition reaction of dimethyl disulfide (DMDS) to mono-unsaturated fatty acid methyl esters is well-known for analytical purposes to determine the position of double bonds by mass spectrometry. In this work, the classical iodine-catalyzed reaction is expanded to other dialkyl disulfides (RSSR), ...

A DIRECT ROUTE TO ACYLHYDROQUINONES FROM ALPHA-KETO ACIDS AND ALPHA-CARBOXAMIDO ACIDS. (R825330)

EPA Science Inventory

Abstract

The reaction of quinones with in situ generated acyl- or carboxamido radicals provides a direct route to the synthesis of acylhydroquinones not accessible by the photochemical reaction of quinones with aldehydes.

Preferential hydrophobic interactions are responsible for a preference of D-amino acids in the aminoacylation of 5'-AMP with hydrophobic amino acids

NASA Technical Reports Server (NTRS)

Lacey, J. C. Jr; Wickramasinghe, N. S.; Sabatini, R. S.

1992-01-01

We have studied the chemistry of aminoacyl AMP to model reactions at the 3' terminus of aminoacyl tRNA for the purpose of understanding the origin of protein synthesis. The present studies relate to the D, L preference in the esterification of 5'-AMP. All N-acetyl amino acids we studied showed faster reaction of the D-isomer, with a generally decreasing preference for D-isomer as the hydrophobicity of the amino acid decreased. The beta-branched amino acids, Ile and Val, showed an extreme preference for D-isomer. Ac-Leu, the gamma-branched amino acid, showed a slightly low D/L ratio relative to its hydrophobicity. The molecular basis for these preferences for D-isomer is understandable in the light of our previous studies and seems to be due to preferential hydrophobic interaction of the D-isomer with adenine. The preference for hydrophobic D-amino acids can be decreased by addition of an organic solvent to the reaction medium. Conversely, peptidylation with Ac-PhePhe shows a preference for the LL isomer over the DD isomer.

Conversion of polar and non-polar algae oil lipids to fatty acid methyl esters with solid acid catalysts--A model compound study.

PubMed

Asikainen, Martta; Munter, Tony; Linnekoski, Juha

2015-09-01

Bio-based fuels are becoming more and more important due to the depleting fossil resources. The production of biodiesel from algae oil is challenging compared to terrestrial vegetable oils, as algae oil consists of polar fatty acids, such as phospholipids and glycolipids, as well as non-polar triglycerides and free fatty acids common in vegetable oils. It is shown that a single sulphonated solid acid catalyst can perform the esterification and transesterification reactions of both polar and non-polar lipids. In mild reaction conditions (60-70 °C) Nafion NR50 catalyst produces methyl palmitate (FAME) from the palmitic acid derivatives of di-, and tri-glyceride, free fatty acid, and phospholipid with over 80% yields, with the glycolipid derivative giving nearly 40% yields of FAME. These results demonstrate how the polar and non-polar lipid derivatives of algal oil can be utilised as feedstocks for biodiesel production with a single catalyst in one reaction step. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis of structured lipid enriched with omega fatty acids and sn-2 palmitic acid by enzymatic esterification and its incorporation in powdered infant formula.

PubMed

Nagachinta, Supakana; Akoh, Casimir C

2013-05-08

Structured lipid (SL) enriched with arachidonic (ARA) and docosahexaenoic (DHA) acids was produced from tripalmitin using Lipozyme TL IM. The effects of acyl donors, that is, free fatty acids vs fatty acid ethyl esters, on the reactions were compared. The highest total incorporation of ARA and DHA was obtained when the reaction continued for 24 h, at a substrate mole ratio of 9, using free fatty acids as acyl donors (acidolysis). The SL prepared by a large-scale acidolysis reaction contained 17.69 ± 0.09% total ARA, 10.75 ± 0.15% total DHA, and 48.53 ± 1.40% sn-2 palmitic acid. SL thermograms exhibited multiple peaks indicating complexity of the triacylglycerol (TAG) distribution. RP-HPLC analysis of SL revealed nine of 26 TAG molecular species that were similar to those of human milk fat. Powdered infant formulas containing the SL were prepared by wet-mixing/spray-drying and dry-blending methods. Formula prepared with microencapsulated SL and the dry-blending method had better oxidative stability and color quality.

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

Simic, M.G.; Jovanovic, S.V.

One-electron oxidation of uric acid generates the urate radical, which was studied in aqueous solution by pulse radiolysis and oxygen-uptake measurements. Acid-base properties of the uric acid radical were determined, i.e., pK{sub a1} = 3.1 {plus minus} 0.1 and pK{sub a2} = 9.5 {plus minus} 0.1. The reaction of the radical with oxygen was too slow to be measured, k < 10{sup {minus}2} dm{sup 3} mol{sup {minus}1} s{sup {minus}1}. The one-electron-redox potential vs NHE, E{sub 7} = 0.59 V, was derived from the pH dependence of the redox potential, which was fitted through the values measured at pH 7 andmore » 8.9 and those previously determined at pH 13. Rapid reactions of uric acid with oxidizing species and peroxy radicals were indicative of uric acid as a possible water-soluble physiological antioxidant. Rapid reaction of uric acid with the guanyl radical indicates that uric acid may also act as a repair agent of oxidative damage to DNA bases.« less

Improved synthesis with high yield and increased molecular weight of poly(alpha,beta-malic acid) by direct polycondensation.

PubMed

Kajiyama, Tetsuto; Kobayashi, Hisatoshi; Taguchi, Tetsushi; Kataoka, Kazunori; Tanaka, Junzo

2004-01-01

The development of synthetic biodegradable polymers, such as poly(alpha-hydroxy acid), is particularly important for constructing medical devices, including scaffolds and sutures, and has attracted growing interest in the biomedical field. Here, we report a novel approach to preparing high molecular weight poly(malic acid) (HMW--PMA) as a biodegradable and bioabsorbable water-soluble polymer. We investigated in detail the reaction conditions for the simple direct polycondensation of l-malic acid, including the reaction times, temperatures, and catalysts. The molecular weight of synthesized alpha,beta-PMA is dependent on both the reaction temperature and time. The optimum reaction condition to obtain alpha,beta-PMA by direct polycondensation using tin(II) chloride as a catalyst was thus determined to be 110 degrees C for 45 h with a molecular weight of 5300. The method for alpha,beta-PMA synthesis established here will facilitate production of alpha,beta-PMA of various molecular weights, which may have a potential utility as biomaterials.

Production and Characterization of Ethyl Ester from Crude Jatropha curcas Oil having High Free Fatty Acid Content

NASA Astrophysics Data System (ADS)

Kumar, Rajneesh; Dixit, Anoop; Singh, Shashi Kumar; Singh, Gursahib; Sachdeva, Monica

2015-09-01

The two step process was carried out to produce biodiesel from crude Jatropha curcas oil. The pretreatment process was carried out to reduce the free fatty acid content by (≤2 %) acid catalyzed esterification. The optimum reaction conditions for esterification were reported to be 5 % H2SO4, 20 % ethanol and 1 h reaction time at temperature of 65 °C. The pretreatment process reduced the free fatty acid of oil from 7 to 1.85 %. In second process, alkali catalysed transesterification of pretreated oil was carried and the effects of the varying concentrations of KOH and ethanol: oil ratios on percent ester recovery were investigated. The optimum reaction conditions for transesterification were reported to be 3 % KOH (w/v of oil) and 30 % (v/v) ethanol: oil ratio and reaction time 2 h at 65 °C. The maximum percent recovery of ethyl ester was reported to be 60.33 %.

Mechanism of chemical activation of sodium chloride in the presence of amino acids.

PubMed

Rahn, Anja K K; Yaylayan, Varoujan A

2015-01-01

Sodium chloride has been shown to promote chlorination of glycerol during thermal processing. However, the detailed mechanism of this reaction is not well understood. Preliminary experiments have indicated that the reaction mixture should contain an amino acid and it should be dissolved thoroughly in water in order to induce chlorination. These observations are consistent with the process of dissociation of sodium chloride and its re-association with amino acid and eventual formation of the chlorinating agent in the form of the hydrochloride salt. Release of HCl from this salt can be manifested in chlorination and hydrolytic reactions occurring during thermal processing. The generation of HCl at room temperature from a mixture of sodium chloride and glycine was confirmed through spectrophotometric monitoring of the pH. Hydrolytic and chlorination reactions were demonstrated through monitoring of formation of HMF and chlorinated products under pyrolytic conditions using glucose or sucrose and amino acid mixtures. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of ultrasound on the dissolution of copper from copper converter slag by acid leaching.

PubMed

Beşe, Ayşe Vildan

2007-09-01

This work presents the optimum conditions of dissolution of copper in copper converter slag in sulphuric acid ferric sulphate mixtures in the presence and absence of ultrasound. The Taguchi method was used to determine the optimum conditions. The parameters investigated were the reaction temperature, acid concentration, ferric sulphate concentration and reaction time. The optimum conditions for the maximum dissolution of copper were determined as follows: reaction temperature, 65 degrees C; acid concentration, 0.2M; ferric sulphate concentration, 0.15M; reaction time 180 min. Under these conditions, extraction efficiency of copper, zinc, cobalt, and iron from slag were 89.28%, 51.32%, 69.87%, and 13.73%, respectively, in the presence of ultrasound, while they are 80.41%, 48.28%, 64.52%, and 12.16%, respectively, in the absence of ultrasound. As seen from the above results, it is clear that ultrasound enhances on the dissolution of Cu, Zn, Co and Fe in the slag.

Application of artificial intelligent tools to modeling of glucosamine preparation from exoskeleton of shrimp.

PubMed

Valizadeh, Hadi; Pourmahmood, Mohammad; Mojarrad, Javid Shahbazi; Nemati, Mahboob; Zakeri-Milani, Parvin

2009-04-01

The objective of this study was to forecast and optimize the glucosamine production yield from chitin (obtained from Persian Gulf shrimp) by means of genetic algorithm (GA), particle swarm optimization (PSO), and artificial neural networks (ANNs) as tools of artificial intelligence methods. Three factors (acid concentration, acid solution to chitin ratio, and reaction time) were used as the input parameters of the models investigated. According to the obtained results, the production yield of glucosamine hydrochloride depends linearly on acid concentration, acid solution to solid ratio, and time and also the cross-product of acid concentration and time and the cross-product of solids to acid solution ratio and time. The production yield significantly increased with an increase of acid concentration, acid solution ratio, and reaction time. The production yield is inversely related to the cross-product of acid concentration and time. It means that at high acid concentrations, the longer reaction times give lower production yields. The results revealed that the average percent error (PE) for prediction of production yield by GA, PSO, and ANN are 6.84, 7.11, and 5.49%, respectively. Considering the low PE, it might be concluded that these models have a good predictive power in the studied range of variables and they have the ability of generalization to unknown cases.

Pulse radiolytic study of the oxidation reactions of uric acid in presence of bovine serum albumin. Evidence of possible complex formation in the transient state

NASA Astrophysics Data System (ADS)

Adhikari, S.; Joshi, R.; Gopinathan, C.

1997-01-01

The pulse radiolytic and spectrophotometric study of uric acid in presence of bovine serum albumin (BSA) has been carried out. In the spectrophotometric study there is no evidence for ground state interaction between BSA and uric acid. The oxidation reactions of uric acid in presence and absence of BSA employing CCl 3OO and Br radicals have been carried out. In a composition of equal concentration of uric acid and BSA, the CCl 3OO and Br radicals produce a transient absorption spectrum which show two peaks at 330 and 360 nm. The peak at 360 nm is ascribed due to weak complex formation between semioxidised BSA and uric acid radicals. The rate constant of CCl 3OO . radical with uric acid increases with the increase in BSA concentration which is explained as protection of BSA by uric acid from radical attack. The Br radical attacks uric acid and BSA in a manner similar to CCl 3OO radical. The bimolecular rate constants for the reaction of Br radical with BSA and uric acid have been found as 2.9 × 10 10 dm 3 mol -1 s -1 and 6.33 × 10 9 dm 3 mol -1 s -, respectively.

Evidence from Meteorites for Multiple Possible Amino Acid Alphabets for the Origins of Life

NASA Technical Reports Server (NTRS)

Burton, A. S.; Elsila, J. E.; Callahan, M. P.; Glavin, D. P.; Dworkin, J. P.

2015-01-01

A key question for the origins of life is understanding which amino acids made up the first proteins synthesized during the origins of life. The canonical set of 20 - 22 amino acids used in proteins are all alpha-amino, alpha-hydrogen isomers that, nevertheless, show considerable variability in properties including size, hydrophobicity, and ionizability. Abiotic amino acid synthesis experiments such as Miller-Urey spark discharge reactions produce a set of up to 23 amino acids, depending on starting materials and reaction conditions, with significant abundances of both alpha- and non-alpha-amino acid isomers. These two sets of amino acids do not completely overlap; of the 23 spark discharge amino acids, only 11 are used in modern proteins. Furthermore, because our understanding of conditions on the early Earth are limited, it is unclear which set(s) of conditions employed in spark discharge or hydrothermal reactions are correct, leaving us with significant uncertainty about the amino acid alphabet available for the origins of life on Earth. Meteorites, the surviving remnants of asteroids and comets that fall to the Earth, offer the potential to study authentic samples of naturally-occurring abiotic chemistry, and thus can provide an alternative approach to constraining the amino acid library during the origins of life.

Competition between organics and bromide at the aqueous solution-air interface as seen from ozone uptake kinetics and X-ray photoelectron spectroscopy.

PubMed

Lee, Ming-Tao; Brown, Matthew A; Kato, Shunsuke; Kleibert, Armin; Türler, Andreas; Ammann, Markus

2015-05-14

A more detailed understanding of the heterogeneous chemistry of halogenated species in the marine boundary layer is required. Here, we studied the reaction of ozone (O3) with NaBr solutions in the presence and absence of citric acid (C6H8O7) under ambient conditions. Citric acid is used as a proxy for oxidized organic material present at the ocean surface or in sea spray aerosol. On neat NaBr solutions, the observed kinetics is consistent with bulk reaction-limited uptake, and a second-order rate constant for the reaction of O3 + Br(-) is 57 ± 10 M(-1) s(-1). On mixed NaBr-citric acid aqueous solutions, the uptake kinetics was faster than that predicted by bulk reaction-limited uptake and also faster than expected based on an acid-catalyzed mechanism. X-ray photoelectron spectroscopy (XPS) on a liquid microjet of the same solutions at 1.0 × 10(-3)-1.0 × 10(-4) mbar was used to obtain quantitative insight into the interfacial composition relative to that of the bulk solutions. It revealed that the bromide anion becomes depleted by 30 ± 10% while the sodium cation gets enhanced by 40 ± 20% at the aqueous solution-air interface of a 0.12 M NaBr solution mixed with 2.5 M citric acid in the bulk, attributed to the role of citric acid as a weak surfactant. Therefore, the enhanced reactivity of bromide solutions observed in the presence of citric acid is not necessarily attributable to a surface reaction but could also result from an increased solubility of ozone at higher citric acid concentrations. Whether the acid-catalyzed chemistry may have a larger effect on the surface than in the bulk to offset the effect of bromide depletion also remains open.

Organic syntheses employing supercritical carbon dioxide as a reaction solvent

NASA Technical Reports Server (NTRS)

Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

1991-01-01

Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

Organic syntheses employing supercritical carbon dioxide as a reaction solvent

NASA Technical Reports Server (NTRS)

Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

1993-01-01

Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

Photoacid generator study for chemically amplified negative resists for high-resolution lithography

NASA Astrophysics Data System (ADS)

Dentinger, Paul M.; Knapp, Kurtis G.; Reynolds, Geoffrey W.; Taylor, James W.; Fedynyshyn, Theodore H.; Richardson, Todd A.

1998-06-01

The effect of photoacid generator and photogenerated acid molecular structures on a negative-tone chemically-amplified resist was tested using two different sets of acid generators, each set with one formulation creating a 'volatile' acid, and the other formulation creating a 'non- volatile' acid when exposed to x-rays. The acids from one set were generated from a derivative of iodonium salt and the acids from the other set were generated from a covalently bound photoacid generator. Both sets were compared to Shipley SAL 605 resist. In this study of five formulations, normalized remaining thickness (NRT) curves, SEM images of printed lines, spectrophotometric titration of the photogenerated acid, real-time curves, SEM images of printed lines, spectrophotometric titration of the photogenerated acid, real-time FTIR for kinetics of the PEB reaction, dissolution rate measurements, and atomic force microscopy for surface roughness were employed. RT-FTIR suggested that both the proposed 'volatile' and 'non- volatile' acids were retained to approximately the same extent within the films cast from these formulations. A mechanism is suggested where the type of photogenerated acid has an effect on the kinetics of the reaction and the photogenerated acid or photoacid effect on the kinetics of the reaction and the photogenerated acid or photoacid generator has a large effect on the ability of the aqueous developer to penetrate or dissolve the film.

Optimisation and Characterisation of Lipase-Catalysed Synthesis of a Kojic Monooleate Ester in a Solvent-Free System by Response Surface Methodology.

PubMed

Jumbri, Khairulazhar; Al-Haniff Rozy, Mohd Fahruddin; Ashari, Siti Efliza; Mohamad, Rosfarizan; Basri, Mahiran; Fard Masoumi, Hamid Reza

2015-01-01

Kojic acid is widely used to inhibit the browning effect of tyrosinase in cosmetic and food industries. In this work, synthesis of kojic monooleate ester (KMO) was carried out using lipase-catalysed esterification of kojic acid and oleic acid in a solvent-free system. Response Surface Methodology (RSM) based on central composite rotatable design (CCRD) was used to optimise the main important reaction variables, such as enzyme amount, reaction temperature, substrate molar ratio, and reaction time along with immobilised lipase from Candida Antarctica (Novozym 435) as a biocatalyst. The RSM data indicated that the reaction temperature was less significant in comparison to other factors for the production of a KMO ester. By using this statistical analysis, a quadratic model was developed in order to correlate the preparation variable to the response (reaction yield). The optimum conditions for the enzymatic synthesis of KMO were as follows: an enzyme amount of 2.0 wt%, reaction temperature of 83.69°C, substrate molar ratio of 1:2.37 (mmole kojic acid:oleic acid) and a reaction time of 300.0 min. Under these conditions, the actual yield percentage obtained was 42.09%, which is comparably well with the maximum predicted value of 44.46%. Under the optimal conditions, Novozym 435 could be reused for 5 cycles for KMO production percentage yield of at least 40%. The results demonstrated that statistical analysis using RSM can be used efficiently to optimise the production of a KMO ester. Moreover, the optimum conditions obtained can be applied to scale-up the process and minimise the cost.

Optimisation and Characterisation of Lipase-Catalysed Synthesis of a Kojic Monooleate Ester in a Solvent-Free System by Response Surface Methodology

PubMed Central

Jumbri, Khairulazhar; Al-Haniff Rozy, Mohd Fahruddin; Ashari, Siti Efliza; Mohamad, Rosfarizan; Basri, Mahiran; Fard Masoumi, Hamid Reza

2015-01-01

Kojic acid is widely used to inhibit the browning effect of tyrosinase in cosmetic and food industries. In this work, synthesis of kojic monooleate ester (KMO) was carried out using lipase-catalysed esterification of kojic acid and oleic acid in a solvent-free system. Response Surface Methodology (RSM) based on central composite rotatable design (CCRD) was used to optimise the main important reaction variables, such as enzyme amount, reaction temperature, substrate molar ratio, and reaction time along with immobilised lipase from Candida Antarctica (Novozym 435) as a biocatalyst. The RSM data indicated that the reaction temperature was less significant in comparison to other factors for the production of a KMO ester. By using this statistical analysis, a quadratic model was developed in order to correlate the preparation variable to the response (reaction yield). The optimum conditions for the enzymatic synthesis of KMO were as follows: an enzyme amount of 2.0 wt%, reaction temperature of 83.69°C, substrate molar ratio of 1:2.37 (mmole kojic acid:oleic acid) and a reaction time of 300.0 min. Under these conditions, the actual yield percentage obtained was 42.09%, which is comparably well with the maximum predicted value of 44.46%. Under the optimal conditions, Novozym 435 could be reused for 5 cycles for KMO production percentage yield of at least 40%. The results demonstrated that statistical analysis using RSM can be used efficiently to optimise the production of a KMO ester. Moreover, the optimum conditions obtained can be applied to scale-up the process and minimise the cost. PMID:26657030