Catalytic chemical amide synthesis at room temperature: one more step toward peptide synthesis.

Science.gov (United States)

Mohy El Dine, Tharwat; Erb, William; Berhault, Yohann; Rouden, Jacques; Blanchet, Jérôme

2015-05-01

An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature for a large range of substrates with slightly higher temperatures required for challenging ones. This methodology can be applied to aliphatic, α-hydroxyl, aromatic, and heteroaromatic acids as well as primary, secondary, heterocyclic, and even functionalized amines. Notably, N-Boc-protected amino acids were successfully coupled in good yields with very little racemization. An example of catalytic dipeptide synthesis is reported.

Biosynthesis, degradation, and pharmacological importance of the fatty acid amides

Science.gov (United States)

Farrell, Emma K.; Merkler, David J.

2008-01-01

The identification of two biologically active fatty acid amides, N-arachidonoylethanolamine (anandamide) and oleamide, has generated a great deal of excitement and stimulated considerable research. However, anandamide and oleamide are merely the best-known and best-understood members of a much larger family of biologically-occurring fatty acid amides. In this review, we will outline which fatty acid amides have been isolated from mammalian sources, detail what is known about how these molecules are made and degraded in vivo, and highlight their potential for the development of novel therapeutics. PMID:18598910

Identification of fatty acids and fatty acid amides in human meibomian gland secretions.

Science.gov (United States)

Nichols, Kelly K; Ham, Bryan M; Nichols, Jason J; Ziegler, Corrie; Green-Church, Kari B

2007-01-01

The complex superficial lipid layer of the tear film functions to prevent evaporation and maintain tear stability. Although classes of lipids found in the tear film have been reported, individual lipid species are currently being studied with more sophisticated. The purpose of this work was to show the identification of fatty acids and the fatty acid amides in human meibomian gland secretions by using electrospray mass spectrometry. methods. Human meibomian gland secretions (meibum) were analyzed by electrospray quadrupole time-of-flight mass spectrometry (positive- and negative-ion mode). Accurate mass determination and collision-induced dissociation of meibum, and lipid standards were used to identify lipid species. Mass analysis of meibum in an acidic chloroform-methanol solution in positive-ion mode revealed a mass peak of m/z 282.3, which was identified as the protonated molecule of oleamide [C(18)H(35)NO+H](+). The high-resolution mass analysis of the m/z 282.2788 peak (oleamide) demonstrated a mass accuracy of 3.2 parts per million (ppm). Collision-induced dissociation of this species from meibum, compared with an oleamide standard, confirmed its identification. Myristic, palmitic, stearic, and oleic free fatty acids were identified in a similar manner, as were the other fatty acid amides (myristamide, palmitamide, stearamide, and erucamide). The findings indicate that oleamide (cis-9-octadecenamide), an endogenous fatty acid primary amide, is a predominant component of meibum when examined by electrospray mass spectrometry. The novel finding of oleamide and other members of the fatty acid amide family in the tear film could lead to additional insights into the role of fatty acid amide activity in human biological systems and may indicate a new function for this lipid class of molecules in ocular surface signaling and/or in the maintenance of the complex tear film.

The dynamics of acid-soluble phosphorus compounds in the course of winter and spring wheat germination under various thermic conditions. Part II. Labile phosphorus after hydrolysis of the acid-soluble fraction

Directory of Open Access Journals (Sweden)

A. Barbaro

2015-06-01

Full Text Available The changes in labile phosphorus compounds content during germination of wheat were investigated. These compounds were determined in acid-soluble germ extracts separated into fractions according to the solubility of their barium salts. Low germination temperature was found to raise the labile phosphorus content in the fraction of insoluble barium salts. If we assume that labile P of this fraction consisted mainly of adenosinedi- and triphosphates, it would seem that the rise, in the ATP and ADP level under the influence of low temperature may be essential for initiating flowering in winter varieties.

Composition of amino acid using carbon monoxide. Amide carbonylation reaction

Energy Technology Data Exchange (ETDEWEB)

Izawa, Kunisuke (Ajinomoto Co., Inc., Tokyo (Japan))

1989-02-01

Amide carbonylation reaction is a method to compose N-acyl-{alpha}-amino acid from aldehyde, carboxylic acid amide, and carbon monoxide in a phase and with high yield. Unlike the conventional Strecker reaction, this method does not use HCN which is in question on public pollution and does not require hydrolysis. This amide carbonylation reaction was discovered by Wakamatsu and others of Ajinomoto Co.,Ltd. Present application examples of this method are the composition of N-acetyl amino acid from the aldehyde class, the composition of N-Acyl amino acid from olefin, the composition of N-acyl or acetyl amino acid from the raw material of alcohol and the halide class, the composition of N-acyl or acetyl amino acid via the isomerization of epoxide and allyl alcohol, the composition of amino dicarboxylic acid, applying deoxidation of ring acid anhydride, the composition of N-acyl amino acid from the raw material of the amine class, the stereoselective composition of -substitution ring-{alpha}-amino acid, and the composition of amino aldehyde. 24 refs., 2 figs., 2 tabs.

Synthesis and antituberculosis activity of new fatty acid amides.

Science.gov (United States)

D'Oca, Caroline Da Ros Montes; Coelho, Tatiane; Marinho, Tamara Germani; Hack, Carolina Rosa Lopes; Duarte, Rodrigo da Costa; da Silva, Pedro Almeida; D'Oca, Marcelo Gonçalves Montes

2010-09-01

This work reports the synthesis of new fatty acid amides from C16:0, 18:0, 18:1, 18:1 (OH), and 18:2 fatty acids families with cyclic and acyclic amines and demonstrate for the first time the activity of these compounds as antituberculosis agents against Mycobacterium tuberculosis H(37)Rv, M. tuberculosis rifampicin resistance (ATCC 35338), and M. tuberculosis isoniazid resistance (ATCC 35822). The fatty acid amides derivate from ricinoleic acid were the most potent one among a series of tested compounds, with a MIC 6.25 microg/mL for resistance strains. Copyright 2010 Elsevier Ltd. All rights reserved.

New and Efficient Synthesis of Amides from Acid Chlorides Using Diisobutyl(amino)aluminum

Energy Technology Data Exchange (ETDEWEB)

Park, Jae Kyo; Shin, Won Kyu; An, Duk Keun [Kangwon National Univ., Chuncheon (Korea, Republic of)

2013-05-15

In conclusion, we have developed a facile, alternative method for the formation of secondary and tertiary amides including morpholine amides from acid chlorides by using diisobutyl(amino)aluminum under mild reaction conditions. The advantages of the present method include the high product yields, simple experimental procedure, short reaction time (10 min), and the fact that an excess amount of amine is not required. This result suggests that our new method can provide an alternative method for the synthesis of useful amides from acid chlorides. Amides are valuable functional groups in biological, agrochemical, and pharmaceutical molecules. Several amides such as Weinreb amides, morpholine amides, and pyrrolidine amides are useful intermediates for the synthesis of aldehydes or ketones. Among them, morpholine amides are a cheap and good substitute for Weinreb amides.

New and Efficient Synthesis of Amides from Acid Chlorides Using Diisobutyl(amino)aluminum

International Nuclear Information System (INIS)

Park, Jae Kyo; Shin, Won Kyu; An, Duk Keun

2013-01-01

In conclusion, we have developed a facile, alternative method for the formation of secondary and tertiary amides including morpholine amides from acid chlorides by using diisobutyl(amino)aluminum under mild reaction conditions. The advantages of the present method include the high product yields, simple experimental procedure, short reaction time (10 min), and the fact that an excess amount of amine is not required. This result suggests that our new method can provide an alternative method for the synthesis of useful amides from acid chlorides. Amides are valuable functional groups in biological, agrochemical, and pharmaceutical molecules. Several amides such as Weinreb amides, morpholine amides, and pyrrolidine amides are useful intermediates for the synthesis of aldehydes or ketones. Among them, morpholine amides are a cheap and good substitute for Weinreb amides

Reaction mechanism of the acidic hydrolysis of highly twisted amides: Rate acceleration caused by the twist of the amide bond.

Science.gov (United States)

Mujika, Jon I; Formoso, Elena; Mercero, Jose M; Lopez, Xabier

2006-08-03

We present an ab initio study of the acid hydrolysis of a highly twisted amide and a planar amide analogue. The aim of these studies is to investigate the effect that the twist of the amide bond has on the reaction barriers and mechanism of acid hydrolysis. Concerted and stepwise mechanisms were investigated using density functional theory and polarizable continuum model calculations. Remarkable differences were observed between the mechanism of twisted and planar amide, due mainly to the preference for N-protonation of the former and O-protonation of the latter. In addition, we were also able to determine that the hydrolytic mechanism of the twisted amide will be pH dependent. Thus, there is a preference for a stepwise mechanism with formation of an intermediate in the acid hydrolysis, whereas the neutral hydrolysis undergoes a concerted-type mechanism. There is a nice agreement between the characterized intermediate and available X-ray data and a good agreement with the kinetically estimated rate acceleration of hydrolysis with respect to analogous undistorted amide compounds. This work, along with previous ab initio calculations, describes a complex and rich chemistry for the hydrolysis of highly twisted amides as a function of pH. The theoretical data provided will allow for a better understanding of the available kinetic data of the rate acceleration of amides upon twisting and the relation of the observed rate acceleration with intrinsic differential reactivity upon loss of amide bond resonance.

Expression of Flk-1 and Cyclin D2 mRNA in the Myocardium of Rats with Doxorubicin-Induced Cardiomyopathy and after Treatment with Betulonic Acid Amide.

Science.gov (United States)

Mzhelskaya, M M; Klinnikova, M G; Koldysheva, E V; Lushnikova, E L

2017-10-01

The expression of VEGFR2 (Flk-1, according to immunohistochemistry) and of cyclin D2 mRNA (according to real-time PCR) in the myocardium of rats is studied in doxorubicin-induced cardiomyopathy and in response to betulonic acid amide. Doxorubicin alone and in combination with betulonic acid amide causes after 3 days a manifest reduction of cyclin D2 mRNA expression (by 38 and 63%, respectively), while injection of betulonic acid amide alone causes a 23-fold increase of cyclin D2 mRNA expression. An increase of cyclin D2 mRNA expression has been detected in all experimental groups after 14 days of experiment, the most pronounced in response to betulonic acid amide (63 times). The expression of Flk-1 in cardiomyocytes increases significantly in response to both chemical agents starting from day 3 of experiment. These results indicate that doxorubicin and betulonic acid amide induce cytoprotective reactions in the myocardium, first at the intracellular, then at the cellular levels.

Molecular characterization of an enzyme that degrades neuromodulatory fatty-acid amides.

Science.gov (United States)

Cravatt, B F; Giang, D K; Mayfield, S P; Boger, D L; Lerner, R A; Gilula, N B

1996-11-07

Endogenous neuromodulatory molecules are commonly coupled to specific metabolic enzymes to ensure rapid signal inactivation. Thus, acetylcholine is hydrolysed by acetylcholine esterase and tryptamine neurotransmitters like serotonin are degraded by monoamine oxidases. Previously, we reported the structure and sleep-inducing properties of cis-9-octadecenamide, a lipid isolated from the cerebrospinal fluid of sleep-deprived cats. cis-9-Octadecenamide, or oleamide, has since been shown to affect serotonergic systems and block gap-junction communication in glial cells (our unpublished results). We also identified a membrane-bound enzyme activity that hydrolyses oleamide to its inactive acid, oleic acid. We now report the mechanism-based isolation, cloning and expression of this enzyme activity, originally named oleamide hydrolase, from rat liver plasma membranes. We also show that oleamide hydrolase converts anandamide, a fatty-acid amide identified as the endogenous ligand for the cannabinoid receptor, to arachidonic acid, indicating that oleamide hydrolase may serve as the general inactivating enzyme for a growing family of bioactive signalling molecules, the fatty-acid amides. Therefore we will hereafter refer to oleamide hydrolase as fatty-acid amide hydrolase, in recognition of the plurality of fatty-acid amides that the enzyme can accept as substrates.

Lipophilic ester and amide derivatives of rosmarinic acid protect cells against H2O2-induced DNA damage and apoptosis: The potential role of intracellular accumulation and labile iron chelation

Directory of Open Access Journals (Sweden)

Paraskevi S. Gerogianni

2018-05-01

Full Text Available Phenolic acids represent abundant components contained in human diet. However, the negative charge in their carboxylic group limits their capacity to diffuse through biological membranes, thus hindering their access to cell interior. In order to promote the diffusion of rosmarinic acid through biological membranes, we synthesized several lipophilic ester- and amide-derivatives of this compound and evaluated their capacity to prevent H2O2-induced DNA damage and apoptosis in cultured human cells. Esterification of the carboxylic moiety with lipophilic groups strongly enhanced the capacity of rosmarinic acid to protect cells. On the other hand, the amide-derivatives were somewhat less effective but exerted less cytotoxicity at high concentrations. Cell uptake experiments, using ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS, illustrated different levels of intracellular accumulation among the ester- and amide-derivatives, with the first being more effectively accumulated, probably due to their extensive hydrolysis inside the cells. In conclusion, these results highlight the hitherto unrecognized fundamental importance of derivatization of diet-derived phenolic acids to unveil their biological potential.

Enzymatically and reductively degradable α-amino acid-based poly(ester amide)s: Synthesis, cell compatibility, and intracellular anticancer drug delivery

NARCIS (Netherlands)

Sun, H.; Cheng, Ru; Deng, Chao; Meng, Fenghua; Dias, Aylvin A.; Hendriks, Marc; Feijen, Jan; Zhong, Zhiyuan

2015-01-01

A novel and versatile family of enzymatically and reductively degradable α-amino acid-based poly(ester amide)s (SS-PEAs) were developed from solution polycondensation of disulfide-containing di-p-toluenesulfonic acid salts of bis-l-phenylalanine diesters (SS-Phe-2TsOH) with di-p-nitrophenyl adipate

Predicting protein amidation sites by orchestrating amino acid sequence features

Science.gov (United States)

Zhao, Shuqiu; Yu, Hua; Gong, Xiujun

2017-08-01

Amidation is the fourth major category of post-translational modifications, which plays an important role in physiological and pathological processes. Identifying amidation sites can help us understanding the amidation and recognizing the original reason of many kinds of diseases. But the traditional experimental methods for predicting amidation sites are often time-consuming and expensive. In this study, we propose a computational method for predicting amidation sites by orchestrating amino acid sequence features. Three kinds of feature extraction methods are used to build a feature vector enabling to capture not only the physicochemical properties but also position related information of the amino acids. An extremely randomized trees algorithm is applied to choose the optimal features to remove redundancy and dependence among components of the feature vector by a supervised fashion. Finally the support vector machine classifier is used to label the amidation sites. When tested on an independent data set, it shows that the proposed method performs better than all the previous ones with the prediction accuracy of 0.962 at the Matthew's correlation coefficient of 0.89 and area under curve of 0.964.

Hydrogen abstraction reactions by amide electron adducts

International Nuclear Information System (INIS)

Sevilla, M.D.; Sevilla, C.L.; Swarts, S.

1982-01-01

Electron reactions with a number of peptide model compounds (amides and N-acetylamino acids) in aqueous glasses at low temperature have been investigated using ESR spectroscopy. The radicals produced by electron attachment to amides, RC(OD)NDR', are found to act as hydrogen abstracting agents. For example, the propionamide electron adduct is found to abstract from its parent propionamide. Electron adducts of other amides investigated show similar behavior except for acetamide electron adduct which does not abstract from its parent compound, but does abstract from other amides. The tendency toward abstraction for amide electron adducts are compared to electron adducts of several carboxylic acids, ketones, aldehydes and esters. The comparison suggests the hydrogen abstraction tendency of the various deuterated electron adducts (DEAs) to be in the following order: aldehyde DEA > acid DEA = approximately ester DEA > ketone DEA > amide DEA. In basic glasses the hydrogen abstraction ability of the amide electron adducts is maintained until the concentration of base is increased sufficiently to convert the DEA to its anionic form, RC(O - )ND 2 . In this form the hydrogen abstracting ability of the radical is greatly diminished. Similar results were found for the ester and carboxylic acid DEA's tested. (author)

Influence of aliphatic amides on the temperature of maximum density of water

International Nuclear Information System (INIS)

Torres, Andrés Felipe; Romero, Carmen M.

2017-01-01

Highlights: • The addition of amides decreases the temperature of maximum density of water suggesting a disruptive effect on water structure. • The amides in aqueous solution do not follow the Despretz equation in the concentration range considered. • The temperature shift Δθ as a function of molality is represented by a second order equation. • The Despretz constants were determined considering the dilute concentration region for each amide solution. • Solute disrupting effect of amides becomes smaller as its hydrophobic character increases. - Abstract: The influence of dissolved substances on the temperature of the maximum density of water has been studied in relation to their effect on water structure as they can change the equilibrium between structured and unstructured species of water. However, most work has been performed using salts and the studies with small organic solutes such as amides are scarce. In this work, the effect of acetamide, propionamide and butyramide on the temperature of maximum density of water was determined from density measurements using a magnetic float densimeter. Densities of aqueous solutions were measured within the temperature range from T = (275.65–278.65) K at intervals of 0.50 K in the concentration range between (0.10000 and 0.80000) mol·kg −1 . The temperature of maximum density was determined from the experimental results. The effect of the three amides is to decrease the temperature of maximum density of water and the change does not follow the Despretz equation. The results are discussed in terms of solute-water interactions and the disrupting effect of amides on water structure.

The temperature dependent amide I band of crystalline acetanilide

Energy Technology Data Exchange (ETDEWEB)

Cruzeiro, Leonor [CCMAR, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); Physics Department, FCT, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); Freedman, Holly [CCMAR, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal)

2013-10-01

The temperature dependent anomalous peak in the amide I band of crystalline acetanilide is thought to be due to self-trapped states. On the contrary, according to the present model, the anomalous peak comes from the fraction of ACN molecules strongly hydrogen-bonded to a neighboring ACN molecule, and its intensity decreases because, on average, this fraction decreases as temperature increases. This model provides, for the first time, an integrated and theoretically consistent view of the temperature dependence of the full amide I band and a qualitative explanation of some of the features of nonlinear pump–probe experiments.

The temperature dependent amide I band of crystalline acetanilide

Science.gov (United States)

Cruzeiro, Leonor; Freedman, Holly

2013-10-01

The temperature dependent anomalous peak in the amide I band of crystalline acetanilide is thought to be due to self-trapped states. On the contrary, according to the present model, the anomalous peak comes from the fraction of ACN molecules strongly hydrogen-bonded to a neighboring ACN molecule, and its intensity decreases because, on average, this fraction decreases as temperature increases. This model provides, for the first time, an integrated and theoretically consistent view of the temperature dependence of the full amide I band and a qualitative explanation of some of the features of nonlinear pump-probe experiments.

The temperature dependent amide I band of crystalline acetanilide

International Nuclear Information System (INIS)

Cruzeiro, Leonor; Freedman, Holly

2013-01-01

The temperature dependent anomalous peak in the amide I band of crystalline acetanilide is thought to be due to self-trapped states. On the contrary, according to the present model, the anomalous peak comes from the fraction of ACN molecules strongly hydrogen-bonded to a neighboring ACN molecule, and its intensity decreases because, on average, this fraction decreases as temperature increases. This model provides, for the first time, an integrated and theoretically consistent view of the temperature dependence of the full amide I band and a qualitative explanation of some of the features of nonlinear pump–probe experiments.

Amide and Ester-Functionalized Humic Acid for Fuel Combustion Enhancement

Science.gov (United States)

Riggs, Mark

Humic acid is a class of naturally occurring molecules composed of large sheet-like regions of cyclic aromatic hydrocarbon networks with surface and edge functional groups including phenols, carboxylic acids, and epoxides. These naturally occurring molecules are found in brown coal deposits near lignite formations. Humic acid has gained attention from the scientific community as a precursor for graphene. Graphene is a 2-dimensional honeycomb structure of fully unsaturated carbon atoms that has exceptional material properties and inherent aromaticity. Graphene's incredible properties are matched by the difficulty associated with reproducibly manufacturing it on a large scale. This issue has limited the use of graphene for commercial applications. The polar functional groups of humic acid contribute to the hydrophilic nature of the molecule, limiting its miscibility in any alkyl-based solvent. Surfactants containing long alkyl chains can affect the miscibility of the molecule in an organic solvent. Surfactants are often difficult to remove from the system. It is theorized that alkylation of the functional sites of humic acid can affect the hydrophilic nature of the molecule, and effectively enable its dispersion into organic solvents without simultaneous incorporation of surfactants. This dissertation investigated the amidation and esterification of humic acid molecules extracted from leonardite. The resulting change in the modified humic acid dispersibility in organic solvents and its potential usage as a fuel additive were evaluated. Butyl, hexyl, octyl, and decyl amide-modified and ester-modified humic acids were synthesized. These products were characterized to confirm successful chemical reaction through thermogravimetric analysis, Fourier-transform infrared spectroscopy, and scanning electron microscopy. The decyl-modified humic acids remained suspended in kerosene mixtures for longer than 1 week. Other organo-humic acids showed varying degrees of flocculation

Synthesis and preliminary biological evaluations of (+)-isocampholenic acid-derived amides.

Science.gov (United States)

Grošelj, Uroš; Golobič, Amalija; Knez, Damijan; Hrast, Martina; Gobec, Stanislav; Ričko, Sebastijan; Svete, Jurij

2016-08-01

The synthesis of two novel (+)-isocampholenic acid-derived amines has been realized starting from commercially available (1S)-(+)-10-camphorsulfonic acid. The novel amines as well as (+)-isocampholenic acid have been used as building blocks in the construction of a library of amides using various aliphatic, aromatic, and amino acid-derived coupling partners using BPC and CDI as activating agents. Amide derivatives have been assayed against several enzymes that hold potential for the development of new drugs to battle bacterial infections and Alzheimer's disease. Compounds 20c and 20e showed promising selective sub-micromolar inhibition of human butyrylcholinesterase [Formula: see text] ([Formula: see text] values [Formula: see text] and [Formula: see text], respectively).

Selective Formation of Secondary Amides via the Copper-Catalyzed Cross-Coupling of Alkylboronic Acids with Primary Amides

Science.gov (United States)

Rossi, Steven A.; Shimkin, Kirk W.; Xu, Qun; Mori-Quiroz, Luis M.; Watson, Donald A.

2014-01-01

For the first time, a general catalytic procedure for the cross coupling of primary amides and alkylboronic acids is demonstrated. The key to the success of this reaction was the identification of a mild base (NaOSiMe3) and oxidant (di-tert-butyl peroxide) to promote the copper-catalyzed reaction in high yield. This transformation provides a facile, high-yielding method for the mono-alkylation of amides. PMID:23611591

Simple Amides of Oleanolic Acid as Effective Penetration Enhancers

Science.gov (United States)

Bednarczyk-Cwynar, Barbara; Partyka, Danuta; Zaprutko, Lucjusz

2015-01-01

Transdermal transport is now becoming one of the most convenient and safe pathways for drug delivery. In some cases it is necessary to use skin penetration enhancers in order to allow for the transdermal transport of drugs that are otherwise insufficiently skin-permeable. A series of oleanolic acid amides as potential transdermal penetration enhancers was formed by multistep synthesis and the synthesis of all newly prepared compounds is presented. The synthetized amides of oleanolic acid were tested for their in vitro penetration promoter activity. The above activity was evaluated by means of using the Fürst method. The relationships between the chemical structure of the studied compounds and penetration activity are presented. PMID:26010090

Simple amides of oleanolic acid as effective penetration enhancers.

Science.gov (United States)

Bednarczyk-Cwynar, Barbara; Partyka, Danuta; Zaprutko, Lucjusz

2015-01-01

Transdermal transport is now becoming one of the most convenient and safe pathways for drug delivery. In some cases it is necessary to use skin penetration enhancers in order to allow for the transdermal transport of drugs that are otherwise insufficiently skin-permeable. A series of oleanolic acid amides as potential transdermal penetration enhancers was formed by multistep synthesis and the synthesis of all newly prepared compounds is presented. The synthetized amides of oleanolic acid were tested for their in vitro penetration promoter activity. The above activity was evaluated by means of using the Fürst method. The relationships between the chemical structure of the studied compounds and penetration activity are presented.

Substituted Amides of Pyrazine-2-carboxylic acids: Synthesis and Biological Activity

Directory of Open Access Journals (Sweden)

Katarina Kralova

2002-03-01

Full Text Available Condensation of 6-chloro-, 5-tert-butyl- or 6-chloro-5-tert-butylpyrazine-2-carboxylic acid chloride with ring substituted anilines yielded a series of amides, which were tested for their in vitro antimycobacterial, antifungal and photosynthesis-inhibiting activities. The highest antituberculotic activity (72% inhibition against Mycobacterium tuberculosis and the highest lipophilicity (log P = 6.85 were shown by the 3,5-bistrifluoromethylphenyl amide of 5-tert-butyl-6-chloropyrazine-2-carboxylic acid (2o. The 3-methylphenyl amides of 6-chloro- and 5-tert-butyl-6-chloro-pyrazine-2-carboxylic acid (2d and 2f exhibited only a poor in vitro antifungal effect (MIC = 31.25-500 μmol·dm-3 against all strains tested, although the latter was the most active antialgal compound (IC50 = 0.063 mmol·dm-3. The most active inhibitor of oxygen evolution rate in spinach chloroplasts was the (3,5-bis-trifluoromethylphenylamide of 6-chloropyrazine-2-carboxylic acid (2m, IC50 = 0.026 mmol·dm-3.

Biomimetic L-aspartic acid-derived functional poly(ester amide)s for vascular tissue engineering.

Science.gov (United States)

Knight, Darryl K; Gillies, Elizabeth R; Mequanint, Kibret

2014-08-01

Functionalization of polymeric biomaterials permits the conjugation of cell signaling molecules capable of directing cell function. In this study, l-phenylalanine and l-aspartic acid were used to synthesize poly(ester amide)s (PEAs) with pendant carboxylic acid groups through an interfacial polycondensation approach. Human coronary artery smooth muscle cell (HCASMC) attachment, spreading and proliferation was observed on all PEA films. Vinculin expression at the cell periphery suggested that HCASMCs formed focal adhesions on the functional PEAs, while the absence of smooth muscle α-actin (SMαA) expression implied the cells adopted a proliferative phenotype. The PEAs were also electrospun to yield nanoscale three-dimensional (3-D) scaffolds with average fiber diameters ranging from 130 to 294nm. Immunoblotting studies suggested a potential increase in SMαA and calponin expression from HCASMCs cultured on 3-D fibrous scaffolds when compared to 2-D films. X-ray photoelectron spectroscopy and immunofluorescence demonstrated the conjugation of transforming growth factor-β1 to the surface of the functional PEA through the pendant carboxylic acid groups. Taken together, this study demonstrates that PEAs containing aspartic acid are viable biomaterials for further investigation in vascular tissue engineering. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

One-pot synthesis of polyunsaturated fatty acid amides with anti-proliferative properties.

Science.gov (United States)

Tremblay, Hugo; St-Georges, Catherine; Legault, Marc-André; Morin, Caroline; Fortin, Samuel; Marsault, Eric

2014-12-15

A one-pot environmentally friendly transamidation of ω-3 fatty acid ethyl esters to amides and mono- or diacylglycerols was investigated via the use of a polymer-supported lipase. The method was used to synthesize a library of fatty acid monoglyceryl esters and amides. These new derivatives were found to have potent growth inhibition effects against A549 lung cancer cells. Copyright © 2014 Elsevier Ltd. All rights reserved.

Enzymatically and reductively degradable α-amino acid-based poly(ester amide)s: synthesis, cell compatibility, and intracellular anticancer drug delivery.

Science.gov (United States)

Sun, Huanli; Cheng, Ru; Deng, Chao; Meng, Fenghua; Dias, Aylvin A; Hendriks, Marc; Feijen, Jan; Zhong, Zhiyuan

2015-02-09

A novel and versatile family of enzymatically and reductively degradable α-amino acid-based poly(ester amide)s (SS-PEAs) were developed from solution polycondensation of disulfide-containing di-p-toluenesulfonic acid salts of bis-l-phenylalanine diesters (SS-Phe-2TsOH) with di-p-nitrophenyl adipate (NA) in N,N-dimethylformamide (DMF). SS-PEAs with Mn ranging from 16.6 to 23.6 kg/mol were obtained, depending on NA/SS-Phe-2TsOH molar ratios. The chemical structures of SS-PEAs were confirmed by (1)H NMR and FTIR spectra. Thermal analyses showed that the obtained SS-PEAs were amorphous with a glass transition temperature (Tg) in the range of 35.2-39.5 °C. The in vitro degradation studies of SS-PEA films revealed that SS-PEAs underwent surface erosion in the presence of 0.1 mg/mL α-chymotrypsin and bulk degradation under a reductive environment containing 10 mM dithiothreitol (DTT). The preliminary cell culture studies displayed that SS-PEA films could well support adhesion and proliferation of L929 fibroblast cells, indicating that SS-PEAs have excellent cell compatibility. The nanoparticles prepared from SS-PEA with PVA as a surfactant had an average size of 167 nm in phosphate buffer (PB, 10 mM, pH 7.4). SS-PEA nanoparticles while stable under physiological environment undergo rapid disintegration under an enzymatic or reductive condition. The in vitro drug release studies showed that DOX release was accelerated in the presence of 0.1 mg/mL α-chymotrypsin or 10 mM DTT. Confocal microscopy observation displayed that SS-PEA nanoparticles effectively transported DOX into both drug-sensitive and -resistant MCF-7 cells. MTT assays revealed that DOX-loaded SS-PEA nanoparticles had a high antitumor activity approaching that of free DOX in drug-sensitive MCF-7 cells, while more than 10 times higher than free DOX in drug-resistant MCF-7/ADR cells. These enzymatically and reductively degradable α-amino acid-based poly(ester amide)s have provided an appealing platform for

The effect of pH on the toxicity of fatty acids and fatty acid amides to rainbow trout gill cells.

Science.gov (United States)

Bertin, Matthew J; Voronca, Delia C; Chapman, Robert W; Moeller, Peter D R

2014-01-01

Harmful algal blooms (HABs) expose aquatic organisms to multiple physical and chemical stressors during an acute time period. Algal toxins themselves may be altered by water chemistry parameters affecting their bioavailability and resultant toxicity. The purpose of this study was to determine the effects of two abiotic parameters (pH, inorganic metal salts) on the toxicity of fatty acid amides and fatty acids, two classes of lipids produced by harmful algae, including the golden alga, Prymnesium parvum, that are toxic to aquatic organisms. Rainbow trout gill cells were used as a model of the fish gill and exposed to single compounds and mixtures of compounds along with variations in pH level and concentration of inorganic metal salts. We employed artificial neural networks (ANNs) and standard ANOVA statistical analysis to examine and predict the effects of these abiotic parameters on the toxicity of fatty acid amides and fatty acids. Our results demonstrate that increasing pH levels increases the toxicity of fatty acid amides and inhibits the toxicity of fatty acids. This phenomenon is reversed at lower pH levels. Exposing gill cells to complex mixtures of chemical factors resulted in dramatic increases in toxicity compared to tests of single compounds for both the fatty acid amides and fatty acids. These findings highlight the potential of physicochemical factors to affect the toxicity of chemicals released during algal blooms and demonstrate drastic differences in the effect of pH on fatty acid amides and fatty acids. Published by Elsevier B.V.

Human acid-labile subunit deficiency: clinical, endocrine and metabolic consequences

NARCIS (Netherlands)

Domené, Horacio M.; Hwa, Vivian; Argente, Jesús; Wit, Jan M.; Wit, Jaan M.; Camacho-Hübner, Cecilia; Jasper, Héctor G.; Pozo, Jesús; van Duyvenvoorde, Hermine A.; Yakar, Shoshana; Fofanova-Gambetti, Olga V.; Rosenfeld, Ron G.; Scaglia, Paula A.; Bengolea, Sonia V.; Lteif, Aida; Kirmani, Salman; Mahmud, Farid H.; Frystyk, Jan; Hermus, Ad; Twickler, T. B.; Kempers, Marlies J. E.; Barrios, Vicente; Martos-Moreno, Gabriel A.; David, Alessia; Rose, Stephen

2009-01-01

The majority of insulin-like growth factor (IGF)-I and IGF-II circulate in the serum as a complex with the insulin-like growth factor binding protein (IGFBP)-3 or IGFBP-5, and an acid-labile subunit (ALS). The function of ALS is to prolong the half-life of the IGF-I-IGFBP-3/IGFBP-5 binary complexes.

Cinnamic acid amides from Tribulus terrestris displaying uncompetitive α-glucosidase inhibition.

Science.gov (United States)

Song, Yeong Hun; Kim, Dae Wook; Curtis-Long, Marcus J; Park, Chanin; Son, Minky; Kim, Jeong Yoon; Yuk, Heung Joo; Lee, Keun Woo; Park, Ki Hun

2016-05-23

The α-glucosidase inhibitory potential of Tribulus terrestris extracts has been reported but as yet the active ingredients are unknown. This study attempted to isolate the responsible metabolites and elucidate their inhibition mechanism of α-glucosidase. By fractionating T. terristris extracts, three cinnamic acid amide derivatives (1-3) were ascertained to be active components against α-glucosidase. The lead structure, N-trans-coumaroyltyramine 1, showed significant inhibition of α-glucosidase (IC50 = 0.42 μM). Moreover, all active compounds displayed uncompetitive inhibition mechanisms that have rarely been reported for α-glucosidase inhibitors. This kinetic behavior was fully demonstrated by showing a decrease of both Km and Vmax, and Kik/Kiv ratio ranging between 1.029 and 1.053. We progressed to study how chemical modifications to the lead structure 1 may impact inhibition. An α, β-unsaturation carbonyl group and hydroxyl group in A-ring of cinnamic acid amide emerged to be critical functionalities for α-glucosidase inhibition. The molecular modeling study revealed that the inhibitory activities are tightly related to π-π interaction as well as hydrogen bond interaction between enzyme and inhibitors. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Formulation of enterosoluble microparticles for an acid labile protein.

Science.gov (United States)

Alavi, Ahmed Kashif; Squillante, Emilio; Mehta, Ketan A

2002-01-01

A microencapsulation method that preserves the activity of an acid labile protein was developed. Solvent evaporation technique that employed ICH class 2 and 3 solvents methanol and acetone, respectively to dissolve pH-sensitive Eudragit polymers was investigated. Total protein released and lactase activities were measured using the USP method A for enteric cores and optimized with respect to process parameters. The percentage yields and entrapment efficiencies were directly proportional to solid content. The mean percentage yield and entrapment efficiency of selected sample was 84 +/- 0.9% and 88 +/- 0.7%, respectively. The residual specific activity of lactase in the selected sample was 89% +/- 0.8 with a net activity loss of 2 +/- 0.28% and 4 +/- 0.52% under ambient and stressed storage, respectively. Dibutyl sebacate levels, lower processing temperatures and lower processing speeds were influential in modulating enzyme activity. The most important formulation factor affecting lactase stability was Eudragit type, followed in decreasing order by processing temperature, processing speed, and solid percentage. Reliable control of lactase release was achieved by microencapsulating the enzyme with pH-sensitive Eudragit L and S enteric polymers using either acetone- or methanol-based solvent but lactase activity was preserved only in acetone-based formulations.

A Convenient One-Pot Method for the Synthesis of N-Methoxy-N-methyl Amides from Carboxylic Acids

International Nuclear Information System (INIS)

Kim, Joong Gon; Jang, Doo Ok

2010-01-01

We have developed a mild and convenient method for one-pot synthesis of Weinreb amides from carboxylic acids. The process is general for the preparation of Weinreb amides from a variety of carboxylic acids. The reaction was also applicable to the preparation of α-amino Weinreb amides and proceeded without deprotection of the N-Fmoc protecting group or racemization of the stereogenic centers. N-Methoxy-N-methyl amides, or Weinreb amides, have been widely used as versatile synthetic intermediates in organic syntheses. These amides serve as excellent acylating agents for organolithium or organomagnesium reagents and as robust aldehyde group equivalents. The utility of Weinreb amides has been extended to the preparation of N-protected amino aldehydes, useful intermediates for many chemoselective transformations in peptide chemistry

Safety Assessment of Amino Acid Alkyl Amides as Used in Cosmetics.

Science.gov (United States)

Burnett, Christina L; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

The Cosmetic Ingredient Review Expert Panel (Panel) reviewed the product use, formulation, and safety data of 115 amino acid alkyl amides, which function as skin and hair conditioning agents and as surfactants-cleansing agents in personal care products. Safety test data on dermal irritation and sensitization for the ingredients with the highest use concentrations, lauroyl lysine and sodium lauroyl glutamate, were reviewed and determined to adequately support the safe use of the ingredients in this report. The Panel concluded that amino acid alkyl amides are safe in the present practices of use and concentration in cosmetics, when formulated to be nonirritating.

The DIRT on Q10: In situ depletion of labile-inputs does not increase temperature sensitivity in a laboratory incubation (Invited)

Science.gov (United States)

Reynolds, L. L.; Lajtha, K.; Bowden, R.; Johnson, B. R.; Bridgham, S. D.

2013-12-01

The decomposition of soil organic matter is expected to increase with global warming and has been commonly described by kinetic models with at least two pools with differing turnover times. Pools characterized by rapid turnover are thought to consist of labile substrates. Meanwhile, slower turnover is attributed, in part, to greater chemical complexity and a necessarily higher activation energy which should in turn lead to a higher sensitivity (Q10) to temperature and a proportionally larger response to warming. Experimental tests of the relative Q10 of these pools have been inconclusive and contradictory in part due the fact that all pools are decomposing simultaneously and soils kept under differing conditions over long periods of time diverge in more than the Q10 response making them less comparable over time. We present here a test of the temperature response on soils from a 20 yr litter manipulation experiment incubated under an experimental regime that minimizes divergence among the soils. We hypothesize that 1) if exclusion of inputs has depleted labile substrates and 2) the remaining carbon is more chemically complex, then the input exclusion treatments should show a higher Q10 compared to the ambient or increased input treatments. The soils are taken from the Detritus Input and Removal Treatment (DIRT) plots in the Bousson Forest, Pennsylvania, US. The DIRT treatments consist of litter and root exclusion (no inputs = NI), no roots (NR), no litter (NL), double litter (DL), and ambient conditions (C). Soils were incubated at 25oC for 525 days. Periodically, replicate sets were rotated into 15oC, 35oC or remained at 25oC for 24 hr. The headspace CO2 concentration was measured before and after the 24 hr temperature treatments, and then all replicate sets were returned to 25oC. Twenty years of input exclusion decreased respiration rate, with NI DIRT treatments, despite the clear differences in their carbon pools. Similar studies have examined the temperature

Synthesis, properties and applications of biodegradable polymers derived from diols and dicarboxylic acids: from polyesters to poly(ester amide)s.

Science.gov (United States)

Díaz, Angélica; Katsarava, Ramaz; Puiggalí, Jordi

2014-04-25

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

Synthesis of 3H-3-azido-salicyl-N-(n-decyl) amide

International Nuclear Information System (INIS)

Lu Bin; Xu Jianxing; Chen Shizhi

2000-01-01

A novel method for the synthesis of molecular probe of ubiquinone-binding protein is described. With 3-nitrosalicylic acid and decylamine as initial compounds and under the existence of DCC, the 3-nitro-salicyl-N-(n-decyl)amide is synthesized at room temperature. Then, 3-nitro-salicyl-N-(n-decyl)amide is reduced by hydrogen with 5 % Pd/C as catalyst to form 3-amino-salicyl-N-(n-decyl)amide which is exchanged with tritium to be 3 H-3-amino-salicyl-N-(n-decyl)amide. At the temperature below 5 degree C, 3 H-3-amino-salicyl-N-(n-decyl)amide reacts with NaNO 2 and HCl, and the 3-diazo-salicyl-N-(n-decyl)amide is formed in an ice salt bath. As soon as the reaction is completed, NaN 3 is added to the mixture and stirred for 3 h at the temperature between 0 - 5 degree C and in the dark, the molecular probe of studying ubiquinone-binding protein, i. e., 3 H-3-azido-salicyl-N-(n-decyl)amide is produced

Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

Science.gov (United States)

Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger

2016-05-01

Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enantioselective synthesis of α-oxy amides via Umpolung amide synthesis.

Science.gov (United States)

Leighty, Matthew W; Shen, Bo; Johnston, Jeffrey N

2012-09-19

α-Oxy amides are prepared through enantioselective synthesis using a sequence beginning with a Henry addition of bromonitromethane to aldehydes and finishing with Umpolung Amide Synthesis (UmAS). Key to high enantioselection is the finding that ortho-iodo benzoic acid salts of the chiral copper(II) bis(oxazoline) catalyst deliver both diastereomers of the Henry adduct with high enantiomeric excess, homochiral at the oxygen-bearing carbon. Overall, this approach to α-oxy amides provides an innovative complement to alternatives that focus almost entirely on the enantioselective synthesis of α-oxy carboxylic acids.

Poly(ether amide) segmented block copolymers with adipicacid based tetra amide segments

NARCIS (Netherlands)

Biemond, G.J.E.; Feijen, Jan; Gaymans, R.J.

2007-01-01

Poly(tetramethylene oxide)-based poly(ether ester amide)s with monodisperse tetraamide segments were synthesized. The tetraamide segment was based on adipic acid, terephthalic acid, and hexamethylenediamine. The synthesis method of the copolymers and the influence of the tetraamide concentration,

Design, synthesis, and evaluation of caffeic acid amides as synergists to sensitize fluconazole-resistant Candida albicans to fluconazole.

Science.gov (United States)

Dai, Li; Zang, Chengxu; Tian, Shujuan; Liu, Wei; Tan, Shanlun; Cai, Zhan; Ni, Tingjunhong; An, Maomao; Li, Ran; Gao, Yue; Zhang, Dazhi; Jiang, Yuanying

2015-01-01

A series of caffeic acid amides were designed, synthesized, and their synergistic activity with fluconazole against fluconazole-resistant Candida albicans was evaluated in vitro. The title caffeic acid amides 3-30 except 26 exhibited potent activity, and the subsequent SAR study was conducted. Compound 3, 5, 21, and 34c, at a concentration of 1.0 μg/ml, decreased the MIC₈₀ of fluconazole from 128.0 μg/ml to 1.0-0.5 μg/ml against the fluconazole-resistant C. albicans. This result suggests that the caffeic acid amides, as synergists, can sensitize drug-resistant fungi to fluconazole. The SAR study indicated that the dihydroxyl groups and the amido groups linking to phenyl or heterocyclic rings are the important pharmacophores of the caffeic acid amides.

Amino acid amides of piperic acid (PA) and 4-ethylpiperic acid (EPA) as NorA efflux pump inhibitors of Staphylococcus aureus.

Science.gov (United States)

Wani, Naiem Ahmad; Singh, Samsher; Farooq, Saleem; Shankar, Sudha; Koul, Surrinder; Khan, Inshad Ali; Rai, Rajkishor

2016-09-01

A total of eighteen piperic acid (PA) and 4-ethylpiperic acid (EPA) amides (C1-C18) with α-, β- and γ-amino acids were synthesized, characterized and evaluated for their efflux pump inhibitory activity against ciprofloxacin resistant Staphylococcus aureus. The amides were screened against NorA overexpressing S. aureus SA-1199B and wild type S. aureus SA-1199 using ethidium bromide as NorA efflux pump substrate. EPI C6 was found to be most potent and reduced the MIC of ciprofloxacin by 16 fold followed by C18 which showed 4 fold reduction of MIC. Ethidium bromide efflux inhibition and accumulation assay proved these compounds as NorA inhibitors. Copyright © 2016 Elsevier Ltd. All rights reserved.

Method for enhancing amidohydrolase activity of fatty acid amide hydrolase

Science.gov (United States)

John, George; Nagarajan, Subbiah; Chapman, Kent; Faure, Lionel; Koulen, Peter

2017-12-26

A method for enhancing amidohydrolase activity of Fatty Acid Amide Hydrolase (FAAH) is disclosed. The method comprising administering a phenoxyacyl-ethanolamide that causes the enhanced activity. The enhanced activity can have numerous effects on biological organisms including, for example, enhancing the growth of certain seedlings.

Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: general strategy for amide N-C bond activation.

Science.gov (United States)

Meng, Guangrong; Szostak, Michal

2016-06-15

The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined ().

Effect of temperature on the decomposition of labile and recalcitrant organic matter in Chernozem

Science.gov (United States)

Larioinova, Alla; Kvitkina, Anna; Bykhovets, Sergey; Stulin, Alexandr; Blagodatskaya, Evgenia

2017-04-01

We tested the hypothesis that the recalcitrant pool of soil organic matter (SOM) is more temperature sensitive to decomposition than the labile one. The hypothesis was verified for Chernozem soil sampled from the control (unfertilized) and fertilized with NPK experimental plots of the 50 year field experiment with maize monoculture in Voronezh Region, Russia (51o41'N, 39o15'E). The labile and recalcitrant SOM pools at 2, 12, and 22°C in a long-term (430 d) incubation experiment were traced using the method of 13C natural abundance by C3-C4 transition. Based on decomposition rate constants, the SOM pools followed the order plant residues < new (C4) SOM < old (C3) SOM, with plant residues as the most labile C pool. The hypothesis was valid only for the temperature interval of 12-22°C, where Q10 values increased in the recalcitrance order from 1.2 (plant residues) to 4.3 (C3 SOM). At low temperatures (2-12°C), the values of Q10 varied in the narrow range of 2.2-2.8 irrespective of a SOM pool. In the soil under maize monoculture fertilized with NPK, the increased decomposition of C3 SOM was observed compared to the unfertilized control. The input of new C4 carbon decreased the rate of CO2 emission during the decomposition of the old C3 SOM, i.e. induced negative priming effect (PE). To the contrast, the fertilization increased the positive PE for the C3 SOM. Along with the SOM decomposition rate constants, the magnitude of PE was also temperature dependent. The maximal negative PE in control treatment was found at the lowest temperature of 2oC, while the highest positive PE in NPK fertilized soil was observed at the highest temperature of 22oC.

Engineering Escherichia coli Nicotinic Acid Mononucleotide Adenylyltransferase for Fully Active Amidated NAD Biosynthesis.

Science.gov (United States)

Wang, Xueying; Zhou, Yongjin J; Wang, Lei; Liu, Wujun; Liu, Yuxue; Peng, Chang; Zhao, Zongbao K

2017-07-01

NAD and its reduced form NADH function as essential redox cofactors and have major roles in determining cellular metabolic features. NAD can be synthesized through the deamidated and amidated pathways, for which the key reaction involves adenylylation of nicotinic acid mononucleotide (NaMN) and nicotinamide mononucleotide (NMN), respectively. In Escherichia coli , NAD de novo biosynthesis depends on the protein NadD-catalyzed adenylylation of NaMN to nicotinic acid adenine dinucleotide (NaAD), followed by NAD synthase-catalyzed amidation. In this study, we engineered NadD to favor NMN for improved amidated pathway activity. We designed NadD mutant libraries, screened by a malic enzyme-coupled colorimetric assay, and identified two variants, 11B4 (Y84V/Y118D) and 16D8 (A86W/Y118N), with a high preference for NMN. Whereas in the presence of NMN both variants were capable of enabling the viability of cells of E. coli BW25113-derived NAD-auxotrophic strain YJE003, for which the last step of the deamidated pathway is blocked, the 16D8 expression strain could grow without exogenous NMN and accumulated a higher cellular NAD(H) level than BW25113 in the stationary phase. These mutants established fully active amidated NAD biosynthesis and offered a new opportunity to manipulate NAD metabolism for biocatalysis and metabolic engineering. IMPORTANCE Adenylylation of nicotinic acid mononucleotide (NaMN) and adenylylation of nicotinamide mononucleotide (NMN), respectively, are the key steps in the deamidated and amidated pathways for NAD biosynthesis. In most organisms, canonical NAD biosynthesis follows the deamidated pathway. Here we engineered Escherichia coli NaMN adenylyltransferase to favor NMN and expressed the mutant enzyme in an NAD-auxotrophic E. coli strain that has the last step of the deamidated pathway blocked. The engineered strain survived in M9 medium, which indicated the implementation of a functional amidated pathway for NAD biosynthesis. These results enrich

A Single Enzyme Transforms a Carboxylic Acid into a Nitrile through an Amide Intermediate.

Science.gov (United States)

Nelp, Micah T; Bandarian, Vahe

2015-09-01

The biosynthesis of nitriles is known to occur through specialized pathways involving multiple enzymes; however, in bacterial and archeal biosynthesis of 7-deazapurines, a single enzyme, ToyM, catalyzes the conversion of the carboxylic acid containing 7-carboxy-7-deazaguanine (CDG) into its corresponding nitrile, 7-cyano-7-deazaguanine (preQ0 ). The mechanism of this unusual direct transformation was shown to proceed via the adenylation of CDG, which activates it to form the newly discovered amide intermediate 7-amido-7-deazaguanine (ADG). This is subsequently dehydrated to form the nitrile in a process that consumes a second equivalent of ATP. The authentic amide intermediate is shown to be chemically and kinetically competent. The ability of ToyM to activate two different substrates, an acid and an amide, accounts for this unprecedented one-enzyme catalysis of nitrile synthesis, and the differential rates of these two half reactions suggest that this catalytic ability is derived from an amide synthetase that gained a new function. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfonated reduced graphene oxide as a highly efficient catalyst for direct amidation of carboxylic acids with amines using ultrasonic irradiation.

Science.gov (United States)

Mirza-Aghayan, Maryam; Tavana, Mahdieh Molaee; Boukherroub, Rabah

2016-03-01

Sulfonated reduced graphene oxide nanosheets (rGO-SO3H) were prepared by grafting sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide (rGO) under sonochemical conditions. rGO-SO3H catalyst was characterized by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). rGO-SO3H catalyst was successfully applied as a reusable solid acid catalyst for the direct amidation of carboxylic acids with amines into the corresponding amides under ultrasonic irradiation. The direct sonochemical amidation of carboxylic acid takes place under mild conditions affording in good to high yields (56-95%) the corresponding amides in short reaction times. Copyright © 2015 Elsevier B.V. All rights reserved.

Fatty acid amide supplementation decreases impulsivity in young adult heavy drinkers

Science.gov (United States)

van Kooten, Maria J.; Veldhuizen, Maria G.; de Araujo, Ivan E.; O’Malley, Stephanie; Small, Dana M.

2016-01-01

Compromised dopamine signaling in the striatum has been associated with the expression of impulsive behaviors in addiction, obesity and alcoholism. In rodents, Intragastric infusion of the fatty acid amide oleoylethanolamide increases striatal extracellular dopamine levels via vagal afferent signaling. Here we tested whether supplementation with PhosphoLean™, a dietary supplement that contains the precursor of the fatty acid amide oleoylethanolamide (N-oleyl-phosphatidylethanolamine), would reduce impulsive responding and alcohol use in heavy drinking young adults. Twenty-two individuals were assigned to a three-week supplementation regimen with PhosphoLean™ or placebo. Impulsivity was assessed with self-report questionnaires and behavioral tasks pre- and post-supplementation. Although self-report measures of impulsivity did not change, supplementation with PhosphoLean™, but not placebo, significantly reduced false alarm rate on a Go/No-Go task. In addition, an association was found between improved sensitivity on the Go/No-Go task and reduced alcohol intake. These findings provide preliminary evidence that promoting fatty acid derived gut-brain dopamine communication may have therapeutic potential for reducing impulsivity in heavy drinkers. PMID:26656766

Identification of genetic determinants and enzymes involved with the amidation of glutamic acid residues in the peptidoglycan of Staphylococcus aureus.

Directory of Open Access Journals (Sweden)

Teresa A Figueiredo

2012-01-01

Full Text Available The glutamic acid residues of the peptidoglycan of Staphylococcus aureus and many other bacteria become amidated by an as yet unknown mechanism. In this communication we describe the identification, in the genome of S. aureus strain COL, of two co-transcribed genes, murT and gatD, which are responsible for peptidoglycan amidation. MurT and GatD have sequence similarity to substrate-binding domains in Mur ligases (MurT and to the catalytic domain in CobB/CobQ-like glutamine amidotransferases (GatD. The amidation of glutamate residues in the stem peptide of S. aureus peptidoglycan takes place in a later step than the cytoplasmic phase--presumably the lipid phase--of the biosynthesis of the S. aureus cell wall precursor. Inhibition of amidation caused reduced growth rate, reduced resistance to beta-lactam antibiotics and increased sensitivity to lysozyme which inhibited culture growth and caused degradation of the peptidoglycan.

The ortho backbone amide linker (o-BAL) is an easily prepared and highly acid-labile handle for solid-phase synthesis

DEFF Research Database (Denmark)

Boas, Ulrik; Brask, Jesper; Christensen, J.B.

2002-01-01

The tris(alkoxy)benzyl backbone amide linker (BAL) has found widespread application in solid-phase synthesis. The key intermediate for preparation of para BAL (p-BAL) is 2,6-dimethoxy-4-hydroxybenzaldehyde; several reports on its synthesis have appeared. However, the ortho analogue of the handle (o...

A comparative study of the complexation of uranium(VI) with oxydiacetic acid and its amide derivatives

International Nuclear Information System (INIS)

Rao, Linfeng; Tian, Guoxin

2005-01-01

There has been significant interest in recent years in the studies of alkyl-substituted amides as extractants for actinide separation because the products of radiolytic and hydrolytic degradation of amides are less detrimental to separation processes than those of organophosphorus compounds traditionally used in actinide separations. Stripping of actinides from the amide-containing organic solvents is relatively easy. In addition, the amide ligands are completely incinerable so that the amount of secondary wastes generated in nuclear waste treatment could be significantly reduced. One group of alkyl-substituted oxa-diamides have been shown to be promising in the separation of actinides from nuclear wastes. For example, tetraoctyl-3-oxa-glutaramide and tetraisobutyl-oxa-glutaramide form actinide complexes that can be effectively extracted from nitric acid solutions. To understand the thermodynamic principles governing the complexation of actinides with oxa-diamides, we have studied the complexation of U(VI) with dimethyl-3-oxa-glutaramic acid (DMOGA) and tetramethyl-3-oxa-glutaramide (TMOGA) in aqueous solutions, in comparison with oxydiacetic acid (ODA) (Figure 1). Previous studies have indicated that the complexation of U(VI) with ODA is strong and entropy-driven. Comparing the results for DMOGA and TMOGA with those for ODA could provide insight into the energetics of amide complexation with U(VI) and the relationship between the thermodynamic properties and the ligand structure

Quantitative structure-cytotoxicity relationship of piperic acid amides.

Science.gov (United States)

Shimada, Chiyako; Uesawa, Yoshihiro; Ishihara, Mariko; Kagaya, Hajime; Kanamoto, Taisei; Terakubo, Shigemi; Nakashima, Hideki; Takao, Koichi; Miyashiro, Takaki; Sugita, Yoshiaki; Sakagami, Hiroshi

2014-09-01

A total of 12 piperic acid amides, including piperine, were subjected to quantitative structure-activity relationship (QSAR) analysis, based on their cytotoxicity, tumor selectivity and anti-HIV activity, in order to find new biological activities. Cytotoxicity against four human oral squamous cell carcinoma (OSCC) cell lines and three human oral normal cells was determined by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) method. Tumor selectivity was evaluated by the ratio of the mean 50% cytotoxic concentration (CC50) against normal oral cells to that against OSCC cell lines. Anti-HIV activity was evaluated by the ratio of the CC50 to 50% HIV infection-cytoprotective concentration (EC50). Physicochemical, structural, and quantum-chemical parameters were calculated based on the conformations optimized by LowModeMD method followed by density functional theory method. All compounds showed low-to-moderate tumor selectivity, but no anti-HIV activity. N-Piperoyldopamine ( 8: ) which has a catechol moiety, showed the highest tumor selectivity, possibly due to its unique molecular shape and electrostatic interaction, especially its largest partial equalization of orbital electronegativities and vsurf descriptors. The present study suggests that molecular shape and ability for electrostatic interaction are useful parameters for estimating the tumor selectivity of piperic acid amides. Copyright© 2014 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

Method for enhancing amidohydrolase activity of fatty acid amide hydrolase

Science.gov (United States)

John, George; Nagarajan, Subbiah; Chapman, Kent; Faure, Lionel; Koulen, Peter

2016-10-25

A method for enhancing amidohydrolase activity of Fatty Acid Amide Hydrolase (FAAH) is disclosed. The method comprising administering a phenoxyacylethanolamide that causes the enhanced activity. The enhanced activity can have numerous effects on biological organisms including, for example, enhancing the growth of certain seedlings. The subject matter disclosed herein relates to enhancers of amidohydrolase activity.

Phenotypic assessment of THC discriminative stimulus properties in fatty acid amide hydrolase knockout and wildtype mice

OpenAIRE

Walentiny, D. Matthew; Vann, Robert E.; Wiley, Jenny L.

2015-01-01

A number of studies have examined the ability of the endogenous cannabinoid anandamide to elicit Δ9 -tetrahydrocannabinol (THC)-like subjective effects, as modeled through the THC discrimination paradigm. In the present study, we compared transgenic mice lacking fatty acid amide hydrolase (FAAH), the enzyme primarily responsible for anandamide catabolism, to wildtype counterparts in a THC discrimination procedure. THC (5.6 mg/kg) served as a discriminative stimulus in both genotypes, with sim...

Water-stable helical structure of tertiary amides of bicyclic β-amino acid bearing 7-azabicyclo[2.2.1]heptane. Full control of amide cis-trans equilibrium by bridgehead substitution.

Science.gov (United States)

Hosoya, Masahiro; Otani, Yuko; Kawahata, Masatoshi; Yamaguchi, Kentaro; Ohwada, Tomohiko

2010-10-27

Helical structures of oligomers of non-natural β-amino acids are significantly stabilized by intramolecular hydrogen bonding between main-chain amide moieties in many cases, but the structures are generally susceptible to the environment; that is, helices may unfold in protic solvents such as water. For the generation of non-hydrogen-bonded ordered structures of amides (tertiary amides in most cases), control of cis-trans isomerization is crucial, even though there is only a small sterical difference with respect to cis and trans orientations. We have established methods for synthesis of conformationally constrained β-proline mimics, that is, bridgehead-substituted 7-azabicyclo[2.2.1]heptane-2-endo-carboxylic acids. Our crystallographic, 1D- and 2D-NMR, and CD spectroscopic studies in solution revealed that a bridgehead methoxymethyl substituent completely biased the cis-trans equilibrium to the cis-amide structure along the main chain, and helical structures based on the cis-amide linkage were generated independently of the number of residues, from the minimalist dimer through the tetramer, hexamer, and up to the octamer, and irrespective of the solvent (e.g., water, alcohol, halogenated solvents, and cyclohexane). Generality of the control of the amide equilibrium by bridgehead substitution was also examined.

Mapping temperature-induced conformational changes in the Escherichia coli heat shock transcription factor sigma 32 by amide hydrogen exchange

DEFF Research Database (Denmark)

Rist, Wolfgang; Jørgensen, Thomas J D; Roepstorff, Peter

2003-01-01

Stress conditions such as heat shock alter the transcriptional profile in all organisms. In Escherichia coli the heat shock transcription factor, sigma 32, out-competes upon temperature up-shift the housekeeping sigma-factor, sigma 70, for binding to core RNA polymerase and initiates heat shock...... gene transcription. To investigate possible heat-induced conformational changes in sigma 32 we performed amide hydrogen (H/D) exchange experiments under optimal growth and heat shock conditions combined with mass spectrometry. We found a rapid exchange of around 220 of the 294 amide hydrogens at 37...... degrees C, indicating that sigma 32 adopts a highly flexible structure. At 42 degrees C we observed a slow correlated exchange of 30 additional amide hydrogens and localized it to a helix-loop-helix motif within domain sigma 2 that is responsible for the recognition of the -10 region in heat shock...

Mechanical characterization of porous asphalt mixes modified with fatty acid amides -FAA-

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Vanessa Senior Arrieta

2017-01-01

Full Text Available Porous asphalt mixes (PAM, form a special road surface for asphalt pavement structures, have a special particle size distribution that lets infiltrate to the runoff storm water through of it because of its voids content about 20 %. Many researchers conducted studies and have concluded that the use of modified asphalts is completely necessary to design PAM. Organic and chemical additives and special procedures as foamed asphalt have enhanced the performance of PAM, during their service life. This paper is focused on the mechanical characterization of PAM and how the asphalt modified with fatty acid amides, influenced on their behavior and performance. Based on an experimental methodology with laboratory tests aimed at establishing a comparison between porous asphalt mixes, using for its design and production a penetration 60-70 pure asphalt and another one asphalt modified with fatty acid amides.

Primary fatty acid amide metabolism: conversion of fatty acids and an ethanolamine in N18TG2 and SCP cells1[S

Science.gov (United States)

Farrell, Emma K.; Chen, Yuden; Barazanji, Muna; Jeffries, Kristen A.; Cameroamortegui, Felipe; Merkler, David J.

2012-01-01

Primary fatty acid amides (PFAM) are important signaling molecules in the mammalian nervous system, binding to many drug receptors and demonstrating control over sleep, locomotion, angiogenesis, and many other processes. Oleamide is the best-studied of the primary fatty acid amides, whereas the other known PFAMs are significantly less studied. Herein, quantitative assays were used to examine the endogenous amounts of a panel of PFAMs, as well as the amounts produced after incubation of mouse neuroblastoma N18TG2 and sheep choroid plexus (SCP) cells with the corresponding fatty acids or N-tridecanoylethanolamine. Although five endogenous primary amides were discovered in the N18TG2 and SCP cells, a different pattern of relative amounts were found between the two cell lines. Higher amounts of primary amides were found in SCP cells, and the conversion of N-tridecanoylethanolamine to tridecanamide was observed in the two cell lines. The data reported here show that the N18TG2 and SCP cells are excellent model systems for the study of PFAM metabolism. Furthermore, the data support a role for the N-acylethanolamines as precursors for the PFAMs and provide valuable new kinetic results useful in modeling the metabolic flux through the pathways for PFAM biosynthesis and degradation. PMID:22095832

Antiproliferative activity of synthetic fatty acid amides from renewable resources.

Science.gov (United States)

dos Santos, Daiane S; Piovesan, Luciana A; D'Oca, Caroline R Montes; Hack, Carolina R Lopes; Treptow, Tamara G M; Rodrigues, Marieli O; Vendramini-Costa, Débora B; Ruiz, Ana Lucia T G; de Carvalho, João Ernesto; D'Oca, Marcelo G Montes

2015-01-15

In the work, the in vitro antiproliferative activity of a series of synthetic fatty acid amides were investigated in seven cancer cell lines. The study revealed that most of the compounds showed antiproliferative activity against tested tumor cell lines, mainly on human glioma cells (U251) and human ovarian cancer cells with a multiple drug-resistant phenotype (NCI-ADR/RES). In addition, the fatty methyl benzylamide derived from ricinoleic acid (with the fatty acid obtained from castor oil, a renewable resource) showed a high selectivity with potent growth inhibition and cell death for the glioma cell line-the most aggressive CNS cancer. Copyright © 2014 Elsevier Ltd. All rights reserved.

CD44 Binding to Hyaluronic Acid Is Redox Regulated by a Labile Disulfide Bond in the Hyaluronic Acid Binding Site.

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Helena Kellett-Clarke

Full Text Available CD44 is the primary leukocyte cell surface receptor for hyaluronic acid (HA, a component of the extracellular matrix. Enzymatic post translational cleavage of labile disulfide bonds is a mechanism by which proteins are structurally regulated by imparting an allosteric change and altering activity. We have identified one such disulfide bond in CD44 formed by Cys77 and Cys97 that stabilises the HA binding groove. This bond is labile on the surface of leukocytes treated with chemical and enzymatic reducing agents. Analysis of CD44 crystal structures reveal the disulfide bond to be solvent accessible and in the-LH hook configuration characteristic of labile disulfide bonds. Kinetic trapping and binding experiments on CD44-Fc chimeric proteins show the bond is preferentially reduced over the other disulfide bonds in CD44 and reduction inhibits the CD44-HA interaction. Furthermore cells transfected with CD44 no longer adhere to HA coated surfaces after pre-treatment with reducing agents. The implications of CD44 redox regulation are discussed in the context of immune function, disease and therapeutic strategies.

Solvent extraction of uranium(VI) and thorium(IV) from nitrate media by carboxylic acid amides

International Nuclear Information System (INIS)

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

1995-01-01

A series of nineteen N-alkyl carboxylic acid amides (R.CO.NHR') has been prepared, in which the alkyl groups R and R' have been varied in order to introduce different degrees of steric complexity into the compounds. A smaller number of N,N-dialkyl amides (R.CO.NR 2 ') and non-substituted amides (R.CO.NH 2 ) has also been prepared for comparison purposes. These amides were characterized by measurement of their boiling points, melting points, refractive indices and densities. The solvent extraction of uranium(VI) and thorium(IV) from sodium nitrate media by solutions of the amides in toluene was studied. Increasing steric bulk of the alkyl groups R and R' was found to cause a marked decrease in the extraction of thorium, with a much smaller effect on the extraction of uranium, thus considerably enhancing the separation between these metals. Vapour pressure osmometry studies indicate that the N-alkyl amides are self-associated in toluene solution, with aggregation numbers up to about 2.5 for 0.6 M solutions at 35 degree C. In contrast, the N,N-dialkyl amides behave as monomers under these conditions. The distribution ratios for the extraction of uranium and thorium show second- and third-order dependences, respectively, on the extractant concentration for both the N-alkyl and N,N-dialkyl amides. 15 refs., 8 figs., 8 tabs

Synthesis, Anti-HCV, Antioxidant and Reduction of Intracellular Reactive Oxygen Species Generation of a Chlorogenic Acid Analogue with an Amide Bond Replacing the Ester Bond.

Science.gov (United States)

Wang, Ling-Na; Wang, Wei; Hattori, Masao; Daneshtalab, Mohsen; Ma, Chao-Mei

2016-06-08

Chlorogenic acid is a well known natural product with important bioactivities. It contains an ester bond formed between the COOH of caffeic acid and the 3-OH of quinic acid. We synthesized a chlorogenic acid analogue, 3α-caffeoylquinic acid amide, using caffeic and quinic acids as starting materials. The caffeoylquinc acid amide was found to be much more stable than chlorogenic acid and showed anti-Hepatitis C virus (anti-HCV) activity with a potency similar to chlorogenic acid. The caffeoylquinc acid amide potently protected HepG2 cells against oxidative stress induced by tert-butyl hydroperoxide.

Biosynthesis and function of simple amides in Xenorhabdus doucetiae.

Science.gov (United States)

Bode, Edna; He, Yue; Vo, Tien Duy; Schultz, Roland; Kaiser, Marcel; Bode, Helge B

2017-11-01

Xenorhabdus doucetiae, the bacterial symbiont of the entomopathogenic nematode Steinernema diaprepesi produces several different fatty acid amides. Their biosynthesis has been studied using a combination of analysis of gene deletions and promoter exchanges in X. doucetiae and heterologous expression of candidate genes in E. coli. While a decarboxylase is required for the formation of all observed phenylethylamides and tryptamides, the acyltransferase XrdE encoded in the xenorhabdin biosynthesis gene cluster is responsible for the formation of short chain acyl amides. Additionally, new, long-chain and cytotoxic acyl amides were identified in X. doucetiae infected insects and when X. doucetiae was grown in Galleria Instant Broth (GIB). When the bioactivity of selected amides was tested, a quorum sensing modulating activity was observed for the short chain acyl amides against the two different quorum sensing systems from Chromobacterium and Janthinobacterium. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

synthesis, antimicrobial and phytotoxic activity of amide derivatives of L-(+)-2,3-diacetoxy-4-methoxy-4-oxo-butanoic acid

International Nuclear Information System (INIS)

Malik, M.; Khan, S.W.; Zaidi, J.H.; Khan, K.M.; Hussain, S.

2014-01-01

A short, versatile, an efficient asymmetric synthesis of substituted aromatic amides is described. L-Tartaric acid conveniently converted into diacetyl-L-tartaric anhydride. Diacetyl-L-tartaric anhydride was then transformed into half ester which was then reacted with substituted anilines to yield respective chiral amides 3-8. These chiral amides were characterized by spectroscopic techniques i.e. 1H-NMR, 13C-NMR, IR and mass spectrometry. Amides 3-8 were tested for their antimicrobial as well as phytotoxic activities. (author)

Synthesis and characterization of poly(ester amide from remewable resources through melt polycondensation

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B. B. Wang

2014-01-01

Full Text Available Biodegradable poly(ester amides (PEAs were synthesized from lactic acid and 11-aminoundecanoic acid via melt polycondensation. Molecular weights, chemical structures and thermal properties of the poly(ester amides were characterized in terms of gel permeation chromatography (GPC, Fourier transform infrared spectroscopy (FTIR, 1H nuclear magnetic resonance (1H NMR, differential scanning calorimetry (DSC and thermogravimetric analysis (TGA, respectively. The PEAs have low molecular weights and display a lower cold crystallization temperature as well as smaller crystallinity by comparison with the pure poly(lactic acid (PLA. The incorporation of the 11-aminoundecanoic acid into the PLA chain not only improved the thermal stability but changed the decomposition process.

Lability of Nanoparticulate Metal Complexes at a Macroscopic Metal Responsive (Bio)interface

NARCIS (Netherlands)

Duval, Jérôme F.L.; Town, Raewyn M.; Leeuwen, Van Herman P.

2018-01-01

The lability of metal complexes expresses the extent of the dissociative contribution of the complex species to the flux of metal ions toward a macroscopic metal-responsive (bio)interface, for example, an electrodic sensor or an organism. While the case of molecular ligands is well-established, it

Microbial control of soil organic matter mineralization responses to labile carbon in subarctic climate change treatments.

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Rousk, Kathrin; Michelsen, Anders; Rousk, Johannes

2016-12-01

Half the global soil carbon (C) is held in high-latitude systems. Climate change will expose these to warming and a shift towards plant communities with more labile C input. Labile C can also increase the rate of loss of native soil organic matter (SOM); a phenomenon termed 'priming'. We investigated how warming (+1.1 °C over ambient using open top chambers) and litter addition (90 g m -2  yr -1 ) treatments in the subarctic influenced the susceptibility of SOM mineralization to priming, and its microbial underpinnings. Labile C appeared to inhibit the mineralization of C from SOM by up to 60% within hours. In contrast, the mineralization of N from SOM was stimulated by up to 300%. These responses occurred rapidly and were unrelated to microbial successional dynamics, suggesting catabolic responses. Considered separately, the labile C inhibited C mineralization is compatible with previously reported findings termed 'preferential substrate utilization' or 'negative apparent priming', while the stimulated N mineralization responses echo recent reports of 'real priming' of SOM mineralization. However, C and N mineralization responses derived from the same SOM source must be interpreted together: This suggested that the microbial SOM-use decreased in magnitude and shifted to components richer in N. This finding highlights that only considering SOM in terms of C may be simplistic, and will not capture all changes in SOM decomposition. The selective mining for N increased in climate change treatments with higher fungal dominance. In conclusion, labile C appeared to trigger catabolic responses of the resident microbial community that shifted the SOM mining to N-rich components; an effect that increased with higher fungal dominance. Extrapolating from these findings, the predicted shrub expansion in the subarctic could result in an altered microbial use of SOM, selectively mining it for N-rich components, and leading to a reduced total SOM-use. © 2016 John Wiley

Synthesis and Characterization of Ethylene DiamineTetera Acetic Acid Polyester-amides polymer with Aminoalcohol

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Dakhil Nasser Taha

2017-02-01

Full Text Available linear aromatic and aliphatic polyester-amides (PEAs have been synthesized by polycondensation of aliphatic and aromatic aminoalcohol (Ethanol amine, 2-amino-2-methyl-propan-1-ol, m-amino phenol with Ethylenediaminetetraacetic acid (EDTA as a favorable and combined complexing compound was joined into the polymer backbone with poly addition reactions. These polymers were characterized by FTIR, 1H NMR, solubility studies , elemental analysis, , Thermal analyses such as TGA were measured, intrinsic viscosity. The poly(ester-amides obtained show good thermal stability.

Picolyl amides of betulinic acid as antitumor agents causing tumor cell apoptosis

Czech Academy of Sciences Publication Activity Database

Bildziukevich, Uladzimir; Rárová, L.; Šaman, David; Wimmer, Zdeněk

2018-01-01

Roč. 145, FEB 10 (2018), s. 41-50 ISSN 0223-5234 R&D Projects: GA MPO(CZ) FV10599 Institutional support: RVO:61389030 ; RVO:61388963 Keywords : Amide * Betulinic acid * Cytotoxicity * Picolyl amine * Therapeutic index Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 4.519, year: 2016

Antitumor activity of newly synthesized oxo and ethylidene derivatives of bile acids and their amides and oxazolines.

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Bjedov, Srđan; Jakimov, Dimitar; Pilipović, Ana; Poša, Mihalj; Sakač, Marija

2017-04-01

Bile acid derivatives with modifications in side chain and modifications on steroid skeleton were synthetized and their antitumor activity against five human cancer cell lines was investigated. Modifications in side chain include amid group, formed in reaction with 2-amino-2-methylpropanol, and 4,4-dimethyloxazoline group, obtained after cyclization of amides. In the steroid skeleton oxo groups were introduced in position 7 (2, 2a, 2b) and 7,12 (3, 3a, 3b). Ethylidene groups were introduced regio- and stereoselectively on C-7, and/or without stereoselectivity on C-3 by Wittig reaction. By combination of these modifications, a series of 19 bile acid derivatives were synthesized. Compounds containing both C-7 ethylidene and C-12 carbonyl groups (6, 6a, 6b) shown very good antitumor activity with IC 50 amide or oxazoline group has positive effect on cytotoxicity. Different molecular descriptors were determined in silico and after principal component analysis was found that molecular descriptor BLTF96 can be used for fast assessment of experimental cytotoxicity of bile acid derivatives. Copyright © 2017 Elsevier Inc. All rights reserved.

Transgenic tomato plants overexpressing tyramine N-hydroxycinnamoyltransferase exhibit elevated hydroxycinnamic acid amide levels and enhanced resistance to Pseudomonas syringae.

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Campos, Laura; Lisón, Purificación; López-Gresa, María Pilar; Rodrigo, Ismael; Zacarés, Laura; Conejero, Vicente; Bellés, José María

2014-10-01

Hydroxycinnamic acid amides (HCAA) are secondary metabolites involved in plant development and defense that have been widely reported throughout the plant kingdom. These phenolics show antioxidant, antiviral, antibacterial, and antifungal activities. Hydroxycinnamoyl-CoA:tyramine N-hydroxycinnamoyl transferase (THT) is the key enzyme in HCAA synthesis and is induced in response to pathogen infection, wounding, or elicitor treatments, preceding HCAA accumulation. We have engineered transgenic tomato plants overexpressing tomato THT. These plants displayed an enhanced THT gene expression in leaves as compared with wild type (WT) plants. Consequently, leaves of THT-overexpressing plants showed a higher constitutive accumulation of the amide coumaroyltyramine (CT). Similar results were found in flowers and fruits. Moreover, feruloyltyramine (FT) also accumulated in these tissues, being present at higher levels in transgenic plants. Accumulation of CT, FT and octopamine, and noradrenaline HCAA in response to Pseudomonas syringae pv. tomato infection was higher in transgenic plants than in the WT plants. Transgenic plants showed an enhanced resistance to the bacterial infection. In addition, this HCAA accumulation was accompanied by an increase in salicylic acid levels and pathogenesis-related gene induction. Taken together, these results suggest that HCAA may play an important role in the defense of tomato plants against P. syringae infection.

Influence of ascorbic acid on in vivo amidation of alpha-melanocyte stimulating hormone in guinea pig pituitary

DEFF Research Database (Denmark)

Fenger, M; Hilsted, L

1988-01-01

The effect of ascorbic acid depletion on the amidation of alphamelanocyte stimulating hormone (alpha MSH) was studied in vivo in guinea pig pituitary. After four weeks, the concentration of ascorbic acid was 1.20 +/- 0.11 mumol/g tissue (mean +/- SD) in the pituitary and 0.34 +/- 0.07 mumol......-39) immunoreactivity was observed in the depleted guinea pigs. Gel chromatography and reversed-phase high-performance luquid chromatography showed that the alpha MSH and ACTH (1-14) immunoreactivity was of low molecular weight and partly mono- or diacetylated. Depletion of ascorbic acid had no influence on the degree...... of acetylation of alpha MSH and ACTH (1-14). It is concluded that depletion of ascorbic acid reduces the in vivo amidation of ACTH (1-14) in the guinea pig pituitary....

Poly(Amide-imide Aerogel Materials Produced via an Ice Templating Process

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Matthew D. Gawryla

2018-02-01

Full Text Available Low density composites of sodium montmorillonite and poly(amide-imide polymers have been created using an ice templating method, which serves as an alternative to the often-difficult foaming of high temperature/high performance polymers. The starting polymer was received in the poly(amic acid form which can be cured using heat, into a water insoluble amide-imide copolymer. The resulting materials have densities in the 0.05 g/cm3 range and have excellent mechanical properties. Using a tertiary amine as a processing aid provides for lower viscosity and allows more concentrated polymer solutions to be used. The concentration of the amine relative to the acid groups on the polymer backbone has been found to cause significant difference in the mechanical properties of the dried materials. The synthesis and characterization of low density versions of two poly(amide-imide polymers and their composites with sodium montmorillonite clay are discussed in the present work.

Poly(Amide-imide) Aerogel Materials Produced via an Ice Templating Process.

Science.gov (United States)

Gawryla, Matthew D; Arndt, Eric M; Sánchez-Soto, Miguel; Schiraldi, David A

2018-02-03

Low density composites of sodium montmorillonite and poly(amide-imide) polymers have been created using an ice templating method, which serves as an alternative to the often-difficult foaming of high temperature/high performance polymers. The starting polymer was received in the poly(amic acid) form which can be cured using heat, into a water insoluble amide-imide copolymer. The resulting materials have densities in the 0.05 g/cm³ range and have excellent mechanical properties. Using a tertiary amine as a processing aid provides for lower viscosity and allows more concentrated polymer solutions to be used. The concentration of the amine relative to the acid groups on the polymer backbone has been found to cause significant difference in the mechanical properties of the dried materials. The synthesis and characterization of low density versions of two poly(amide-imide) polymers and their composites with sodium montmorillonite clay are discussed in the present work.

Biaryl amide compounds reduce the inflammatory response in macrophages by regulating Dectin-1.

Science.gov (United States)

Hyung, Kyeong Eun; Lee, Mi Ji; Lee, Yun-Jung; Lee, Do Ik; Min, Hye Young; Park, So-Young; Min, Kyung Hoon; Hwang, Kwang Woo

2016-03-01

Macrophages are archetypal innate immune cells that play crucial roles in the recognition and phagocytosis of invading pathogens, which they identify using pattern recognition receptors (PRRs). Dectin-1 is essential for antifungal immune responses, recognizing the fungal cellular component β-glucan, and its role as a PRR has been of increasing interest. Previously, we discovered and characterized a novel biaryl amide compound, MPS 03, capable of inhibiting macrophage phagocytosis of zymosan. Therefore, in this study we aimed to identify other biaryl amide compounds with greater effectiveness than MPS 03, and elucidate their cellular mechanisms. Several MPS 03 derivatives were screened, four of which reduced zymosan phagocytosis in a similar manner to MPS 03. To establish whether such phagocytosis inhibition influenced the production of inflammatory mediators, pro-inflammatory cytokine and nitric oxide (NO) levels were measured. The production of TNF-α, IL-6, IL-12, and NO was significantly reduced in a dose-dependent manner. Moreover, the inflammation-associated MAPK signaling pathway was also affected by biaryl amide compounds. To investigate the underlying cellular mechanism, PRR expression was measured. MPS 03 and its derivatives were found to inhibit zymosan phagocytosis by decreasing Dectin-1 expression. Furthermore, when macrophages were stimulated by zymosan after pretreatment with biaryl amide compounds, downstream transcription factors such as NFAT, AP-1, and NF-κB were downregulated. In conclusion, biaryl amide compounds reduce zymosan-induced inflammatory responses by downregulating Dectin-1 expression. Therefore, such compounds could be used to inhibit Dectin-1 in immunological experiments and possibly regulate excessive inflammatory responses. Copyright © 2016. Published by Elsevier B.V.

Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

Science.gov (United States)

Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

2014-02-05

The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

Gold recovery from acidic leach solutions using as extractants trialkylamines of N,N'-di-alkyl-aliphatic amides

Energy Technology Data Exchange (ETDEWEB)

Baroncelli, F.; Carlini, D.; Gasparini, G.M.; Simonetti, E.

1988-07-01

TriOctylAmine (TOA) and a di-substituted aliphatic amide, N,N-Di-N-ButylOctanamide (DBOA), were examined in batch and in mini mixer-settler experiments using leachates of Peruvian and Bolivian concentrates. With these minerals, very rich in sulfur (pyrites, stybine), 90-95% gold recovery in 12-24 hours was reached by leaching with 4M aqua regia (HCl 3M nitric acid 1M) at room temperature and with 1/3 solid/liquid ratio. With these leachate solutions (2-3M total acidity, 10-60 ppm ao Au), the two processes with TOA (GAMEX PROCESS) and with DBOA (AUMIDEX PROCESS) were tested and compared. Experimental results strongly support the possibility of using TOA and DBOA on an industrial scale.

Evaluation of amides and centrifugation temperature in boar semen cryopreservation.

Science.gov (United States)

Bianchi, I; Calderam, K; Maschio, E F; Madeira, E M; da Rosa Ulguim, R; Corcini, C D; Bongalhardo, D C; Corrêa, E K; Lucia, T; Deschamps, J C; Corrêa, M N

2008-03-15

Two experiments were conducted to evaluate the use of amides as cryoprotectants and two centrifugation temperatures (15 or 24 degrees C) in boar semen cryopreservation protocols. Semen was diluted in BTS, cooled centrifuged, added to cooling extenders, followed by the addition of various cryoprotectants. In experiment 1, mean (+/-S.E.M.) sperm motility for 5% dimethylformamide (DMF; 50.6+/-1.9%) and 5% dimethylacetamide (DMA; 53.8+/-1.7%) were superior (P0.05). In experiment 2, we tested MF, DMF, and DMA at 3, 5, and 7%. Sperm motility and membrane integrity were higher for 5% DMA (53.8+/-1.7 and 50.9+/-1.9%) and 5% DMF (50.6+/-1.9 and 47.9+/-2.1%), in comparison with 7% DMF and all MF concentrations (P0.05). In conclusion, boar semen was successfully cryopreserved by replacement of glycerol with amides (especially 5% DMA) and centrifugation at 15 degrees C, with benefits for post-thaw sperm motility and membrane integrity.

Characterization of fatty acid amide hydrolase activity by a fluorescence-based assay.

Science.gov (United States)

Dato, Florian M; Maaßen, Andreas; Goldfuß, Bernd; Pietsch, Markus

2018-04-01

Fatty acid amide hydrolase (FAAH) is involved in many human diseases, particularly cancer, pain and inflammation as well as neurological, metabolic and cardiovascular disorders. Therefore, FAAH is an attractive target for the development of low-molecular-weight inhibitors as therapeutics, which requires robust assays that can be used for high-throughput screening (HTS) of compound libraries. Here, we report the development of a fluorometric assay based on FAAH's ability to effectively hydrolyze medium-chain fatty acid amides, introducing N-decanoyl-substituted 5-amino-2-methoxypyridine (D-MAP) as new amide substrate. D-MAP is cleaved by FAAH with an 8-fold larger specificity constant than the previously reported octanoyl-analog Oc-MAP (V max /K m of 1.09 and 0.134 mL min -1 mg -1 , respectively), with both MAP derivatives possessing superior substrate properties and much increased aqueous solubility compared to the respective p-nitroaniline compounds D-pNA and Oc-pNA. The new assay with D-MAP as substrate is highly sensitive using a lower enzyme concentration (1 μg mL -1 ) than literature-reported fluorimetric FAAH assays. In addition, D-MAP was validated in comparison to the substrate Oc-MAP for the characterization of FAAH inhibitors by means of the reference compounds URB597 and TC-F2 and was shown to be highly suitable for HTS in both kinetic and endpoint assays (Z' factors of 0.81 and 0.78, respectively). Copyright © 2018 Elsevier Inc. All rights reserved.

Design, docking, synthesis and anticancer activity of some novel 2-(4-methylbenzenesulphonamidopentanedioic acid amide derivatives

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Satyajit Dutta

2014-08-01

Full Text Available In the present work few novel 2-(4-methylbenzenesulphonamidopentanedioic acid amide derivatives and the basic compound 2-(4-methylphenylsulfon-amidopentanedioic acid have been designed, synthesized, characterized and screened for their possible antineoplastic activity both in vitro and in vivo. The modified drugs were docked against the protein histone deacetylase the energy value obtained was o-iodoanilide (-10.370504 and m-iodoanilide (-10.218276 of the titled compound. The in vitro activity was performed against five human cell lines like human breast cancer (MCF-7, leukemia (K-562, ova-rian cancer (OVACAR-3, human colon adenocarcinoma (HT-29 and Human kidney carcinoma (A-498. The in vivo activity was performed in female Swiss albino mice against Ehrlich Ascites Carcinoma (EAC. Among the synthesized compounds, o-iodoanilide, m-iodoanilide and p-iodoanilide derivatives of 2-(4-methyl benzene sulphonyl-pentanedioic acid amides showed encouraging activity in both the in vitro and in vivo compared to other compounds.

Engineering an ATP-dependent D-Ala:D-Ala ligase for synthesizing amino acid amides from amino acids.

Science.gov (United States)

Miki, Yuta; Okazaki, Seiji; Asano, Yasuhisa

2017-05-01

We successfully engineered a new enzyme that catalyzes the formation of D-Ala amide (D-AlaNH 2 ) from D-Ala by modifying ATP-dependent D-Ala:D-Ala ligase (EC 6.3.2.4) from Thermus thermophilus, which catalyzes the formation of D-Ala-D-Ala from two molecules of D-Ala. The new enzyme was created by the replacement of the Ser293 residue with acidic amino acids, as it was speculated to bind to the second D-Ala of D-Ala-D-Ala. In addition, a replacement of the position with Glu performed better than that with Asp with regards to specificity for D-AlaNH 2 production. The S293E variant, which was selected as the best enzyme for D-AlaNH 2 production, exhibited an optimal activity at pH 9.0 and 40 °C for D-AlaNH 2 production. The apparent K m values of this variant for D-Ala and NH 3 were 7.35 mM and 1.58 M, respectively. The S293E variant could catalyze the synthesis of 9.3 and 35.7 mM of D-AlaNH 2 from 10 and 50 mM D-Ala and 3 M NH 4 Cl with conversion yields of 93 and 71.4 %, respectively. This is the first report showing the enzymatic formation of amino acid amides from amino acids.

Biotic and abiotic controls on diurnal fluctuations in labile soil phosphorus of a wet tropical forest.

Science.gov (United States)

Vandecar, Karen L; Lawrence, Deborah; Wood, Tana; Oberbauer, Steven F; Das, Rishiraj; Tully, Katherine; Schwendenmann, Luitgard

2009-09-01

The productivity of many tropical wet forests is generally limited by bioavailable phosphorus (P). Microbial activity is a key regulator of P availability in that it determines both the supply of P through organic matter decomposition and the depletion of bioavailable P through microbial uptake. Both microbial uptake and mineralization occur rapidly, and their net effect on P availability varies with soil moisture, temperature, and soil organic matter quantity and quality. Exploring the mechanisms driving P availability at fine temporal scales can provide insight into the coupling of carbon, water, and nutrient cycles, and ultimately, the response of tropical forests to climate change. Despite the recognized importance of P cycling to the dynamics of wet tropical forests and their potential sensitivity to short-term fluctuations in bioavailable P, the diurnal pattern of P remains poorly understood. This study quantifies diurnal fluctuations in labile soil P and evaluates the importance of biotic and abiotic factors in driving these patterns. To this end, measurements of labile P were made every other hour in a Costa Rican wet tropical forest oxisol. Spatial and temporal variation in Bray-extractable P were investigated in relation to ecosystem carbon flux, soil CO2 efflux, soil moisture, soil temperature, solar radiation, and sap-flow velocity. Spatially averaged bi-hourly (every two hours) labile P ranged from 0.88 to 2.48 microg/g across days. The amplitude in labile P throughout the day was 0.61-0.82 microg/g (41-54% of mean P concentrations) and was characterized by a bimodal pattern with a decrease at midday. Labile P increased with soil CO2 efflux and soil temperature and declined with increasing sap flow and solar radiation. Together, soil CO2 efflux, soil temperature, and sap flow explained 86% of variation in labile P.

Coordination compounds of cobalt and cadmium with isobutyric acid amide

International Nuclear Information System (INIS)

Tsivadze, A.Yu.; Ivanova, I.S.; Solovkina, O.A.

1983-01-01

Coordination compounds of cobalt and cadmium with isobutyric acid amide (IBAA) of Co(NCS) 2 x(IBAA) 2 (H 2 O) 2 , CoCl 2 (IBAA) 4 , CoI 2 (IBAA) 8 (H 2 O) 2 , CdI 2 (IBAA) 2 composition have been synthesized and characterized. Their infrared absorption spectra (200-400 cm -1 ), electron reflection spectra (200-750 nm) were studied. It is shown that in all compounds there are IBAA molecUles coordinated through an oxygen atom. Thiocyanogroups are coordinated throUgh nitrogen atoms

Isolation and characterization of racemase from Ensifer sp. 23-3 that acts on α-aminolactams and α-amino acid amides.

Science.gov (United States)

Matsui, Daisuke; Fuhshuku, Ken-Ichi; Nagamori, Shingo; Takata, Momoko; Asano, Yasuhisa

2017-11-01

Limited information is available on α-amino-ε-caprolactam (ACL) racemase (ACLR), a pyridoxal 5'-phosphate-dependent enzyme that acts on ACL and α-amino acid amides. In the present study, eight bacterial strains with the ability to racemize α-amino-ε-caprolactam were isolated and one of them was identified as Ensifer sp. strain 23-3. The gene for ACLR from Ensifer sp. 23-3 was cloned and expressed in Escherichia coli. The recombinant ACLR was then purified to homogeneity from the E. coli transformant harboring the ACLR gene from Ensifer sp. 23-3, and its properties were characterized. This enzyme acted not only on ACL but also on α-amino-δ-valerolactam, α-amino-ω-octalactam, α-aminobutyric acid amide, and alanine amide.

Complexation efficiency of differently fixed 8-hydroxyquinoline and salicylic acid ligand groups for labile aluminium species determination in soils-comparison of two methods

International Nuclear Information System (INIS)

Matus, Peter; Kubova, Jana

2006-01-01

Two methods utilizing the complexation of labile Al species by 8-hydroxyquinoline (HQN) and salicylic acid (SA) ligand groups were developed for aluminium operationally defined fractionation in acid soils. First, the solid phase extraction (SPE) procedure by a short-term ion-exchange batch reaction with chelating resins Iontosorb Oxin and Iontosorb Salicyl containing both ligand groups was used previously. Second, the 8-hydroxyquinoline, salicylic acid and ammonium salicylate agents with different concentrations by a single extraction protocol were applied in this paper. The flame atomic absorption spectrometry (FAAS) and optical emission spectrometry with inductively coupled plasma were used for aluminium quantification. The comparison of results from both methods show the possibility to supersede the first laborious method for the second simpler one in Al environmental risk assessment. The use of 1% 8-hydroxyquinoline in 2% acetic acid and 0.2% salicylic acid by a single extraction protocol without a need of sample filtration can supersede the SPE procedure in the Al pollution soil monitoring. Finally, the new scheme usable in a laboratory and moreover, directly in a field was proposed for Al fractionation in solid and liquid environmental samples. The labile Al species in soils and sediments are separated after their single leaching by 8-hydroxyquinoline or salicylic acid without a need of sample filtration. The labile Al species in soil solutions and natural waters are separated after their ultrafiltration followed by the SPE procedure with Iontosorb Oxin or Iontosorb Salicyl

Selective rhodium-catalyzed reduction of tertiary amides in amino acid esters and peptides.

Science.gov (United States)

Das, Shoubhik; Li, Yuehui; Bornschein, Christoph; Pisiewicz, Sabine; Kiersch, Konstanze; Michalik, Dirk; Gallou, Fabrice; Junge, Kathrin; Beller, Matthias

2015-10-12

Efficient reduction of the tertiary amide bond in amino acid derivatives and peptides is described. Functional group selectivity has been achieved by applying a commercially available rhodium precursor and bis(diphenylphosphino)propane (dppp) ligand together with phenyl silane as a reductant. This methodology allows for specific reductive derivatization of biologically interesting peptides and offers straightforward access to a variety of novel peptide derivatives for chemical biology studies and potential pharmaceutical applications. The catalytic system tolerates a variety of functional groups including secondary amides, ester, nitrile, thiomethyl, and hydroxy groups. This convenient hydrosilylation reaction proceeds at ambient conditions and is operationally safe because no air-sensitive reagents or highly reactive metal hydrides are needed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Iterative O-Methyltransferase Catalyzes 1,11-Dimethylation of Aspergillus fumigatus Fumaric Acid Amides.

Science.gov (United States)

Kalb, Daniel; Heinekamp, Thorsten; Schieferdecker, Sebastian; Nett, Markus; Brakhage, Axel A; Hoffmeister, Dirk

2016-10-04

S-adenosyl-l-methionine (SAM)-dependent methyltransfer is a common biosynthetic strategy to modify natural products. We investigated the previously uncharacterized Aspergillus fumigatus methyltransferase FtpM, which is encoded next to the bimodular fumaric acid amide synthetase FtpA. Structure elucidation of two new A. fumigatus natural products, the 1,11-dimethyl esters of fumaryl-l-tyrosine and fumaryl-l-phenylalanine, together with ftpM gene disruption suggested that FtpM catalyzes iterative methylation. Final evidence that a single enzyme repeatedly acts on fumaric acid amides came from an in vitro biochemical investigation with recombinantly produced FtpM. Size-exclusion chromatography indicated that this methyltransferase is active as a dimer. As ftpA and ftpM homologues are found clustered in other fungi, we expect our work will help to identify and annotate natural product biosynthesis genes in various species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lipopolysaccharide-induced pulmonary inflammation is not accompanied by a release of anandamide into the lavage fluid or a down-regulation of the activity of fatty acid amide hydrolase

DEFF Research Database (Denmark)

Holt, S.; J. Fowler, C.; Rocksén, D.

2004-01-01

The effect of lipopolysaccharide inhalation upon lung anandamide levels, anandamide synthetic enzymes and fatty acid amide hydrolase has been investigated. Lipopolysaccharide exposure produced a dramatic extravasation of neutrophils and release of tumour necrosis factor a into the bronchoalveolar......-acyltransferase and N-acylphosphatidylethanolamine phospholipase D and the activity of fatty acid amide hydrolase in lung membrane fractions did not change significantly following the exposure to lipopolysaccharide. The non-selective fatty acid amide hydrolase inhibitor phenylmethylsulfonyl fluoride was a less potent...... inhibitor of lung fatty acid amide hydrolase than expected from the literature, and a dose of 30 mg/kg i.p. of this compound, which produced a complete inhibition of brain anandamide metabolism, only partially inhibited the lung metabolic activity....

Friedel-Crafts Acylation with Amides

Science.gov (United States)

Raja, Erum K.; DeSchepper, Daniel J.; Nilsson Lill, Sten O.; Klumpp, Douglas A.

2012-01-01

Friedel-Crafts acylation has been known since the 1870s and it is an important organic synthetic reaction leading to aromatic ketone products. Friedel-Crafts acylation is usually done with carboxylic acid chlorides or anhydrides while amides are generally not useful substrates in these reactions. Despite being the least reactive carboxylic acid derivative, we have found a series of amides capable of providing aromatic ketones in good yields (55–96%, 17 examples). We propose a mechanism involving diminished C-N resonance through superelectrophilic activation and subsequent cleavage to acyl cations. PMID:22690740

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

Science.gov (United States)

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

2015-01-21

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

Synthesis of antimalarial amide analogues based on the plant serrulatane diterpenoid 3,7,8-trihydroxyserrulat-14-en-19-oic acid.

Science.gov (United States)

Kumar, Rohitesh; Duffy, Sandra; Avery, Vicky M; Davis, Rohan A

2017-09-01

A plant-derived natural product scaffold, 3,7,8-trihydroxyserrulat-14-en-19-oic acid (1) was isolated in high yield from the aerial parts of the endemic Australian desert plant Eremophila microtheca. This scaffold (1) was subsequently used in the generation of a series of new amide analogues via a one-pot mixed anhydride amidation using pivaloyl chloride. The structures of all analogues were characterized using MS, NMR, and UV data. The major serrulatane natural products (1-3), isolated from the plant extract, and all amide analogues (6-15) together with several pivaloylated derivatives of 3,7,8-trihydroxyserrulat-14-en-19-oic acid (16-18) were evaluated for their antimalarial activity against 3D7 (chloroquine sensitive) and Dd2 (chloroquine resistant) Plasmodium falciparum strains, and preliminary cytotoxicity data were also acquired using the human embryonic kidney cell line HEK293. The natural product scaffold (1) did not display any antimalarial activity at 10µM. Replacing the carboxylic acid of 1 with various amides resulted in moderate activity against the P. falciparum 3D7 strain with IC 50 values ranging from 1.25 to 5.65µM. Copyright © 2017 Elsevier Ltd. All rights reserved.

Citral derived amides as potent bacterial NorA efflux pump inhibitors

DEFF Research Database (Denmark)

Thota, Niranjan; Koul, Surrinder; Reddy, Mallepally V

2008-01-01

Monoterpene citral and citronellal have been used as starting material for the preparation of 5,9-dimethyl-deca-2,4,8-trienoic acid amides and 9-formyl-5-methyl-deca-2,4,8-trienoic acid amides. The amides on bioevaluation as efflux pump inhibitors (EPIs) against Staphylococcus aureus 1199 and NorA...

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

Science.gov (United States)

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.

Electrical behavior of amide functionalized graphene oxide and graphene oxide films annealed at different temperatures

International Nuclear Information System (INIS)

Rani, Sumita; Kumar, Mukesh; Kumar, Dinesh; Sharma, Sumit

2015-01-01

Films of graphene oxide (GO) and amide functionalized graphene oxides (AGOs) were deposited on SiO 2 /Si(100) by spin coating and were thermally annealed at different temperatures. Sheet resistance of GO and AGOs films was measured using four probe resistivity method. GO an insulator at room temperature, exhibits decrease in sheet resistance with increase in annealing temperature. However, AGOs' low sheet resistance (250.43 Ω) at room temperature further decreases to 39.26 Ω after annealing at 800 °C. It was observed that the sheet resistance of GO was more than AGOs up to 700 °C, but effect was reversed after annealing at higher temperature. At higher annealing temperatures the oxygen functionality reduces in GO and sheet resistance decreases. Sheet resistance was found to be annealing time dependent. Longer duration of annealing at a particular temperature results in decrease of sheet resistance. - Highlights: • Amide functionalized graphene oxides (AGOs) were synthesized at room temperature (RT). • AGO films have low sheet resistance at RT as compared to graphene oxide (GO). • Fast decrease in the sheet resistance of GO with annealing as compared to AGOs • AGOs were found to be highly dispersible in polar solvents

Physiological control of the distribution of translocated amino acids and amides in young soybean plants

Energy Technology Data Exchange (ETDEWEB)

Nelson, C D; Gorham, P R

1959-01-01

Each of 10 C/sup 14/-labelled amino acids or amides was introduced into young soybean plants through the cut petiole of one primary leaf. The compounds used were asparagine, glutamine, urea, aspartic acid, glutamic acid, glycine, serine, alanine, norleucine, and arginine. The rates of uptake of all the solutions except arginine were in the range 1.0 to 1.5 ..mu..l per minute. After 1 to 5 minutes, the distribution of C/sup 14/ throughout the plants was determined. Each amino acid was translocated as such without conversion to other compounds. From the point of introduction, translocation of each amino acid or amide was mainly downward toward the root; very little was translocated upward. The amount of asparagine or glutamine that was translocated into the primary leaf opposite the cut petiole increased as the leaf aged, while the amount of the other eight compounds decreased as the leaf aged. When asparagine and serine were administered together, serine moved into the young primary leaf while asparagine was excluded. Both excision of the roots and chilling the roots decreased the velocity of downward translocation of aspartic acid indicating that the roots exert a strong demand which favors translocation in a downward direction more than an upward direction in the stem. 17 references, 1 figure, 5 tables.

Direct Enantioselective Conjugate Addition of Carboxylic Acids with Chiral Lithium Amides as Traceless Auxiliaries

Science.gov (United States)

2016-01-01

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

Direct methylation procedure for converting fatty amides to fatty acid methyl esters in feed and digesta samples.

Science.gov (United States)

Jenkins, T C; Thies, E J; Mosley, E E

2001-05-01

Two direct methylation procedures often used for the analysis of total fatty acids in biological samples were evaluated for their application to samples containing fatty amides. Methylation of 5 mg of oleamide (cis-9-octadecenamide) in a one-step (methanolic HCl for 2 h at 70 degrees C) or a two-step (sodium methoxide for 10 min at 50 degrees C followed by methanolic HCl for 10 min at 80 degrees C) procedure gave 59 and 16% conversions of oleamide to oleic acid, respectively. Oleic acid recovery from oleamide was increased to 100% when the incubation in methanolic HCl was lengthened to 16 h and increased to 103% when the incubation in methoxide was modified to 24 h at 100 degrees C. However, conversion of oleamide to oleic acid in an animal feed sample was incomplete for the modified (24 h) two-step procedure but complete for the modified (16 h) one-step procedure. Unsaturated fatty amides in feed and digesta samples can be converted to fatty acid methyl esters by incubation in methanolic HCl if the time of exposure to the acid catalyst is extended from 2 to 16 h.

Coordination compounds of cobalt and cadmium with isobutyric acid amide

Energy Technology Data Exchange (ETDEWEB)

Tsivadze, A.Yu.; Ivanova, I.S.; Solovkina, O.A. (AN SSSR, Moscow. Inst. Obshchej i Neorganicheskoj Khimii)

1983-06-01

Coordination compounds of cobalt and cadmium with isobutyric acid amide (IBAA) of Co(NCS)/sub 2/x(IBAA)/sub 2/(H/sub 2/O)/sub 2/, CoCl/sub 2/(IBAA)/sub 4/, CoI/sub 2/(IBAA)/sub 8/(H/sub 2/O)/sub 2/, CdI/sub 2/(IBAA)/sub 2/ composition have been synthesized and characterized. Their infrared absorption spectra (200-400 cm/sup -1/), electron reflection spectra (200-750 nm) were studied. It is shown that in all compounds there are IBAA molecUles coordinated through an oxygen atom. Thiocyanogroups are coordinated through nitrogen atoms.

Photochemical reduction of uranyl ion with amides

International Nuclear Information System (INIS)

Brar, A.S.; Chander, R.; Sandhu, S.S.

1981-01-01

The photochemical reduction of uranyl ion by formamide, acetamide, propionamide, butyramide, iso butyramids, n-methylformamide, N, N-dimethylformamide and N, N-diethylformamide in aqueous medium using radiation >= 380 nm from a medium pressure mercury vapour lamp has been investigated. The reduction with the said amides has been found to obey pseudo first order kinetics. The magnitude of the rate of reduction for the simple amides has been found to follow the following order formamide > isobutyramide approx. butyramide > propionamide > acetamide while the rate order for N-alkylformamides compared with that of the formamide has been found to be formamide > N-methylformamide > N,N-diethylformamide approx. N,N-dimethylformamide. The pseudo first order rate constants and quenching constants have been found from the kinetic data. It has been found that physical and chemical quenching compete with each other. Plots of reciprocal of quantum yields versus reciprocal [amide] have been found to be linear with intercepts on the ordinate axis. Absorption spectra of uranyl ion in doubly distilled water, in the presence of acid and in the presence of acid and amide reveal that there is no ground state interaction between uranyl ion and the amide. A mechanism of photoreduction of uranyl ion with amides has been proposed. (author)

Maximized PUFA measurements improve insight in changes in fatty acid composition in response to temperature

NARCIS (Netherlands)

Van Dooremalen, C.; Pel, R.; Ellers, J.

2009-01-01

A general mechanism underlying the response of ectotherms to environmental changes often involves changes in fatty acid composition. Theory predicts that a decrease in temperature causes an increase in unsaturation of fatty acids, with an important role for long-chain poly-unsaturated fatty acids

Maximized PUFA measurements improve insight in changes in fatty acid composition in response to temperature.

NARCIS (Netherlands)

van Dooremalen, J.A.; Pel, R.; Ellers, J.

2009-01-01

A general mechanism underlying the response of ectotherms to environmental changes often involves changes in fatty acid composition. Theory predicts that a decrease in temperature causes an increase in unsaturation of fatty acids, with an important role for long-chain poly-unsaturated fatty acids

Investigation of the complex reaction coordinate of acid catalyzed amide hydrolysis from molecular dynamics simulations

International Nuclear Information System (INIS)

Zahn, Dirk

2004-01-01

The rate-determining step of acid catalyzed peptide hydrolysis is the nucleophilic attack of a water molecule to the carbon atom of the amide group. Therein the addition of the hydroxyl group to the amide carbon atom involves the association of a water molecule transferring one of its protons to an adjacent water molecule. The protonation of the amide nitrogen atom follows as a separate reaction step. Since the nucleophilic attack involves the breaking and formation of several bonds, the underlying reaction coordinate is rather complex. We investigate this reaction step from path sampling Car-Parrinello molecular dynamics simulations. This approach does not require the predefinition of reaction coordinates and is thus particularly suited for investigating reaction mechanisms. From our simulations the most relevant components of the reaction coordinate are elaborated. Though the C···O distance of the oxygen atom of the water molecule performing the nucleophilic attack and the corresponding amide carbon atom is a descriptor of the reaction progress, a complete picture of the reaction coordinate must include all three molecules taking part in the reaction. Moreover, the proton transfer is found to depend on favorable solvent configurations. Thus, also the arrangement of non-reacting, i.e. solvent water molecules needs to be considered in the reaction coordinate

An Efficient Amide-Aldehyde-Alkene Condensation: Synthesis for the N-Allyl Amides.

Science.gov (United States)

Quan, Zheng-Jun; Wang, Xi-Cun

2016-02-01

The allylamine skeleton represents a significant class of biologically active nitrogen compounds that are found in various natural products and drugs with well-recognized pharmacological properties. In this personal account, we will briefly discuss the synthesis of allylamine skeletons. We will focus on showing a general protocol for Lewis acid-catalyzed N-allylation of electron-poor N-heterocyclic amides and sulfonamide via an amide-aldehyde-alkene condensation reaction. The substrate scope with respect to N-heterocyclic amides, aldehydes, and alkenes will be discussed. This method is also capable of preparing the Naftifine motif from N-methyl-1-naphthamide or methyl (naphthalene-1-ylmethyl)carbamate, with paraformaldehyde and styrene in a one-pot manner. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The acid-labile subunit of human ternary insulin-like growth factor binding protein complex in serum

DEFF Research Database (Denmark)

Juul, A; Møller, S; Mosfeldt-Laursen, E

1998-01-01

Circulating insulin-like growth factor-I (IGF-I) is predominantly bound in the trimeric complex comprised of IGF binding protein-3 (IGFBP-3) and acid-labile subunit (ALS). Circulating concentrations of IGF-I, IGFBP-3 and ALS are believed to reflect the GH secretory status, but the clinical use...... of ALS determination is not known. We therefore, determined the: 1) hepatosplanchnic release of ALS by liver vein catheterization (n=30); 2) 24-h diurnal variation of ALS (n=8); 3) normal age-related ranges of circulating ALS (n=1158); 4) diagnostic value of ALS in 108 patients with childhood-onset GH...... in adults; and 4) ALS levels were below -2 SD in 57 of 79 GHD patients (sensitivity 72%) and above 2 SD in 22 of 29 patients with normal GH response (specificity 76%), which was similar, compared with the diagnostic utility of IGF-I and IGFBP-3. Finally, our findings indicate that hepatic ALS production...

The Synthesis of Backbone Thermo and pH Responsive Hyperbranched Poly(Bis(N,N-Propyl Acryl Amides by RAFT

Directory of Open Access Journals (Sweden)

Shijiao Zhou

2016-04-01

Full Text Available Hyperbranched poly(methylene-bis-acrylamide, poly(bis(N,N-propyl acryl amide (HPNPAM and poly(bis(N,N-butyl acryl amide were synthesized by reversible addition-fragmentation chain transfer polymerization. HPNPAMs showed lower critical solution temperature (LCST due to an appropriate ratio between hydrophilic and hydrophobic groups. The effects of reaction conditions on polymerization were investigated in detail. The structure of HPNPAM was characterized by 1H NMR, FT-IR, Muti detector-size exclusion chromatography (MDSEC and Ultravioletvisble (UV-Vis. The α value reached 0.20 and DB was 90%, indicating HPNPAMs with compact topology structure were successfully prepared. LCSTs were tuned by Mw and the pH value of the solution. The change of molecular size was assayed by dynamic light scattering and scanning electron microscope. These results indicated that the stable uniform nanomicelles were destroyed and macromolecules aggregated together, forming large particles as temperature exceeded LCST. In addition, after the cells were incubated for 24 h, the cell viability reached 80%, which confirmed this new dual responsive HPNPAM had low cytotoxicity.

Picolyl amides of betulinic acid as antitumor agents causing tumor cell apoptosis.

Science.gov (United States)

Bildziukevich, Uladzimir; Rárová, Lucie; Šaman, David; Wimmer, Zdeněk

2018-02-10

A series of picolyl amides of betulinic acid (3a-3c and 6a-6c) was prepared and subjected to the cytotoxicity screening tests. Structure-activity relationships studies resulted in finding differences in biological activity in dependence on o-, m- and p-substitution of the pyridine ring in the target amides, when cytotoxicity data of 3a-3c and 6a-6c were obtained and compared. The amides 3b and 3a displayed cytotoxicity (given in the IC 50 values) in G-361 (0.5 ± 0.1 μM and 2.4 ± 0.0 μM, respectively), MCF7 (1.4 ± 0.1 μM and 2.2 ± 0.2 μM, respectively), HeLa (2.4 ± 0.4 μM and 2.3 ± 0.5 μM, respectively) and CEM (6.5 ± 1.5 μM and 6.9 ± 0.4 μM, respectively) tumor cell lines, and showed weak effect in the normal human fibroblasts (BJ). Selectivity against all tested cancer cells was determined and compared to normal cells with therapeutic index (TI) between 7 and 100 for compounds 3a and 3b. The therapeutic index (TI = 100) was calculated for human malignant melanoma cell line (G-361) versus normal human fibroblasts (BJ). The cytotoxicity of other target amides (3c and 6a-6c) revealed lower effects than 3a and 3b in the tested cancer cell lines. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Frozen Chirality of Tertiary Aromatic Amides: Access to Enantioenriched Tertiary α-Amino Acid or Amino Alcohol without Chiral Reagent.

Science.gov (United States)

Mai, Thi Thoa; Viswambharan, Baby; Gori, Didier; Guillot, Régis; Naubron, Jean-Valère; Kouklovsky, Cyrille; Alezra, Valérie

2017-04-27

One of the fundamental and intriguing aspects of life is the homochirality of the essential molecules. In this field, the absolute asymmetric synthesis of α-amino acids is a major challenge. Herein, we report access, by chemical means, to tertiary α-amino acid derivatives in up to 96 % ee without using any chiral reagent. In our strategy, the dynamic axial chirality of tertiary aromatic amides is frozen in a crystal and is responsible for the stereoselectivity of the subsequent steps. Furthermore, we could control the configuration of the final product by manually sorting and selecting the initial crystals. Based on vibrational circular dichroism studies, we could rationalize the observed stereoselectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transient acidosis while retrieving a fear-related memory enhances its lability

Science.gov (United States)

Du, Jianyang; Price, Margaret P; Taugher, Rebecca J; Grigsby, Daniel; Ash, Jamison J; Stark, Austin C; Hossain Saad, Md Zubayer; Singh, Kritika; Mandal, Juthika; Wemmie, John A; Welsh, Michael J

2017-01-01

Attenuating the strength of fearful memories could benefit people disabled by memories of past trauma. Pavlovian conditioning experiments indicate that a retrieval cue can return a conditioned aversive memory to a labile state. However, means to enhance retrieval and render a memory more labile are unknown. We hypothesized that augmenting synaptic signaling during retrieval would increase memory lability. To enhance synaptic transmission, mice inhaled CO2 to induce an acidosis and activate acid sensing ion channels. Transient acidification increased the retrieval-induced lability of an aversive memory. The labile memory could then be weakened by an extinction protocol or strengthened by reconditioning. Coupling CO2 inhalation to retrieval increased activation of amygdala neurons bearing the memory trace and increased the synaptic exchange from Ca2+-impermeable to Ca2+-permeable AMPA receptors. The results suggest that transient acidosis during retrieval renders the memory of an aversive event more labile and suggest a strategy to modify debilitating memories. DOI: http://dx.doi.org/10.7554/eLife.22564.001 PMID:28650315

Application of cyanuric chloride-based six new chiral derivatizing reagents having amino acids and amino acid amides as chiral auxiliaries for enantioresolution of proteinogenic amino acids by reversed-phase high-performance liquid chromatography.

Science.gov (United States)

Bhushan, Ravi; Dixit, Shuchi

2012-04-01

Six dichloro-s-triazine (DCT) reagents having L-Leu, D-Phg, L-Val, L-Met, L-Ala and L-Met-NH(2) as chiral auxiliaries in cyanuric chloride were introduced for enantioseparation of 13 proteinogenic amino acids. Four other DCTs and six monochloro-s-triazine (MCT) reagents having amino acid amides as chiral auxiliaries were also synthesized. These 16 chiral derivatizing reagents (CDRs) were used for synthesis of diastereomers of all the 13 analytes using microwave irradiation, which were resolved by reversed-phase high-performance liquid chromatography (RP-HPLC) using C18 column and gradient eluting mixture of aqueous TFA and acetonitrile with UV detection at 230 nm. It required only 60-90 s for derivatization using microwave irradiation. Better resolution and lower retention times were observed for the diastereomers prepared with CDRs having amino acids as chiral auxiliaries as compared to counterparts prepared with reagents having amino acid amides as chiral auxiliaries. As the best resolution of all the 13 analytes was observed for their diastereomers prepared using the DCT reagent having L-Leu as chiral auxiliary, this CDR was further employed for derivatization of Lys, Tyr, His and Arg followed by RP-HPLC analysis of resulting diastereomers. The results are discussed in light of acid and amide groups of chiral auxiliaries constituting CDRs, electronegativities of the atoms of achiral moieties constituting CDRs and hydrophobicities of side chains of amino acids constituting CDRs and analytes.

Picosecond thermometer in the amide I band of myoglobin

DEFF Research Database (Denmark)

Austin, R.H.; Xie, A.; Meer, L. van der

2005-01-01

The amide I and II bands in myoglobin show a heterogeneous temperature dependence, with bands at 6.17 and 6.43 mu m which are more intense at low temperatures. The amide I band temperature dependence is on the long wavelength edge of the band, while the short wavelength side has almost...... can be used to determine the time it takes vibrational energy to flow into the hydration shell. We determine that vibrational energy flow to the hydration shell from the amide I takes approximately 20 ps to occur....

2-Phenyl-tetrahydropyrimidine-4(1H-ones – cyclic benzaldehyde aminals as precursors for functionalised β2-amino acids

Directory of Open Access Journals (Sweden)

Markus Nahrwold

2009-09-01

Full Text Available Novel procedures have been developed to condense benzaldehyde effectively with β-amino acid amides to cyclic benzyl aminals. Double carbamate protection of the heterocycle resulted in fully protected chiral β-alanine derivatives. These serve as universal precursors for the asymmetric synthesis of functionalised β2-amino acids containing acid-labile protected side chains. Diastereoselective alkylation of the tetrahydropyrimidinone is followed by a chemoselective two step degradation of the heterocycle to release the free β2-amino acid. In the course of this study, an L-asparagine derivative was condensed with benzaldehyde and subsequently converted to orthogonally protected (R-β2-homoaspartate.

Shear and dielectric responses of propylene carbonate, tripropylene glycol, and a mixture of two secondary amides

DEFF Research Database (Denmark)

Gainaru, Catalin; Hecksher, Tina; Olsen, Niels Boye

2012-01-01

Propylene carbonate and a mixture of two secondary amides, N-ethylformamide and Nethylacetamide, are investigated by means of broadband dielectric and mechanical shear spectroscopy. The similarities between the rheological and the dielectric responses of these liquids and of the previously invest...... in the secondary amides. In addition, the predictions of the shoving model are confirmed for the investigated liquids...

Metal-Free N-Arylation of Secondary Amides at Room Temperature

OpenAIRE

Tinnis, Fredrik; Stridfeldt, Elin; Lundberg, Helena; Adolfsson, Hans; Olofsson, Berit

2015-01-01

The arylation of secondary acyclic amides has been achieved with diaryliodonium salts under mild and metal-free conditions. The methodology has a wide scope, allows synthesis of tertiary amides with highly congested aryl moieties, and avoids the regioselectivity problems observed in reactions with (diacetoxyiodo)benzene.

Synthesis and uses of the amides extractants

International Nuclear Information System (INIS)

Musikas, C.

1989-01-01

Carboxylic acids amides (RR'NCOCR''), malonic acid amides (RR'NCOCH 2 CONRR') and substituted malonic acid amides (RR'NCOCHR'' CONRR') are extractants of the actinides ions. They show good prospects for use in the nuclear industry because of their complete incinerability. In addition, their degradation products interfer much more less in the separation processes when compared with organophosphorus extractants. The synthesis and the purification of two typical extractants: N-N-di (2-ethylhexyl) butyramide (C 4 H 9 CHC 2 H 5 CH 2 ) 2 NCOC 3 H 7 and N,N'-dimethyl N,N'-dibutyl 1.3 diamide 2(3-oxa)nonyl propane (C 4 H 9 CH 3 NCO) 2 CHC 2 H 4 OC 6 H 13 are described. The purities, checked by NMR, elemental analysis and potentiometry, were in the range 98 to 99.5%. The yields for monoamides were in the range 70 to 90% and for the diamides 20 to 40%. 3 figs, 3 tabs, 10 refs

Monoamine Oxidase Inhibitory Activity of Ferulic Acid Amides: Curcumin-Based Design and Synthesis.

Science.gov (United States)

Badavath, Vishnu N; Baysal, İpek; Uçar, Gülberk; Mondal, Susanta K; Sinha, Barij N; Jayaprakash, Venkatesan

2016-01-01

Ferulic acid has structural similarity with curcumin which is being reported for its monoamine oxidase (MAO) inhibitory activity. Based on this similarity, we designed a series of ferulic acid amides 6a-m and tested for their inhibitory activity on human MAO (hMAO) isoforms. All the compounds were found to inhibit the hMAO isoforms either selectively or non-selectively. Nine compounds (6a, 6b, 6g-m) were found to inhibit hMAO-B selectively, whereas the other four (6c-f) were found to be non-selective. There is a gradual shift from hMAO-B selectivity (6a,b) to non-selectivity (6c-f) as there is an increase in chain length at the amino terminus. In case of compounds having an aromatic nucleus at the amino terminus, increasing the carbon number between N and the aromatic ring increases the potency as well as selectivity toward hMAO-B. Compounds 6f, 6j, and 6k were subjected to membrane permeability and metabolic stability studies by in vitro assay methods. They were found to have a better pharmacokinetic profile than curcumin, ferulic acid, and selegiline. In order to understand the structural features responsible for the potency and selectivity of 6k, we carried out a molecular docking simulation study. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Construction of hierarchically porous metal-organic frameworks through linker labilization

Science.gov (United States)

Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; Li, Jialuo; Huang, Lan; Feng, Liang; Wang, Xuan; Bosch, Mathieu; Alsalme, Ali; Cagin, Tahir; Zhou, Hong-Cai

2017-05-01

A major goal of metal-organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.

Biological activity of some novel synthesized 2-(4-methylbenzenesulphonamidopentanedioic acid bis amide derivatives: In vitro and in vivo antineoplastic activity

Directory of Open Access Journals (Sweden)

Satyajit Dutta

2014-12-01

Full Text Available In the present work few novel 2-(4-methylbenzenesulphonamidopentanedioic acid bis amide derivatives and the basic compound 2-(4-methylphenylsulfonamidopentanedioic acid have been synthesized, characterized and screened for their possible antineoplastic activity both in vitro and in vivo. The in vitro activity was performed against five human cell lines like human breast cancer (MCF-7, leukemia (K-562, ovarian cancer (OVACAR-3, human colon adenocarcinoma (HT-29 and Human kidney carcinoma (A-498. The in vivo activity was performed in female swiss albino mice against Ehrlich ascites carcinoma (EAC. Among the synthesized compounds, ureide, anilide, p-nitoanilide and o-bromoanilide derivatives of 2-(4-methyl benzene sulphonyl-pentanedioic acid bis amides showed encouraging activity in both the in vitro and in vivo compared to other compounds.

Fatty Acid Amide Hydrolase (FAAH) Inhibition Enhances Memory Acquisition through Activation of PPAR-alpha Nuclear Receptors

Science.gov (United States)

Mazzola, Carmen; Medalie, Julie; Scherma, Maria; Panlilio, Leigh V.; Solinas, Marcello; Tanda, Gianluigi; Drago, Filippo; Cadet, Jean Lud; Goldberg, Steven R.; Yasar, Sevil

2009-01-01

Inhibitors of fatty acid amide hydrolase (FAAH) increase endogenous levels of anandamide (a cannabinoid CB[subscript 1]-receptor ligand) and oleoylethanolamide and palmitoylethanolamide (OEA and PEA, ligands for alpha-type peroxisome proliferator-activated nuclear receptors, PPAR-alpha) when and where they are naturally released in the brain.…

Polyimides Containing Amide And Perfluoroisopropyl Links

Science.gov (United States)

Dezem, James F.

1993-01-01

New polyimides synthesized from reactions of aromatic hexafluoroisopropyl dianhydrides with asymmetric amide diamines. Soluble to extent of at least 10 percent by weight at temperature of about 25 degrees C in common amide solvents such as N-methylpyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Polyimides form tough, flexible films, coatings, and moldings. Glass-transition temperatures ranged from 300 to 365 degrees C, and crystalline melting temperatures observed between 543 and 603 degrees C. Display excellent physical, chemical, and electrical properties. Useful as adhesives, laminating resins, fibers, coatings for electrical and decorative purposes, films, wire enamels, and molding compounds.

Simple method for preparation of secondary amides of phosphorylacetic acids and their use for actinide extraction and sorption from nitric acid solutions

International Nuclear Information System (INIS)

Artyushin, O.I.; Sharova, E.V.; Odinets, I.L.; Lenevich, S.V.; Mastruykova, T.A.; Morgalyuk, V.P.; Tananaev, I.G.; Pribylova, G.V.; Myasoedova, G.V.; Myasoedov, B.F.

2004-01-01

An effective method of synthesis of secondary alkylamides of phosphorylacetic acids (APA), based on amidation of ethyl esters of phosphorylacetic acids with primary aliphatic amines, was developed. Extraction of americium(III) complexes with APA solutions in dichloroethane and uranium(VI) sorption by sorbents with non-covalently fixed APA from nitric acid solutions were studied. In the course of americium(III) extraction there is no correlation between Am III distribution factor and APA structure, whereas during uranium(VI) sorption a dependence of U VI extraction degree on the complexing agent structure is observed [ru

Inhibition of Procarcinogen Activating Enzyme CYP1A2 Activity and Free Radical Formation by Caffeic Acid and its Amide Analogues.

Science.gov (United States)

Narongchai, Paitoon; Niwatananun, Kanokporn; Narongchai, Siripun; Kusirisin, Winthana; Jaikang, Churdsak

2016-01-01

Caffeic acid (CAF) and its amide analogues, ethyl 1-(3',4'-dihydroxyphenyl) propen amide (EDPA), phenethyl 1-(3',4'-dihydroxyphenyl) propen amide (PEDPA), phenmethyl 1- (3',4'-dihydroxyphenyl) propen amide (PMDPA) and octyl 1-(3',4'-dihydroxyphenyl) propen amide (ODPA) were investigated for the inhibition of procarcinogen activating enzyme. CYP1A2 and scavenging activity on formation of nitric oxide, superoxide anion, DPPH radical and hydroxyl radical. It was found that they inhibited CYP1A2 enzyme by uncompetitive inhibition. Apparent Ki values of CAF, EDPA, PEDPA, PMDPA and ODPA were 0.59, 0.39, 0.45, 0.75 and 0.80 µM, respectively suggesting potent inhibitors of CYP1A2. Moreover, they potentially scavenged nitric oxide radical with IC 50 values of 0.12, 0.22, 0.28, 0.22 and 0.51 mM, respectively. The IC50 values of superoxide anion scavenging were 0.20, 0.22, 0.44, 2.18 and 2.50 mM, respectively. 1, 1- diphenyl-2- picrylhydrazyl (DPPH) radical-scavenging ability, shown as IC50 values, were 0.41, 0.29, 0.30, 0.89 and 0.84 mM, respectively. Moreover, the hydroxyl radical scavenging in vitro model was shown as IC50 values of 23.22, 21.06, 17.10, 17.21 and 15.81 µM, respectively. From our results, caffeic acid and its amide analogues are in vitro inhibitors of human CYP1A2 catalytic activity and free radical formation. They may be useful to be developed as potential chemopreventive agents that block CYP1A2-mediated chemical carcinogenesis.

Fatty acid amide hydrolase (FAAH) regulates hypercapnia/ischemia-induced increases in n-acylethanolamines in mouse brain.

Science.gov (United States)

Lin, Lin; Metherel, Adam H; Jones, Peter J; Bazinet, Richard P

2017-09-01

N-acylethanolamines (NAEs) are endogenous lipid ligands for several receptors including cannabinoid receptors and peroxisome proliferator-activated receptor-alpha (PPAR-α), which regulate numerous physiological functions. Fatty acid amide hydrolase (FAAH) is largely responsible for the degradation of NAEs. However, at high concentrations of ethanolamines and unesterified fatty acids, FAAH can also catalyze the reverse reaction, producing NAEs. Several brain insults such as ischemia and hypoxia increase brain unesterified fatty acids. Because FAAH can catalyze the synthesis of NAE, we aimed to test whether FAAH was necessary for CO 2 -induced hypercapnia/ischemia increases in NAE. To test this, we examined levels of NAEs, 1- and 2-arachidonoylglycerols as well as their corresponding fatty acid precursors in wild-type and mice lacking FAAH (FAAH-KO) with three Kill methods: (i) head-focused, high-energy microwave irradiation (microwave), (ii) 5 min CO 2 followed by microwave irradiation (CO 2 + microwave), and (iii) 5 min CO 2 only (CO 2 ). Both CO 2 -induced groups increased, to a similar extent, brain levels of unesterified oleic, arachidonic, and docosahexaenoic acid and 1- and 2-arachidonoylglycerols compared to the microwave group in both wild-type and FAAH-KO mice. Oleoylethanolamide (OEA), arachidonoylethanolamide (AEA), and docosahexaenoylethanolamide (DHEA) levels were about 8-, 7-, and 2.5-fold higher, respectively, in the FAAH-KO mice compared with the wild-type mice. Interestingly, the concentrations of OEA, AEA, and DHEA increased 2.5- to 4-fold in response to both CO 2 -induced groups in wild-type mice, but DHEA increased only in the CO 2 group in FAAH-KO mice. Our study demonstrates that FAAH is necessary for CO 2 - induced increases in OEA and AEA but not DHEA. Targeting brain FAAH could impair the production of NAEs in response to brain injuries. © 2017 International Society for Neurochemistry.

The acid-labile subunit of the ternary insulin-like growth factor complex in cirrhosis: relation to liver dysfunction

DEFF Research Database (Denmark)

Møller, S; Juul, A; Becker, U

2000-01-01

BACKGROUND/AIMS: In the circulation, insulin-like growth factor-I (IGF-I) is bound in a trimeric complex of 150 kDa with IGF binding protein-3 (IGFBP-3) and the acid-labile subunit (ALS). Whereas circulating IGF-I and IGFBP-3 are reported to be low in patients with chronic liver failure, the leve...... with significant relations to liver dysfunction and other components of the IGF complex. A small hepatic extraction was found in controls, which suggests extrahepatic production of ALS. Future studies should focus on organ-specific removal of ALS.......BACKGROUND/AIMS: In the circulation, insulin-like growth factor-I (IGF-I) is bound in a trimeric complex of 150 kDa with IGF binding protein-3 (IGFBP-3) and the acid-labile subunit (ALS). Whereas circulating IGF-I and IGFBP-3 are reported to be low in patients with chronic liver failure, the level...... of ALS has not been described in relation to hepatic dysfunction. The aim of the present study was therefore to measure circulating and hepatic venous concentrations of ALS in relation to hepatic function and the IGF axis. METHODS: Twenty-five patients with cirrhosis (Child class A/B/C:5/10/10) and 30...

Detection of a variable intracellular acid-labile carbon pool in Thalassiosira weissflogii (Heterokontophyta) and Emiliania huxleyi (Haptophyta) in response to changes in the seawater carbon system.

Science.gov (United States)

Isensee, Kirsten; Erez, Jonathan; Stoll, Heather M

2014-02-01

Accumulation of an intracellular pool of carbon (C(i) pool) is one strategy by which marine algae overcome the low abundance of dissolved CO2 (CO2 (aq) ) in modern seawater. To identify the environmental conditions under which algae accumulate an acid-labile C(i) pool, we applied a (14) C pulse-chase method, used originally in dinoflagellates, to two new classes of algae, coccolithophorids and diatoms. This method measures the carbon accumulation inside the cells without altering the medium carbon chemistry or culture cell density. We found that the diatom Thalassiosira weissflogii [(Grunow) G. Fryxell & Hasle] and a calcifying strain of the coccolithophorid Emiliania huxleyi [(Lohmann) W. W. Hay & H. P. Mohler] develop significant acid-labile C(i) pools. C(i) pools are measureable in cells cultured in media with 2-30 µmol l(-1) CO2 (aq), corresponding to a medium pH of 8.6-7.9. The absolute C(i) pool was greater for the larger celled diatoms. For both algal classes, the C(i) pool became a negligible contributor to photosynthesis once CO2 (aq) exceeded 30 µmol l(-1) . Combining the (14) C pulse-chase method and (14) C disequilibrium method enabled us to assess whether E. huxleyi and T. weissflogii exhibited thresholds for foregoing accumulation of DIC or reduced the reliance on bicarbonate uptake with increasing CO2 (aq) . We showed that the C(i) pool decreases with higher CO2 :HCO3 (-) uptake rates. © 2013 Scandinavian Plant Physiology Society.

Rapid Vortex Fluidics: Continuous Flow Synthesis of Amides and Local Anesthetic Lidocaine.

Science.gov (United States)

Britton, Joshua; Chalker, Justin M; Raston, Colin L

2015-07-20

Thin film flow chemistry using a vortex fluidic device (VFD) is effective in the scalable acylation of amines under shear, with the yields of the amides dramatically enhanced relative to traditional batch techniques. The optimized monophasic flow conditions are effective in ≤80 seconds at room temperature, enabling access to structurally diverse amides, functionalized amino acids and substituted ureas on multigram scales. Amide synthesis under flow was also extended to a total synthesis of local anesthetic lidocaine, with sequential reactions carried out in two serially linked VFD units. The synthesis could also be executed in a single VFD, in which the tandem reactions involve reagent delivery at different positions along the rapidly rotating tube with in situ solvent replacement, as a molecular assembly line process. This further highlights the versatility of the VFD in organic synthesis, as does the finding of a remarkably efficient debenzylation of p-methoxybenzyl amines. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CO2 Solubilities in Amide-based Brφnsted Acidic Ionic Liquids

International Nuclear Information System (INIS)

Palgunadi, Jelliarko; Im, Jin Kyu; Kang, Je Eun; Kim, Hoon Sik; Cheong, Min Serk

2010-01-01

A distinguished class of hydrophobic ionic liquids bearing a Brφnsted acidic character derived from amide-like compounds were prepared by a neutralization reaction of N,N-diethylformamide, N,N-dibutylformamide, 1-formylpiperidine, and ε-caprolactam with trifluoroacetic acid and physical absorptions of CO 2 in these ionic liquids were demonstrated and evaluated. CO 2 solubilities in these ionic liquids were influenced by the molecular structure of the cation and were apparently increased with the molar volume. Comparison based on a volume unit reveals that CO 2 solubilities in these liquids are relatively higher than those in imidazolium-based ionic liquids. Henry's coefficients calculated from low-pressure solubility tests at 313 to 333 K were used to derive the thermodynamics quantities. Enthalpy and entropy of solvation may share equal contributions in solubility

Polyunsaturated fatty acid amides from the Zanthoxylum genus - from culinary curiosities to probes for chemical biology.

Science.gov (United States)

Chruma, Jason J; Cullen, Douglas J; Bowman, Lydia; Toy, Patrick H

2018-01-25

Covering up to February 2017The pericarps of several species from the Zanthoxylum genus, a.k.a. the "prickly ash", have long been used for culinary purposes throughout Asia, most notably in the Sichuan (previously Szechuan) cuisine of Southwestern China, due to the unique tingling and numbing orosensations arising from a collection of polyunsaturated fatty acid amide (alkamide) constituents. The past decade has experienced dramatically increased academic and industrial interest in these pungent Zanthoxylum-derived alkamides, with a concomitant explosion in studies aimed at elucidating the specific biochemical mechanisms behind several medically-relevant biological activities exhibited by the natural products. This rapid increase in interest is partially fueled by advances in organic synthesis reported within the past few years that finally have allowed for the production of diastereomerically-pure Zanthoxylum alkamides and related analogs in multigram quantities. Herein is a comprehensive review of the discovery, total synthesis, and biological evaluation of Zanthoxylum-derived polyunsaturated fatty acid amides and synthetic analogues. Critical insights into how chemical synthesis can further benefit future chemical biology efforts in the field are also provided.

A sensitive and specific radiochromatographic assay of fatty acid amide hydrolase activity.

Science.gov (United States)

Maccarrone, M; Bari, M; Agrò, A F

1999-02-15

A radiochromatographic method has been set up in order to determine fatty acid amide hydrolase (FAAH) activity, based on reversed-phase high-performance liquid chromatography and on-line scintillation counting. The reaction products were separated using a C18 column eluted with methanol-water-acetic acid and quantitated with an external standard. Baseline separation of the acid product from the substrate was completed in less than 4 min, with a detection limit of 2.5 fmol arachidonic acid at a signal to noise ratio of 4:1. The method enabled to determine the kinetic constants (i.e., apparent Km of 2.0 +/- 0.2 microM and Vmax of 800 +/- 75 pmol. min-1. mg protein-1 toward anandamide) and the substrate specificity of human brain FAAH, as well as the extent of enzyme inhibition by some anandamide congeners. The femtomole sensitivity and the accuracy of the method allow detection and characterization of the activity of FAAH in very minute tissue samples or in samples where the enzymatic activity is very low. Copyright 1999 Academic Press.

Rational design and synthesis of an orally bioavailable peptide guided by NMR amide temperature coefficients

Science.gov (United States)

Wang, Conan K.; Northfield, Susan E.; Colless, Barbara; Chaousis, Stephanie; Hamernig, Ingrid; Lohman, Rink-Jan; Nielsen, Daniel S.; Schroeder, Christina I.; Liras, Spiros; Price, David A.; Fairlie, David P.; Craik, David J.

2014-01-01

Enhancing the oral bioavailability of peptide drug leads is a major challenge in drug design. As such, methods to address this challenge are highly sought after by the pharmaceutical industry. Here, we propose a strategy to identify appropriate amides for N-methylation using temperature coefficients measured by NMR to identify exposed amides in cyclic peptides. N-methylation effectively caps these amides, modifying the overall solvation properties of the peptides and making them more membrane permeable. The approach for identifying sites for N-methylation is a rapid alternative to the elucidation of 3D structures of peptide drug leads, which has been a commonly used structure-guided approach in the past. Five leucine-rich peptide scaffolds are reported with selectively designed N-methylated derivatives. In vitro membrane permeability was assessed by parallel artificial membrane permeability assay and Caco-2 assay. The most promising N-methylated peptide was then tested in vivo. Here we report a novel peptide (15), which displayed an oral bioavailability of 33% in a rat model, thus validating the design approach. We show that this approach can also be used to explain the notable increase in oral bioavailability of a somatostatin analog. PMID:25416591

Catalytic synthesis of amides via aldoximes rearrangement.

Science.gov (United States)

Crochet, Pascale; Cadierno, Victorio

2015-02-14

Amide bond formation reactions are among the most important transformations in organic chemistry because of the widespread occurrence of amides in pharmaceuticals, natural products and biologically active compounds. The Beckmann rearrangement is a well-known method to generate secondary amides from ketoximes. However, under the acidic conditions commonly employed, aldoximes RHC=NOH rarely rearrange into the corresponding primary amides RC(=O)NH2. In recent years, it was demonstrated that this atom-economical transformation can be carried out efficiently and selectively with the help of metal catalysts. Several homogeneous and heterogenous systems have been described. In addition, protocols offering the option to generate the aldoximes in situ from the corresponding aldehydes and hydroxylamine, or even from alcohols, have also been developed, as well as a series of tandem processes allowing the access to N-substituted amide products. In this Feature article a comprehensive overview of the advances achieved in this particular research area is presented.

Quantification and enzyme targets of fatty acid amides from duckweed root exudates involved in the stimulation of denitrification.

Science.gov (United States)

Sun, Li; Lu, Yufang; Kronzucker, Herbert J; Shi, Weiming

2016-07-01

Fatty acid amides from plant root exudates, such as oleamide and erucamide, have the ability to participate in strong plant-microbe interactions, stimulating nitrogen metabolism in rhizospheric bacteria. However, mechanisms of secretion of such fatty acid amides, and the nature of their stimulatory activities on microbial metabolism, have not been examined. In the present study, collection, pre-treatment, and determination methods of oleamide and erucamide in duckweed root exudates are compared. The detection limits of oleamide and erucamide by gas chromatography (GC) (10.3ngmL(-1) and 16.1ngmL(-1), respectively) are shown to be much lower than those by liquid chromatography (LC) (1.7 and 5.0μgmL(-1), respectively). Quantitative GC analysis yielded five times larger amounts of oleamide and erucamide in root exudates of Spirodela polyrrhiza when using a continuous collection method (50.20±4.32 and 76.79±13.92μgkg(-1) FW day(-1)), compared to static collection (10.88±0.66 and 15.27±0.58μgkg(-1) FW day(-1)). Furthermore, fatty acid amide secretion was significantly enhanced under elevated nitrogen conditions (>300mgL(-1)), and was negatively correlated with the relative growth rate of duckweed. Mechanistic assays were conducted to show that erucamide stimulates nitrogen removal by enhancing denitrification, targeting two key denitrifying enzymes, nitrate and nitrite reductases, in bacteria. Our findings significantly contribute to our understanding of the regulation of nitrogen dynamics by plant root exudates in natural ecosystems. Copyright © 2016 Elsevier GmbH. All rights reserved.

Discovery of novel N-(5-(arylcarbonyl)thiazol-2-yl)amides and N-(5-(arylcarbonyl)thiophen-2-yl)amides as potent RORγt inhibitors.

Science.gov (United States)

Wang, Yonghui; Cai, Wei; Zhang, Guifeng; Yang, Ting; Liu, Qian; Cheng, Yaobang; Zhou, Ling; Ma, Yingli; Cheng, Ziqiang; Lu, Sijie; Zhao, Yong-Gang; Zhang, Wei; Xiang, Zhijun; Wang, Shuai; Yang, Liuqing; Wu, Qianqian; Orband-Miller, Lisa A; Xu, Yan; Zhang, Jing; Gao, Ruina; Huxdorf, Melanie; Xiang, Jia-Ning; Zhong, Zhong; Elliott, John D; Leung, Stewart; Lin, Xichen

2014-01-15

Novel series of N-(5-(arylcarbonyl)thiazol-2-yl)amides and N-(5-(arylcarbonyl)thiophen-2-yl)amides were discovered as potent retinoic acid receptor-related orphan receptor-gamma-t (RORγt) inhibitors. SAR studies of the RORγt HTS hit 6a led to identification of thiazole ketone amide 8h and thiophene ketone amide 9g with high binding affinity and inhibitory activity of Th17 cell differentiation. Compound 8h showed in vivo efficacy in both mouse experimental autoimmune encephalomyelitis (EAE) and collagen induced arthritis (CIA) models via oral administration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Stability of Medium-Bridged Twisted Amides in Aqueous Solutions

Science.gov (United States)

Szostak, Michal; Yao, Lei; Aubé, Jeffrey

2012-01-01

“Twisted” amides containing non-standard dihedral angles are typically hypersensitive to hydrolysis, a feature that has stringently limited their utility in water. We have synthesized a series of bridged lactams that contain a twisted amide linkage but which exhibit enhanced stability in aqueous environments. Many of these compounds were extracted unchanged from aqueous mixtures ranging from the strongly basic to the strongly acidic. NMR experiments showed that tricyclic lactams undergo reversible hydrolysis at extreme pH ranges, but that a number of compounds in this structure class are indefinitely stable under physiologically relevant pH conditions; one bicyclic example was additionally water-soluble. We examined the effect of structure on the reversibility of amide bond hydrolysis, which we attributed to the transannular nature of the amino acid analogs. These data suggest that medium-bridged lactams of these types should provide useful platforms for studying the behavior of twisted amides in aqueous systems. PMID:19178141

Synthesis of novel naphthoquinone aliphatic amides and esters and their anticancer evaluation.

Science.gov (United States)

Kongkathip, Boonsong; Akkarasamiyo, Sunisa; Hasitapan, Komkrit; Sittikul, Pichamon; Boonyalai, Nonlawat; Kongkathip, Ngampong

2013-02-01

Fourteen new naphthoquinone aliphatic amides and seventeen naphthoquinone aliphatic esters were synthesized in nine to ten steps from 1-hydroxy-2-naphthoic acid with 9-25% overall yield for the amides, and 16-21% overall yield for the esters. The key step of the amide synthesis is a coupling reaction between amine and various aliphatic acids using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) as a coupling agent while for the ester synthesis, DCC/DMAP or CDI was used as the coupling reagent between aliphatic acids and naphthoquinone alcohol. Both naphthoquinone amides and esters were evaluated for their anticancer activity against KB cells. It was found that naphthoquinone aliphatic amides showed stronger anticancer activity than those of the esters when the chains are longer than 7-carbon atoms. The optimum chain of amides is expected to be 16-carbon atoms. In addition, naphthoquinone aliphatic esters with α-methyl on the ester moiety possessed much stronger anticancer activity than the straight chains. Decatenation assay revealed that naphthoquinone amide with 16-carbon atoms chain at 15 μM and 20 μM can completely inhibit hTopoIIα activity while at 10 μM the enzyme activity was moderately inhibited. Molecular docking result also showed the same trend as the cytotoxicity and decatenation assay. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

Influence of fast pyrolysis temperature on biochar labile fraction and short-term carbon loss in a loamy soil

International Nuclear Information System (INIS)

Bruun, Esben W.; Hauggaard-Nielsen, Henrik; Ibrahim, Norazana; Egsgaard, Helge; Ambus, Per; Jensen, Peter A.; Dam-Johansen, Kim

2011-01-01

Production of bio-oil, gas and biochar from pyrolysis of biomass is considered a promising technology for combined production of bioenergy and recalcitrant carbon (C) suitable for sequestration in soil. Using a fast pyrolysis centrifuge reactor (PCR) the present study investigated the relation between fast pyrolysis of wheat straw at different reactor temperatures and the short-term degradability of biochar in soil. After 115 days incubation 3-12% of the added biochar-C had been emitted as CO 2 . On average, 90% of the total biochar-C loss occurred within the first 20 days of the experiment, emphasizing the importance of knowing the biochar labile fraction when evaluating a specific biochars C sequestration potential. The pyrolysis temperature influenced the outputs of biochar, bio-oil and syngas significantly, as well as the stability of the biochar produced. Contrary to slow pyrolysis a fast pyrolysis process may result in incomplete conversion of biomass due to limitations to heat transfer and kinetics. In our case chemical analysis of the biochars revealed unconverted cellulosic and hemicellulosic fractions, which in turn were found to be proportional with the short-term biochar degradation in soil. As these labile carbohydrates are rapidly mineralized, their presence lowers the biochar-C sequestration potential. By raising the pyrolysis temperature, biochar with none or low contents of these fractions can be produced, but this will be on the expense of the biochar quantity. The yield of CO 2 neutral bio-oil is the other factor to optimize when adjusting the pyrolysis temperature settings to give the overall greatest climate change mitigation effect.

Rhodium(III)-Catalyzed Activation of C(sp3)-H Bonds and Subsequent Intermolecular Amidation at Room Temperature.

Science.gov (United States)

Huang, Xiaolei; Wang, Yan; Lan, Jingbo; You, Jingsong

2015-08-03

Disclosed herein is a Rh(III)-catalyzed chelation-assisted activation of unreactive C(sp3)-H bonds, thus enabling an intermolecular amidation to provide a practical and step-economic route to 2-(pyridin-2-yl)ethanamine derivatives. Substrates with other N-donor groups are also compatible with the amidation. This protocol proceeds at room temperature, has a relatively broad functional-group tolerance and high selectivity, and demonstrates the potential of rhodium(III) in the promotive functionalization of unreactive C(sp3)-H bonds. A rhodacycle having a SbF6(-) counterion was identified as a plausible intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Amide and Ester Derivatives of Cinnamic Acid and Its Analogs: Evaluation of Their Free Radical Scavenging and Monoamine Oxidase and Cholinesterase Inhibitory Activities.

Science.gov (United States)

Takao, Koichi; Toda, Kazuhiro; Saito, Takayuki; Sugita, Yoshiaki

2017-01-01

A series of cinnamic acid derivatives, amides (1-12) and esters (13-22), were synthesized, and structure-activity relationships for antioxidant activity, and monoamine oxidases (MAO) A and B, acetylcholinesterase, and butyrylcholinesterase (BChE) inhibitory activities were analyzed. Among the synthesized compounds, compounds 1-10, 12-18, and rosmarinic acid (23), which contained catechol, o-methoxyphenol or 5-hydroxyindole moieties, showed potent 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity. Compounds 9-11, 15, 17-22 showed potent and selective MAO-B inhibitory activity. Compound 20 was the most potent inhibitor of MAO-B. Compounds 18 and 21 showed moderate BChE inhibitory activity. In addition, compound 18 showed potent antioxidant activity and MAO-B inhibitory activity. In a comparison of the cinnamic acid amides and esters, the amides exhibited more potent DPPH free radical scavenging activity, while the esters showed stronger inhibitory activities against MAO-B and BChE. These results suggested that cinnamic acid derivatives such as compound 18, p-coumaric acid 3,4-dihydroxyphenethyl ester, and compound 20, p-coumaric acid phenethyl ester, may serve as lead compounds for the development of novel MAO-B inhibitors and candidate lead compounds for the prevention or treatment of Alzheimer's disease.

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

Science.gov (United States)

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…

Solvent Exchange Rates of Side-chain Amide Protons in Proteins

International Nuclear Information System (INIS)

Rajagopal, Ponni; Jones, Bryan E.; Klevit, Rachel E.

1998-01-01

Solvent exchange rates and temperature coefficients for Asn/Gln side-chain amide protons have been measured in Escherichia coli HPr. The protons of the eight side-chain amide groups (two Asn and six Gln) exhibit varying exchange rates which are slower than some of the fast exchanging backbone amide protons. Differences in exchange rates of the E and Z protons of the same side-chain amide group are obtained by measuring exchange rates at pH values > 8. An NOE between a side-chain amide proton and a bound water molecule was also observed

Microbial control of soil organic matter mineralization responses to labile carbon in subarctic climate change treatments

DEFF Research Database (Denmark)

Rousk, Kathrin; Michelsen, Anders; Rousk, Johannes

2016-01-01

Half the global soil carbon (C) is held in high-latitude systems. Climate change will expose these to warming and a shift towards plant communities with more labile C input. Labile C can also increase the rate of loss of native soil organic matter (SOM); a phenomenon termed ‘priming’. We investig......Half the global soil carbon (C) is held in high-latitude systems. Climate change will expose these to warming and a shift towards plant communities with more labile C input. Labile C can also increase the rate of loss of native soil organic matter (SOM); a phenomenon termed ‘priming’. We...

Porphyrin amino acids-amide coupling, redox and photophysical properties of bis(porphyrin) amides.

Science.gov (United States)

Melomedov, Jascha; Wünsche von Leupoldt, Anica; Meister, Michael; Laquai, Frédéric; Heinze, Katja

2013-07-14

New trans-AB2C meso-substituted porphyrin amino acid esters with meso-substituents of tunable electron withdrawing power (B = mesityl, 4-C6H4F, 4-C6H4CF3, C6F5) were prepared as free amines 3a-3d, as N-acetylated derivatives Ac-3a-Ac-3d and corresponding zinc(II) complexes Zn-Ac-3a-Zn-Ac-3d. Several amide-linked bis(porphyrins) with a tunable electron density at each porphyrin site were obtained from the amino porphyrin precursors by condensation reactions (4a-4d) and mono- and bis(zinc(II)) complexes Zn(2)-4d and Zn(1)Zn(2)-4d were prepared. The electronic interaction between individual porphyrin units in bis(porphyrins) 4 is probed by electrochemical experiments (CV, EPR), electronic absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy in combination with DFT/PCM calculations on diamagnetic neutral bis(porphyrins) 4 and on respective charged mixed-valent radicals 4(+/-). The interaction via the -C6H4-NHCO-C6H4- bridge, the site of oxidation and reduction and the lowest excited singlet state S1, is tuned by the substituents on the individual porphyrins and the metalation state.

Synthesis and evaluation of fatty acid amides on the N-oleoylethanolamide-like activation of peroxisome proliferator activated receptor α.

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Takao, Koichi; Noguchi, Kaori; Hashimoto, Yosuke; Shirahata, Akira; Sugita, Yoshiaki

2015-01-01

A series of fatty acid amides were synthesized and their peroxisome proliferator-activated receptor α (PPAR-α) agonistic activities were evaluated in a normal rat liver cell line, clone 9. The mRNAs of the PPAR-α downstream genes, carnitine-palmitoyltransferase-1 and mitochondrial 3-hydroxy-3-methylglutaryl-CoA synthase, were determined by real-time reverse transcription-polymerase chain reaction (RT-PCR) as PPAR-α agonistic activities. We prepared nine oleic acid amides. Their PPAR-α agonistic activities were, in decreasing order, N-oleoylhistamine (OLHA), N-oleoylglycine, Oleamide, N-oleoyltyramine, N-oleoylsertonin, and Olvanil. The highest activity was found with OLHA. We prepared and evaluated nine N-acylhistamines (N-acyl-HAs). Of these, OLHA, C16:0-HA, and C18:1Δ(9)-trans-HA showed similar activity. Activity due to the different chain length of the saturated fatty acid peaked at C16:0-HA. The PPAR-α antagonist, GW6471, inhibited the induction of the PPAR-α downstream genes by OLHA and N-oleoylethanolamide (OEA). These data suggest that N-acyl-HAs could be considered new PPAR-α agonists.

Design and Synthesis of Bis-amide and Hydrazide-containing Derivatives of Malonic Acid as Potential HIV-1 Integrase Inhibitors

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Nouri Neamati

2008-10-01

Full Text Available HIV-1 integrase (IN is an attractive and validated target for the development of novel therapeutics against AIDS. In the search for new IN inhibitors, we designed and synthesized three series of bis-amide and hydrazide-containing derivatives of malonic acid. We performed a docking study to investigate the potential interactions of the title compounds with essential amino acids on the IN active site.

Design, synthesis and optimization of bis-amide derivatives as CSF1R inhibitors.

Science.gov (United States)

Ramachandran, Sreekanth A; Jadhavar, Pradeep S; Miglani, Sandeep K; Singh, Manvendra P; Kalane, Deepak P; Agarwal, Anil K; Sathe, Balaji D; Mukherjee, Kakoli; Gupta, Ashu; Haldar, Srijan; Raja, Mohd; Singh, Siddhartha; Pham, Son M; Chakravarty, Sarvajit; Quinn, Kevin; Belmar, Sebastian; Alfaro, Ivan E; Higgs, Christopher; Bernales, Sebastian; Herrera, Francisco J; Rai, Roopa

2017-05-15

Signaling via the receptor tyrosine kinase CSF1R is thought to play an important role in recruitment and differentiation of tumor-associated macrophages (TAMs). TAMs play pro-tumorigenic roles, including the suppression of anti-tumor immune response, promotion of angiogenesis and tumor cell metastasis. Because of the role of this signaling pathway in the tumor microenvironment, several small molecule CSF1R kinase inhibitors are undergoing clinical evaluation for cancer therapy, either as a single agent or in combination with other cancer therapies, including immune checkpoint inhibitors. Herein we describe our lead optimization effort that resulted in the identification of a potent, cellular active and orally bioavailable bis-amide CSF1R inhibitor. Docking and biochemical analysis allowed the removal of a metabolically labile and poorly permeable methyl piperazine group from an early lead compound. Optimization led to improved metabolic stability and Caco2 permeability, which in turn resulted in good oral bioavailability in mice. Copyright © 2017 Elsevier Ltd. All rights reserved.

Amide Bond Formation Assisted by Vicinal Alkylthio Migration in Enaminones: Metal- and CO-Free Synthesis of α,β-Unsaturated Amides.

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Liu, Zhuqing; Huang, Fei; Wu, Ping; Wang, Quannan; Yu, Zhengkun

2018-05-18

Amide bond formation is one of the most important transformations in organic synthesis, drug development, and materials science. Efficient construction of amides has been among the most challenging tasks for organic chemists. Herein, we report a concise methodology for amide bond (-CONH-) formation assisted by vicinal group migration in alkylthio-functionalized enaminones (α-oxo ketene N, S-acetals) under mild conditions. Simple treatment of such enaminones with PhI(OAc) 2 at ambient temperature in air afforded diverse multiply functionalized α,β-unsaturated amides including β-cyclopropylated acrylamides, in which a wide array of functional groups such as aryl, (hetero)aryl, alkenyl, and alkyl can be conveniently introduced to a ketene moiety. The reaction mechanism was investigated by exploring the origins of the amide oxygen and carbon atoms as well as isolation and structural characterization of the reaction intermediates. The amide bond formation reactions could also be efficiently performed under solventless mechanical milling conditions.

Freshwater processing of terrestrial dissolved organic matter: What governs lability?

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D'Andrilli, J.; Smith, H. J.; Junker, J. R.; Scholl, E. A.; Foreman, C. M.

2016-12-01

Aquatic and terrestrial ecosystems are linked through the transfer of energy and materials. Allochthonous organic matter (OM) is central to freshwater ecosystem function, influencing local food webs, trophic state, and nutrient availability. In order to understand the nature and fate of OM from inland headwaters to the open ocean, it is imperative to understand the links between OM lability and ecosystem function. Thus, biological, chemical, and physical factors need to be evaluated together to inform our understanding of environmental lability. We performed a laboratory processing experiment on naturally occurring OM leachates from riparian leaves, grasses, and pine needles. Measures of water chemistry, OM optical and molecular characterization, bacterial abundances, microbial assemblage composition, respiration, and C:N:P were integrated to discern the nature and fate of labile and recalcitrant OM in a freshwater stream. Peak processing of all OM sources in the stream water occurred after two days, with spikes in bacterial cell abundances, respiration rates, microbial assemblage shifts, and maximum C utilization. Respiration rates and microbial assemblages were dependent on the degree of lability of the OM molecular composition. Within the first few days, no differences in respiration rates were observed between leachate sources, however, beyond day five, the rates diverged with C processing efficiency correlated with OM lability. Originally comprised of amino acid-like, labile fluorescent species, the inoculated stream water OM became more recalcitrant after 16 days, indicating humification processing over time. Our study highlights the importance of interdisciplinary approaches for understanding the processing and fate of OM in aquatic ecosystems.

Electrochemical reduction of nitrate in the presence of an amide

Science.gov (United States)

Dziewinski, Jacek J.; Marczak, Stanislaw

2002-01-01

The electrochemical reduction of nitrates in aqueous solutions thereof in the presence of amides to gaseous nitrogen (N.sub.2) is described. Generally, electrochemical reduction of NO.sub.3 proceeds stepwise, from NO.sub.3 to N.sub.2, and subsequently in several consecutive steps to ammonia (NH.sub.3) as a final product. Addition of at least one amide to the solution being electrolyzed suppresses ammonia generation, since suitable amides react with NO.sub.2 to generate N.sub.2. This permits nitrate reduction to gaseous nitrogen to proceed by electrolysis. Suitable amides include urea, sulfamic acid, formamide, and acetamide.

A novel nanoparticulate system for sustained delivery of acid-labile lansoprazole.

Science.gov (United States)

Alai, Milind Sadashiv; Lin, Wen Jen

2013-11-01

In the present study, an effort was made to develop the Eudragit RS100 based nanoparticulate system for sustained delivery of an acid-labile drug, lansoprazole (LPZ). LPZ-loaded Eudragit RS100 nanoparticles (ERSNPs) were prepared by oil-in-water emulsion-solvent evaporation method. The effects of various formulation variables such as polymer concentration, drug amount and solvent composition on physicochemical performance of nanoparticles and in vitro drug release were investigated. All nanoparticles were spherical with particle size 198.9 ± 8.6-376.9 ± 5.6 nm and zeta potential +35.1 ± 1.7 to +40.2 ± 0.8 mV. The yield of nanoparticles was unaffected by change of these three variables. However, the drug loading and encapsulation efficiency were affected by polymer concentration and drug amount. On the other hand, the particle size of nanoparticles was significantly affected by polymer concentration and internal phase composition due to influence of droplet size during emulsification process. All nanoparticles prolonged drug release for 24h which was dominated by a combination of drug diffusion and polymer chain relaxation. The fastest and the slowest release rates were observed in C2-1002-10/0 and C8-4001-10/0, respectively, based on the release rate constant (k). Thus, the developed nanoparticles possessed a potential as a nano-carrier to sustain drug delivery for treatment of acid related disorders. Copyright © 2013 Elsevier B.V. All rights reserved.

Redox regulation of protein tyrosine phosphatase 1B (PTP1B): Importance of steric and electronic effects on the unusual cyclization of the sulfenic acid intermediate to a sulfenyl amide

Science.gov (United States)

Sarma, Bani Kanta

2013-09-01

The redox regulation of protein tyrosine phosphatase 1B (PTP1B) via the unusual transformation of its sulfenic acid (PTP1B-SOH) to a cyclic sulfenyl amide intermediate is studied by using small molecule chemical models. These studies suggest that the sulfenic acids derived from the H2O2-mediated reactions o-amido thiophenols do not efficiently cyclize to sulfenyl amides and the sulfenic acids produced in situ can be trapped by using methyl iodide. Theoretical calculations suggest that the most stable conformer of such sulfenic acids are stabilized by nO → σ*S-OH orbital interactions, which force the -OH group to adopt a position trans to the S⋯O interaction, leading to an almost linear arrangement of the O⋯S-O moiety and this may be the reason for the slow cyclization of such sulfenic acids to their corresponding sulfenyl amides. On the other hand, additional substituents at the 6-position of o-amido phenylsulfenic acids that can induce steric environment and alter the electronic properties around the sulfenic acid moiety by S⋯N or S⋯O nonbonded interactions destabilize the sulfenic acids by inducing strain in the molecule. This may lead to efficient the cyclization of such sulfenic acids. This model study suggests that the amino acid residues in the close proximity of the sulfenic acid moiety in PTP1B may play an important role in the cyclization of PTP1B-SOH to produce the corresponding sulfenyl amide.

Labile and Non-labile Soil Carbon Fractions Equally Contributed to Carbon Changes under Long-term Fertilization

Science.gov (United States)

Liang, F.; Li, J.; Xu, M.; Huang, S.

2017-12-01

Soil organic carbon (SOC) storages are altered under long-term fertilization in croplands, it however remains unclear how fast- to slow-cycling SOC fractions each respond to fertilization practices. Based on five two-decade Chinese long-term fertilization experiments (GZL: Gongzhuling; ZZ: Zhengzhou; CQ: Chongqing; JX: Jinxian; QY: Qiyang) under three fertilization treatments (CK: cropping with no fertilizer input; NPK: chemical nitrogen, phosphorus and potassium fertilizers; and NPKM: NPK with manure input), we quantified very labile, labile, non-labile and total SOC stocks at 0-20cm soil depth. Results showed that SOC stocks varied among sites (GZL, JX, CQ > ZZ, QY) and generally increased with fertilizations (CK-1 at ZZ, GZL, QY, CQ and JX, respectively. The corresponding changes of the sum of very labile and labile SOC fractions were 2.6, 2.0, 1.8, 0.8 and -0.5 Mg ha-1 at ZZ, QY, GZL, CQ and JX, respectively. Also, NPKM increased total SOC stock by 18.3, 16.2, 14.4, 10.5, and 6.5 Mg ha-1 at QY, GZL, ZZ, CQ and JX, respectively. The corresponding changes of the sum of very labile and labile SOC fractions were 8.6, 6.8, 6.6, 3.2 and -1.6 Mg ha-1 at QY, GZL, ZZ, CQ and JX, respectively. These results suggested that about half or more than half SOC stock accretions under fertilization were induced by increase in non-labile SOC fractions. It thus informs the importance of non-labile SOC fractions in contributing to soil C sequestration under long-term fertilizations in Chinese croplands. Future research should improve our mechanistic understanding of biogeochemical transformation of non-labile organic C in soils.

Modulation of fatty acid composition and growth in Sporosarcina species in response to temperatures and exogenous branched-chain amino acids.

Science.gov (United States)

Tsuda, Kentaro; Nagano, Hideaki; Ando, Akinori; Shima, Jun; Ogawa, Jun

2017-06-01

Psychrotolerant endospore-forming Sporosarcina species have been predominantly isolated from minced fish meat (surimi), which is stored under refrigeration after heat treatment. To develop a better method for preserving surimi-based food products, we studied the growth and fatty acid compositions of the isolated strain S92h as well as Sporosarcina koreensis and Sporosarcina aquimarina at cold and moderate temperatures. The growth rates of strain S92h and S. koreensis were the fastest and slowest at cold temperatures, respectively, although these strains grew at a similar rate at moderate temperatures. In all three strains, the proportions of anteiso-C 15:0 and unsaturated fatty acids (UFAs) were significantly higher at cold temperatures than at moderate temperatures. Furthermore, supplementation with valine, leucine, and isoleucine resulted in proportional increases in iso-C 16:0 , iso-C 15:0 , and anteiso-C 15:0 , respectively, among the fatty acid compositions of these strains. The proportions of the UFAs were also altered by the supplementation. At cold temperatures, the growth rates of strain S92h and S. koreensis, but not of S. aquimarina, were affected by supplementation with leucine. Supplementation with isoleucine enhanced the growth of S. koreensis at cold temperatures but not that of the other strains. Valine did not affect the growth of any strain. These results indicate that anteiso-C 15:0 and UFAs both play important roles in the cold tolerance of the genus Sporosarcina and that these bacteria modulate their fatty acid compositions in response to the growth environment.

Alpha-amidated peptides derived from pro-opiomelanocortin in normal human pituitary

DEFF Research Database (Denmark)

Fenger, M; Johnsen, A H

1988-01-01

Normal human pituitaries were extracted in boiling water and acetic acid, and the alpha-amidated peptide products of pro-opiomelanocortin (POMC), alpha-melanocyte-stimulating hormone (alpha MSH), gamma-melanocyte-stimulating hormone (gamma 1MSH), and amidated hinge peptide (HP-N), as well...... (ACTH)-(1-39), ACTH-(1-14) and alpha MSH immunoreactivity]. alpha MSH and ACTH-(1-14) were only present in non- or mono-acetylated forms. Only large forms of gamma 1MSH and gamma 2MSH were present in partly glycosylated states. The hinge peptides were amidated to an extent two to three orders...... amidated POMC-related peptides are present in normal human pituitary. It also shows that cleavage in vivo at all dibasic amino acids but one, takes place at the N-terminal POMC region; the exception is at the POMC-(49-50) N-terminal of the gamma MSH sequence. The pattern of peptides produced suggests...

Higher temperature sensitivity for stable than for labile soil organic carbon - Evidence from incubations of long-term bare fallow soils

DEFF Research Database (Denmark)

Lefèvre, Romain; Barré, Pierre; Moyano, Fernando E.

2014-01-01

The impact of climate change on the stability of soil organic carbon (SOC)remains a major source of uncertainty in predicting future changes in atmospheric CO2 levels. One unsettled issue is whether the mineralization response to temperature depends on SOC mineralization rate. Long-term (>25 years......) bare fallow experiments (LTBF) in which the soil is kept free of any vegetation and organic inputs, and their associated archives of soil samples represent a unique research platform to examine this issue as with increasing duration of fallow, the lability of remaining total SOC decreases. We retrieved...... soils from LTBF experiments situated at Askov (Denmark), Grignon (France), Ultuna (Sweden), and Versailles (France) and sampled at the start of the experiments and after 25, 50, 52, and 79 years of bare fallow, respectively. Soils were incubated at 4, 12, 20, and 35 °C and the evolved CO2 monitored...

Clicked Cinnamic/Caffeic Esters and Amides as Radical Scavengers and 5-Lipoxygenase Inhibitors

Directory of Open Access Journals (Sweden)

Jérémie A. Doiron

2014-01-01

Full Text Available 5-Lipoxygenase (5-LO is the key enzyme responsible for the conversion of arachidonic acid to leukotrienes, a class of lipid mediators implicated in inflammatory disorders. In this paper, we describe the design, synthesis, and preliminary activity studies of novel clicked caffeic esters and amides as radical scavengers and 5-LO inhibitors. From known 5-LO inhibitor 3 as a lead, cinnamic esters 8a–h and amides 9a–h as well as caffeic esters 15a–h and amides 16a–h were synthesized by Cu(I-catalyzed [1,3]-dipolar cycloaddition with the appropriate azide precursors and terminal alkynes. All caffeic analogs are proved to be good radical scavengers (IC50: 10–20 μM. Esters 15g and 15f possessed excellent 5-LO inhibition activity in HEK293 cells and were equipotent with the known 5-LO inhibitor CAPE and more potent than Zileuton. Several synthesized esters possess activities rivaling Zileuton in stimulated human polymorphonuclear leukocytes.

Dehydroacetic Acid Derivatives Bearing Amide or Urea Moieties as Effective Anion Receptors.

Science.gov (United States)

Bregović, Nikola; Cindro, Nikola; Bertoša, Branimir; Barišić, Dajana; Frkanec, Leo; Užarević, Krunoslav; Tomišić, Vladislav

2017-08-01

Derivatives of dehydroacetic acid comprising amide or urea subunits have been synthesized and their anion-binding properties investigated. Among a series of halides and oxyanions, the studied compounds selectively bind acetate and dihydrogen phosphate in acetonitrile and dimethyl sulfoxide. The corresponding complexation processes were characterized by means of 1 H NMR titrations, which revealed a 1:1 complex stoichiometry in most cases, with the exception of dihydrogen phosphate, which formed 2:1 (anion/ligand) complexes in acetonitrile. The complex stability constants were determined and are discussed with respect to the structural properties of the receptors, the hydrogen-bond-forming potential of the anions, and the characteristics of the solvents used. Based on the spectroscopic data and results of Monte Carlo simulations, the amide or urea groups were affirmed as the primary binding sites in all cases. The results of the computational methods indicate that an array of both inter- and intramolecular hydrogen bonds can form in the studied systems, and these were shown to play an important role in defining the overall stability of the complexes. Solubility measurements were carried out in both solvents and the thermodynamics of transfer from acetonitrile to dimethyl sulfoxide were characterized on a quantitative level. This has afforded a detailed insight into the impact of the medium on the complexation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidative activation of dihydropyridine amides to reactive acyl donors

DEFF Research Database (Denmark)

Funder, Erik Daa; Trads, Julie Brender; Gothelf, Kurt Vesterager

2015-01-01

Amides of 1,4-dihydropyridine (DHP) are activated by oxidation for acyl transfer to amines, alcohols and thiols. In the reduced form the DHP amide is stable towards reaction with amines at room temperature. However, upon oxidation with DDQ the acyl donor is activated via a proposed pyridinium...

GC AND LC CHROMATOGRAPHIC AND EI, CE, +/- CI, AND ES MASS SPECTRAL CHARACTERISTICS OF SALTS AND AMIDES OF PERFLUOROOCTANESULFONIC ACID

Science.gov (United States)

In 1976, fluorine in human blood serum was thought to be present as perfluorooctanic acid; however, in the 1990s it was correctly identified by LC/MS as perfluorooctanesulfonate (PFOS). PFOS was both a commercial product and an end-stage metabolite of numerous substituted amides ...

Magnetic-superexchange interactions of uranium(IV) chloride-addition complexes with amides, 2

International Nuclear Information System (INIS)

Miyake, Chie; Hinatsu, Yukio; Imoto, Shosuke

1983-01-01

The magnetic susceptibilities of five cyclic amide (lactam)-addition complexes of uranium(IV) chloride were measured between room temperature and 2 K. Magnetic-exchange interaction was found only for N-methyl-substituted amide complexes, and a dimer structure was assumed for them on the basis of their chemical properties. Treating interdimer interaction with a molecular-field approximation, the magnetic susceptibilities were calculated to be in good agreement with the experimental results in the temperature region of the maxima in chi sub(A). The transmission of antiparallel spin coupling via the π orbitals of the bridging amide ligands is proposed to explain the strong intradimer superexchange interaction for the uranium(IV) chloride-amide complexes with the magnetic-susceptibility maximum. (author)

Synthesis, characterization and biological evaluation of bile acid-aromatic/heteroaromatic amides linked via amino acids as anti-cancer agents.

Science.gov (United States)

Agarwal, Devesh S; Anantaraju, Hasitha Shilpa; Sriram, Dharmarajan; Yogeeswari, Perumal; Nanjegowda, Shankara H; Mallu, P; Sakhuja, Rajeev

2016-03-01

A series of bile acid (Cholic acid and Deoxycholic acid) aryl/heteroaryl amides linked via α-amino acid were synthesized and tested against 3 human cancer cell-lines (HT29, MDAMB231, U87MG) and 1 human normal cell line (HEK293T). Some of the conjugates showed promising results to be new anticancer agents with good in vitro results. More specifically, Cholic acid derivatives 6a (1.35 μM), 6c (1.41 μM) and 6m (4.52 μM) possessing phenyl, benzothiazole and 4-methylphenyl groups showed fairly good activity against the breast cancer cell line with respect to Cisplatin (7.21 μM) and comparable with respect to Doxorubicin (1 μM), while 6e (2.49μM), 6i (2.46 μM) and 6m (1.62 μM) showed better activity against glioblastoma cancer cell line with respect to both Cisplatin (2.60 μM) and Doxorubicin (3.78 μM) drugs used as standards. Greater than 65% of the compounds were found to be safer on human normal cell line. Copyright © 2016 Elsevier Inc. All rights reserved.

Structures of Highly Twisted Amides Relevant to Amide N-C Cross-Coupling: Evidence for Ground-State Amide Destabilization.

Science.gov (United States)

Pace, Vittorio; Holzer, Wolfgang; Meng, Guangrong; Shi, Shicheng; Lalancette, Roger; Szostak, Roman; Szostak, Michal

2016-10-04

Herein, we show that acyclic amides that have recently enabled a series of elusive transition-metal-catalyzed N-C activation/cross-coupling reactions are highly twisted around the N-C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of the N-glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α-carbon atom. The (15) N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground-state twist as a blueprint for activation of amides toward N-C bond cleavage. The new mechanism offers considerable opportunities for organic synthesis and biological processes involving non-planar amide bonds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amides and an alkaloid from Portulaca oleracea.

Science.gov (United States)

Kokubun, Tetsuo; Kite, Geoffrey C; Veitch, Nigel C; Simmonds, Monique S J

2012-08-01

A total of 16 phenolic compounds, including one new and five known N-cinnamoyl phenylethylamides, one new pyrrole alkaloid named portulacaldehyde, five phenylpropanoid acids and amides, and derivatives of benzaldehyde and benzoic acid, were isolated and identified from a polar fraction of an extract of Portulaca oleracea. Their structures were determined through spectroscopic analyses.

Nine of 16 stereoisomeric polyhydroxylated proline amides are potent β-N-acetylhexosaminidase inhibitors.

Science.gov (United States)

Ayers, Benjamin J; Glawar, Andreas F G; Martínez, R Fernando; Ngo, Nigel; Liu, Zilei; Fleet, George W J; Butters, Terry D; Nash, Robert J; Yu, Chu-Yi; Wormald, Mark R; Nakagawa, Shinpei; Adachi, Isao; Kato, Atsushi; Jenkinson, Sarah F

2014-04-18

All 16 stereoisomeric N-methyl 5-(hydroxymethyl)-3,4-dihydroxyproline amides have been synthesized from lactones accessible from the enantiomers of glucuronolactone. Nine stereoisomers, including all eight with a (3R)-hydroxyl configuration, are low to submicromolar inhibitors of β-N-acetylhexosaminidases. A structural correlation between the proline amides is found with the ADMDP-acetamide analogues bearing an acetamidomethylpyrrolidine motif. The proline amides are generally more potent than their ADMDP-acetamide equivalents. β-N-Acetylhexosaminidase inhibition by an azetidine ADMDP-acetamide analogue is compared to an azetidine carboxylic acid amide. None of the amides are good α-N-acetylgalactosaminidase inhibitors.

Labile Zn ions on octacalcium phosphate-derived Zn-containing hydroxyapatite surfaces

Energy Technology Data Exchange (ETDEWEB)

Honda, Yoshitomo; Anada, Takahisa; Morimoto, Shinji [Division of Craniofacial Function Engineering (CFE), Tohoku University Graduate School of Dentistry, Sendai (Japan); Suzuki, Osamu, E-mail: suzuki-o@m.tohoku.ac.jp [Division of Craniofacial Function Engineering (CFE), Tohoku University Graduate School of Dentistry, Sendai (Japan)

2013-05-15

We previously synthesized and characterized zinc-containing octacalcium phosphate (OCP) and its hydrolyzed Ca-deficient hydroxyapatite (HA). In the present report, we attempted to define the state of Zn in the OCP-derived Zn-calcium phosphates (CaPs) in relation to the presence of specific amino acids. Zn-containing OCPs were prepared in solutions that included Zn ions up to a concentration of 3.5 mM, and their hydrolyzates [hydrolyzed (hy)-Zn-CaP] were obtained in hot water. The materials were characterized by x-ray diffraction and scanning electron microscopy. The concentration of Ca and Zn ions at room temperature was determined by analyzing the supernatant after incubating the materials in α-minimal essential medium (α-MEM) and HEPES buffer including cysteine, histidine, lysine, aspartic acid, and glutamic acid. Zn ions were more dissolved in α-MEM than HEPES buffer in the absence of amino acids. The inclusion of the amino acids enhanced Zn dissolution by several hundred fold, even in HEPES buffer. Among the amino acids, both cysteine and histidine enhanced the release of Zn. The effect was particularly remarkable with cysteine even in the presence of the other amino acids tested. These results indicate that Zn ions are present as a surface labile pool, which tends to be preferentially desorbed by cysteine, a ubiquitous molecule present in serum.

Synthesis and characterization of thermally stable poly(amide-imide-montmorillonite nanocomposites based on bis(4-carboxyphenyl-N,N'-pyromellitimide acid

Directory of Open Access Journals (Sweden)

M. Hajibeygi

2013-04-01

Full Text Available Two new poly(amide-imide-montmorillonite reinforced nanocomposites containing bis(4-carboxyphenyl-N,N'-pyromellitimide acid moiety in the main chain were synthesized by a convenient solution intercalation technique. Poly(amide-imide (PAI as a source of polymer matrix was synthesized by the direct polycondensation reaction of bis(4-carboxyphenyl-N,N'-pyromellitimide acid with 4,4'-diamino diphenyl sulfone in the presence of triphenyl phosphite (TPP, CaCl2, pyridine and N-methyl-2-pyrrolidone (NMP. Morphology and structure of the resulting PAI-nanocomposite films with 10 and 20% silicate particles were characterized by FT-IR spectroscopy, X-ray diffraction (XRD and scanning electron microscopy (SEM. The effect of clay dispersion and the interaction between clay and polymeric chains on the properties of nanocomposites films were investigated by using UV-Vis spectroscopy, thermal gravimetry analysis (TGA and water uptake measurements.DOI: http://dx.doi.org/10.4314/bcse.v27i1.10

SOLID-PHASE PEPTIDE SYNTHESIS OF ISOTOCIN WITH AMIDE ...

African Journals Online (AJOL)

SOLID-PHASE PEPTIDE SYNTHESIS OF ISOTOCIN WITH AMIDE OF ASPARAGINE PROTECTED WITH 1-TETRALINYL. TRIFLUOROMETHANESULPHONIC ACID (TFMSA) DEPROTECTION, CLEAVAGE AND AIR OXIDATION OF MERCAPTO GROUPS TO DISULPHIDE.

Direct Lactamization of Azido Amides via Staudinger-Type Reductive Cyclization

Energy Technology Data Exchange (ETDEWEB)

Heo, In Jung; Lee, Su Jeong; Cho, Chang Woo [Kyungpook National University, Daegu (Korea, Republic of)

2012-01-15

The direct lactamization of 1,3- and 1,4-azido amides has been achieved using triphenylphosphine and water, affording various γ- and δ-lactams in good to excellent yields. The direct lactamization of the azido amides was performed via the Staudinger-type reductive cyclization in which the amide group acts as the electrophile for lactam synthesis. This lactamization provides a mild, functional group tolerant and efficient route for the synthesis of various γ- and δ-lactams found in natural products and pharmaceuticals. Further studies will be conducted to develop new synthetic routes for the synthesis of various lactams. The lactam ring system is one of the most ubiquitous structural motifs found in natural products and pharmaceuticals. Owing to the prevalence of lactams, their synthesis has attracted considerable attention. Lactams are usually prepared by the coupling of activated carboxylic acid derivatives with amines. Alternative routes include the Beckmann rearrangement of oximes, the Schmidt reaction of cyclic ketones and hydrazoic acid, the Kinugasa reaction of nitrones and terminal acetylenes, the Diels-Alder reaction of cyclopentadiene and chlorosulfonyl isocyanate, transition metal catalyzed lactamization of amino alcohols, and iodolactamization of amides and alkenes. In particular, the intramolecular Staudinger ligation of azides and activated carboxy acids, including esters, is well known as an environmentally friendly and mild protocol for lactam synthesis.

Direct Lactamization of Azido Amides via Staudinger-Type Reductive Cyclization

International Nuclear Information System (INIS)

Heo, In Jung; Lee, Su Jeong; Cho, Chang Woo

2012-01-01

The direct lactamization of 1,3- and 1,4-azido amides has been achieved using triphenylphosphine and water, affording various γ- and δ-lactams in good to excellent yields. The direct lactamization of the azido amides was performed via the Staudinger-type reductive cyclization in which the amide group acts as the electrophile for lactam synthesis. This lactamization provides a mild, functional group tolerant and efficient route for the synthesis of various γ- and δ-lactams found in natural products and pharmaceuticals. Further studies will be conducted to develop new synthetic routes for the synthesis of various lactams. The lactam ring system is one of the most ubiquitous structural motifs found in natural products and pharmaceuticals. Owing to the prevalence of lactams, their synthesis has attracted considerable attention. Lactams are usually prepared by the coupling of activated carboxylic acid derivatives with amines. Alternative routes include the Beckmann rearrangement of oximes, the Schmidt reaction of cyclic ketones and hydrazoic acid, the Kinugasa reaction of nitrones and terminal acetylenes, the Diels-Alder reaction of cyclopentadiene and chlorosulfonyl isocyanate, transition metal catalyzed lactamization of amino alcohols, and iodolactamization of amides and alkenes. In particular, the intramolecular Staudinger ligation of azides and activated carboxy acids, including esters, is well known as an environmentally friendly and mild protocol for lactam synthesis

Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis.

Science.gov (United States)

Meng, Xiangtao; Edgar, Kevin J

2015-11-05

Cellulose esters with amide functionalities were synthesized by cross-metathesis (CM) reaction of terminally olefinic esters with different acrylamides, catalyzed by Hoveyda-Grubbs 2nd generation catalyst. Chelation by amides of the catalyst ruthenium center caused low conversions using conventional solvents. The effects of both solvent and structure of acrylamide on reaction conversion were investigated. While the inherent tendency of acrylamides to chelate Ru is governed by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides, from 50% to up to 99%. Homogeneous hydrogenation using p-toluenesulfonyl hydrazide successfully eliminated the α,β-unsaturation of the CM products to give stable amide-functionalized cellulose esters. The amide-functionalized product showed higher Tg than its starting terminally olefinic counterpart, which may have resulted from strong hydrogen bonding interactions of the amide functional groups. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biologically labile photoproducts from riverine non-labile dissolved organic carbon in the coastal waters

Science.gov (United States)

Kasurinen, V.; Aarnos, H.; Vähätalo, A.

2015-06-01

In order to assess the production of biologically labile photoproducts (BLPs) from non-labile riverine dissolved organic carbon (DOC), we collected water samples from ten major rivers, removed labile DOC and mixed the residual non-labile DOC with artificial seawater for microbial and photochemical experiments. Bacteria grew on non-labile DOC with a growth efficiency of 11.5% (mean; range from 3.6 to 15.3%). Simulated solar radiation transformed a part of non-labile DOC into BLPs, which stimulated bacterial respiration and production, but did not change bacterial growth efficiency (BGE) compared to the non-irradiated dark controls. In the irradiated water samples, the amount of BLPs stimulating bacterial production depended on the photochemical bleaching of chromophoric dissolved organic matter (CDOM). The apparent quantum yields for BLPs supporting bacterial production ranged from 9.5 to 76 (mean 39) (μmol C mol photons-1) at 330 nm. The corresponding values for BLPs supporting bacterial respiration ranged from 57 to 1204 (mean 320) (μmol C mol photons-1). According to the calculations based on spectral apparent quantum yields and local solar radiation, the annual production of BLPs ranged from 21 (St. Lawrence) to 584 (Yangtze) mmol C m-2 yr-1 in the plumes of the examined rivers. Complete photobleaching of riverine CDOM in the coastal ocean was estimated to produce 10.7 Mt C BLPs yr-1 from the rivers examined in this study and globally 38 Mt yr-1 (15% of riverine DOC flux from all rivers), which support 4.1 Mt yr-1 of bacterial production and 33.9 Mt yr-1 bacterial respiration.

Concurrent Increases and Decreases in Local Stability and Conformational Heterogeneity in Cu, Zn Superoxide Dismutase Variants Revealed by Temperature-Dependence of Amide Chemical Shifts.

Science.gov (United States)

Doyle, Colleen M; Rumfeldt, Jessica A; Broom, Helen R; Sekhar, Ashok; Kay, Lewis E; Meiering, Elizabeth M

2016-03-08

The chemical shifts of backbone amide protons in proteins are sensitive reporters of local structural stability and conformational heterogeneity, which can be determined from their readily measured linear and nonlinear temperature-dependences, respectively. Here we report analyses of amide proton temperature-dependences for native dimeric Cu, Zn superoxide dismutase (holo pWT SOD1) and structurally diverse mutant SOD1s associated with amyotrophic lateral sclerosis (ALS). Holo pWT SOD1 loses structure with temperature first at its periphery and, while having extremely high global stability, nevertheless exhibits extensive conformational heterogeneity, with ∼1 in 5 residues showing evidence for population of low energy alternative states. The holo G93A and E100G ALS mutants have moderately decreased global stability, whereas V148I is slightly stabilized. Comparison of the holo mutants as well as the marginally stable immature monomeric unmetalated and disulfide-reduced (apo(2SH)) pWT with holo pWT shows that changes in the local structural stability of individual amides vary greatly, with average changes corresponding to differences in global protein stability measured by differential scanning calorimetry. Mutants also exhibit altered conformational heterogeneity compared to pWT. Strikingly, substantial increases as well as decreases in local stability and conformational heterogeneity occur, in particular upon maturation and for G93A. Thus, the temperature-dependence of amide shifts for SOD1 variants is a rich source of information on the location and extent of perturbation of structure upon covalent changes and ligand binding. The implications for potential mechanisms of toxic misfolding of SOD1 in disease and for general aspects of protein energetics, including entropy-enthalpy compensation, are discussed.

Synthesis of [14C]-labelled eicosa-5,8,11-triynoic acid and conversion to anti-inflammatory amides

International Nuclear Information System (INIS)

Pilgrim, W.R.; Nedoncelle, P.; Shroot, B.; Maignan, J.; Restle, S.

1991-01-01

A four step synthesis of [5,6- 14 C]-eicosa-5,8,11-triynoic acid from [ 14 C]-labelled acetylene is described. [ 14 C 2 ]-acetylene was converted to 5-chloro-[1,2- 14 C]-pentyne via reaction of its monolithium salt with 3-bromo-1-chloropropane. The doubly labelled 5-chloropentyne thus obtained was transformed to [5,6- 14 C]-hex-5-ynoic acid which was then coupled with 1-chloro-tetradeca-2,5-diyne to give the title compound. Using 2-(2-aminoethoxy)ethanol and 1-(2-hydroxyethyl)piperazine, amides which had previously been found to be potent inhibitors of the 5-lipoxygenase enzyme, were prepared from [ 14 C-labelled eicosatriynoic acid by way of acylimidazole chemistry. (author)

Densities and volumetric properties of (acetonitrile+an amide) binary mixtures at temperatures between 293.15K and 318.15K

International Nuclear Information System (INIS)

Nain, Anil Kumar

2006-01-01

The densities of binary mixtures of acetonitrile (ACN) with formamide (FA), N,N-dimethylformamide (DMF), N-methylacetamide (NMA), and N,N-dimethylacetamide (DMA), including those of pure liquids, over the entire composition range were measured at temperatures (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and atmospheric pressure. From the experimental data, the excess molar volume, V m E , and partial molar volumes, V-bar m,1 and V-bar m,2 , were calculated over whole composition range. The variation of these parameters with composition and temperature of the mixtures has been discussed in terms of molecular interaction in these mixtures. The V m E values were found negative for all the mixtures and at each temperature studied, indicating the presence of specific interactions between ACN and amide molecules. The extent of negative deviations in V m E values follows the order: FA>NMA>DMA>DMF. It is observed that the V m E values depend upon the positions of methyl groups in these amide molecules

Normal growth spurt and final height despite low levels of all forms of circulating insulin-like growth factor-I in a patient with acid-labile subunit deficiency

DEFF Research Database (Denmark)

Domené, Horacio M; Martínez, Alicia S; Frystyk, Jan

2007-01-01

BACKGROUND: In a recently described patient with acid-labile subunit (ALS) deficiency, the inability to form ternary complexes resulted in a marked reduction in circulating total insulin-like growth factor (IGF)-I, whereas skeletal growth was only marginally affected. To further study the role of...

A zinc enolate of amide: Preparation and application in reformasky-like reaction leading to β-hydroxy amides

Energy Technology Data Exchange (ETDEWEB)

Cho, Hyun Hee; Kim, Seung Hoi [Dept. of Chemistry, Dankook University, Cheonan (Korea, Republic of)

2015-04-15

One of the best known functionalized organic complexes is the β-hydroxy carbonyl compound. This unique functionality has been frequently found in naturally occurring bioactive derivatives. The cross-coupling reaction of A with aldehydes were carried out in the absence of any catalyst and completed in most cases within 1.0 h at room temperature. We have developed an efficient synthetic route for the preparation of β-hydroxy amides. The method involved the preparation of room-temperature-stable organo zinc reagents (A, B, and C) in THF and their subsequent coupling reactions with various carbonyl derivatives under mild conditions. Significantly, this approach using zinc enolate of amides could expand the scope of Reformatsky-like reactions. Further studies to elucidate this synthetic protocol are currently under way in our laboratory.

Repeated labilization-reconsolidation processes strengthen declarative memory in humans.

Directory of Open Access Journals (Sweden)

Cecilia Forcato

Full Text Available The idea that memories are immutable after consolidation has been challenged. Several reports have shown that after the presentation of a specific reminder, reactivated old memories become labile and again susceptible to amnesic agents. Such vulnerability diminishes with the progress of time and implies a re-stabilization phase, usually referred to as reconsolidation. To date, the main findings describe the mechanisms associated with the labilization-reconsolidation process, but little is known about its functionality from a biological standpoint. Indeed, two functions have been proposed. One suggests that destabilization of the original memory after the reminder allows the integration of new information into the background of the original memory (memory updating, and the other suggests that the labilization-reconsolidation process strengthens the original memory (memory strengthening. We have previously reported the reconsolidation of human declarative memories, demonstrating memory updating in the framework of reconsolidation. Here we deal with the strengthening function attributed to the reconsolidation process. We triggered labilization-reconsolidation processes successively by repeated presentations of the proper reminder. Participants learned an association between five cue-syllables and their respective response-syllables. Twenty-four hours later, the paired-associate verbal memory was labilized by exposing the subjects to one, two or four reminders. The List-memory was evaluated on Day 3 showing that the memory was improved when at least a second reminder was presented in the time window of the first labilization-reconsolidation process prompted by the earlier reminder. However, the improvement effect was revealed on Day 3, only when at least two reminders were presented on Day 2 and not as a consequence of only retrieval. Therefore, we propose central concepts for the reconsolidation process, emphasizing its biological role and the

Repeated Labilization-Reconsolidation Processes Strengthen Declarative Memory in Humans

Science.gov (United States)

Forcato, Cecilia; Rodríguez, María L. C.; Pedreira, María E.

2011-01-01

The idea that memories are immutable after consolidation has been challenged. Several reports have shown that after the presentation of a specific reminder, reactivated old memories become labile and again susceptible to amnesic agents. Such vulnerability diminishes with the progress of time and implies a re-stabilization phase, usually referred to as reconsolidation. To date, the main findings describe the mechanisms associated with the labilization-reconsolidation process, but little is known about its functionality from a biological standpoint. Indeed, two functions have been proposed. One suggests that destabilization of the original memory after the reminder allows the integration of new information into the background of the original memory (memory updating), and the other suggests that the labilization-reconsolidation process strengthens the original memory (memory strengthening). We have previously reported the reconsolidation of human declarative memories, demonstrating memory updating in the framework of reconsolidation. Here we deal with the strengthening function attributed to the reconsolidation process. We triggered labilization-reconsolidation processes successively by repeated presentations of the proper reminder. Participants learned an association between five cue-syllables and their respective response-syllables. Twenty-four hours later, the paired-associate verbal memory was labilized by exposing the subjects to one, two or four reminders. The List-memory was evaluated on Day 3 showing that the memory was improved when at least a second reminder was presented in the time window of the first labilization-reconsolidation process prompted by the earlier reminder. However, the improvement effect was revealed on Day 3, only when at least two reminders were presented on Day2 and not as a consequence of only retrieval. Therefore, we propose central concepts for the reconsolidation process, emphasizing its biological role and the parametrical constrains

Microencapsulation of caffeic acid phenethyl ester and caffeic acid phenethyl amide by inclusion in hydroxypropyl-β-cyclodextrin.

Science.gov (United States)

Garrido, E Manuela P J; Cerqueira, Ana S; Chavarria, Daniel; Silva, Tiago; Borges, Fernanda; Garrido, Jorge M P J

2018-07-15

Caffeic acid phenethyl ester (CAPE) is a bioactive polyphenolic compound obtained from propolis extract. Although it has a broad therapeutic potential, the bioavailability of CAPE is limited, due to reduced solubility and poor plasmatic stability. Efforts to reduce these pharmacokinetic drawbacks resulted in the synthesis of caffeic acid phenethyl amide (CAPA). Cyclodextrins have been proved as promising excipients for the formulation of active ingredients. Herein, we report the inclusion complexation behavior and binding ability of CAPE and CAPA with hydroxypropyl-β-cyclodextrin (HP-β-CD). The supramolecular interactions were examined through UV and FTIR spectroscopy, DSC, 1 H NMR and 2D ROESY. The CAPE/HP-β-CD and CAPA/HP-β-CD inclusion complexes stability constants were determined to be, respectively, 2911.6 and 584.6 M -1 in water and 2866.2 and 700.1 M -1 at physiological pH. The aqueous solubility increased notably, proving that HP-β-CD can be potentially useful to improve the biological, chemical and physical properties of CAPE and CAPA. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ammonium absorption mechanism of rice seedling roots and 15N-labelling pattern of their glutamine-amide group, 2

International Nuclear Information System (INIS)

Arima, Yasuhiro; Kumazawa, Kikuo

1975-01-01

The processes of producing glutamine and asparagine at the initial stage of the absorption and assimilation of ammonia in rice seedling roots were examined in relation to glutamic acid, aspartic acid and ammonia by 15 N-labelling method. When ( 15 NH 4 ) 2 SO 4 was absorbed into the roots, 15 N concentration appeared very high in glutamine-amide radical and ammonia. It was also higher in amide radical than in amino radical in both glutamine and asparagine, while 15 N concentration in the amino radical of glutamine and asparagine were far lower than that of corresponding glutamine acid and aspartic acid. From these facts, glutamine-amide radical seems to be produced directly from the ammonia in culture media at the contact point of root cells and the culture media, while there is some possibility that asparagine-amide radical is formed from other amino compounds than ammonia. Also the amino radical of aspartic acid seems to be produced not only by the transamination from glutamic acid but also by the reductive amination of oxalautic acid by ammonium. (Kobatake, H.)

Nanostructured lipid carriers for transdermal delivery of acid labile lansoprazole.

Science.gov (United States)

Lin, Wen Jen; Duh, Yi Shein

2016-11-01

The aim of this study was to develop nanostructured lipid carriers (NLCs) for transdermal delivery of acid-labile lansoprazole (LPZ). The drug loading, particle size, zeta potential, thermal behavior and stability of NLCs were evaluated. The particle size of NLCs was in the range of 90-210nm and the zeta potential was -61.9 to +3.2mV dependent of the compositions. Stearylamine (SA) prevented lansoprazole degradation and maintained drug stable in NLCs. The anionic sodium dodecyl sulfate (SDS) adsorbed on the lipid surface and formed complex with cationic SA to prevent NLCs aggregation. The effects of type (e.g., isopropyl myristate (IPM), menthol) and concentration (e.g., 1.25, 2.50, 3.75%w/w) of enhancers on penetration of lansoprazole NLC hydrogels were investigated in vitro using Wistar rat skin. The steady-state flux of lansoprazole NLC hydrogel containing 3.75% IPM was the highest which was enhanced by 2.7 folds as compared to enhancer-free NLC hydrogel. In vivo pharmacokinetics of lansoprazole following transdermal delivery of NLC hydrogel showed that the elimination of drug was significantly reduced and the mean residence time of drug was prominently prolonged as compared to intravenous drug solution (p<0.005). The accumulation of drug in the skin and continuous penetration of drug through the skin accounted for the maintenance of drug concentration for at least 24h. Copyright © 2016 Elsevier B.V. All rights reserved.

Expanding the Library of Uranyl Amide Derivatives: New Complexes Featuring the tert-Butyldimethylsilylamide Ligand.

Science.gov (United States)

Pattenaude, Scott A; Coughlin, Ezra J; Collins, Tyler S; Zeller, Matthias; Bart, Suzanne C

2018-04-16

New uranyl derivatives featuring the amide ligand, -N(SiHMe 2 ) t Bu, were synthesized and characterized by X-ray crystallography, multinuclear NMR spectroscopy, and absorption spectroscopies. Steric properties of these complexes were also quantified using the computational program Solid-G. The increased basicity of the free ligand -N(SiHMe 2 ) t Bu was demonstrated by direct comparison to -N(SiMe 3 ) 2 , a popular supporting ligand for uranyl. Substitutional lability on a uranyl center was also demonstrated by exchange with the -N(SiMe 3 ) 2 ligand. The increased basicity of this ligand and diverse characterization handles discussed here will make these compounds useful synthons for future reactivity.

Fatty acid sulphoalkyl amides and esters as cosmetic surfactants.

Science.gov (United States)

Petter, P J

1984-10-01

Synopsis A review is given of the manufacture, properties and applications of the anionic surfactants commonly known as taurates and isethionates (fatty acid sulphoalkyl amides and esters, respectively). Originally developed in the 1930s for textile processing, these surfactants are used increasingly in the cosmetic field, particularly those derived from coconut fatty acid. Both types are produced from sodium isethionate, HO degrees C(2)H(4)SO(3)Na. The acyl isethionate, R degrees COO degrees C(2)H(4)SO(3)Na, is obtained by reaction with a fatty acid ('direct process'). or fatty acid chloride ('indirect process'). The direct process is cheaper but requires extreme conditions which can lead to discoloration of the product and a loss of shorter chain fatty acid components. The N-methyl-N-acyltaurate, R degrees CON(R(1))C(2)H(4)SO(3)Na, is obtained by Schotten-Baumann reaction of a fatty acid chloride with N-methyltaurine, which is derived from sodium isethionate via methylamine. Taurates and isethionates retain the benefits of the soaps to which they are structurally similar, but chemical modifications have eliminated many undesirable features. Thus they combine good detergency and wetting with high foaming, and maintain their performance in hard or salt water. Taurates are stable to hydrolysis over the whole pH range. Isethionates are prone to hydrolysis at high (>8) or low (soap bars based on isethionate can be formulated at neutral pH ('Dove type'bars) instead of the alkaline pH of soap, and have been shown in various studies to be milder than soap and better tolerated by the young, the old and those with sensitive skins. Similarly, isethionates have been shown to be less irritating than other anionic or amphoteric surfactants used in cosmetics. The difference has been related to the negligible effect of isethionate on the water-binding capacity of stratum corneum. Other cosmetic applications besides toilet bars include shampoos (excellent cleaning, mild to scalp

Zinc(II) complexes with intramolecular amide oxygen coordination as models of metalloamidases.

Science.gov (United States)

Rivas, Juan C Mareque; Salvagni, Emiliano; Prabaharan, Ravi; de Rosales, Rafael Torres Martin; Parsons, Simon

2004-01-07

Polydentate ligands (6-R1-2-pyridylmethyl)-R2(R1= NHCOtBu, R2= bis(2-pyridylmethyl)amine L1, bis(2-(methylthio)ethyl)amine L2 and N(CH2CH2)2S L3) form mononuclear zinc(II) complexes with intramolecular amide oxygen coordination and a range of coordination environments. Thus, the reaction of Zn(ClO4)2.6H2O with L1-3 in acetonitrile affords [(L)Zn](ClO4)2(L=L1, 1; L2, 2) and [(L3)Zn(H2O)(NCCH3)](ClO4)2 3. The simultaneous amide/water binding in resembles the motif that has been proposed to be involved in the double substrate/nucleophile Lewis acidic activation and positioning mechanism of amide bond hydrolysis in metallopeptidases. X-ray diffraction, 1H and 13C NMR and IR data suggests that the strength of amide oxygen coordination follows the trend 1>2 >3. L1-3 and undergo cleavage of the tert-butylamide upon addition of Me4NOH.5H2O (1 equiv.) in methanol at 50(1)degrees C. The rate of amide cleavage follows the order 1> 2> 3, L1-3. The extent by which the amide cleavage reaction is accelerated in 1-3 relative to the free ligands, L1-3, is correlated with the strength of amide oxygen binding and Lewis acidity of the zinc(II) centre in deduced from the X-ray, NMR and IR studies.

Salt forms of the pharmaceutical amide dihydrocarbamazepine.

Science.gov (United States)

Buist, Amanda R; Kennedy, Alan R

2016-02-01

Carbamazepine (CBZ) is well known as a model active pharmaceutical ingredient used in the study of polymorphism and the generation and comparison of cocrystal forms. The pharmaceutical amide dihydrocarbamazepine (DCBZ) is a less well known material and is largely of interest here as a structural congener of CBZ. Reaction of DCBZ with strong acids results in protonation of the amide functionality at the O atom and gives the salt forms dihydrocarbamazepine hydrochloride {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride, C15H15N2O(+)·Cl(-)}, dihydrocarbamazepine hydrochloride monohydrate {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride monohydrate, C15H15N2O(+)·Cl(-)·H2O} and dihydrocarbamazepine hydrobromide monohydrate {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium bromide monohydrate, C15H15N2O(+)·Br(-)·H2O}. The anhydrous hydrochloride has a structure with two crystallographically independent ion pairs (Z' = 2), wherein both cations adopt syn conformations, whilst the two hydrated species are mutually isostructural and have cations with anti conformations. Compared to neutral dihydrocarbamazepine structures, protonation of the amide group is shown to cause changes to both the molecular (C=O bond lengthening and C-N bond shortening) and the supramolecular structures. The amide-to-amide and dimeric hydrogen-bonding motifs seen for neutral polymorphs and cocrystalline species are replaced here by one-dimensional polymeric constructs with no direct amide-to-amide bonds. The structures are also compared with, and shown to be closely related to, those of the salt forms of the structurally similar pharmaceutical carbamazepine.

On the unconventional amide I band in acetanilide

Science.gov (United States)

Tenenbaum, Alexander; Campa, Alessandro; Giansanti, Andrea

1987-04-01

We developed a new model to study the molecular dynamics of the acetanilide (ACN) crystal by computer simulation. Low-frequency oscillations of the molecules as a whole were considered with high-frequency vibrations of the amidic degrees of freedom involved in hydrogen bonding. The low-temperature power spectrum has two peaks, shifted by 15 cm -1, in the region of the amide I band: one of them corresponds to the so-called anomalous amide I band in the IR and Raman spectra of ACN. We found that this peak is due to the coupling of the low-frequency motion in the chain of molecules with the motion of the hydrogen-bonded protons, at variance with current suggestions.

Effects of temperature, packaging and electron beam irradiation processing conditions on the property behaviour of Poly (ether-block-amide) blends.

Science.gov (United States)

Murray, Kieran A; Kennedy, James E; McEvoy, Brian; Vrain, Olivier; Ryan, Damien; Cowman, Richard; Higginbotham, Clement L

2014-06-01

The radiation stability of Poly (ether-block-amide) (PEBA) blended with a multifunctional phenolic antioxidant and a hindered amide light stabiliser was examined under various temperatures, packaging and electron beam processing conditions. FTIR revealed that there were slight alterations to the PEBA before irradiation; however, these became more pronounced following irradiation. The effect of varying the temperature, packaging and processing conditions on the resultant PEBA properties was apparent. For example, rheology demonstrated that the structural properties could be enhanced by manipulating the aforementioned criteria. Mechanical testing exhibited less radiation resistance when the PEBA samples were vacuum packed and exposed to irradiation. MFI and AFM confirmed that the melting strength and surface topography could be reduced/increased depending on the conditions employed. From this study it was concluded that virgin PEBA submerged in dry ice with non-vacuum packaging during the irradiation process, provided excellent radiation resistance (20.9% improvement) in contrast to the traditional method. Copyright © 2014. Published by Elsevier B.V.

Synthesis and quantitation of six phenolic amides in Amaranthus spp

DEFF Research Database (Denmark)

Pedersen, Hans; Steffensen, Stine K; Christophersen, Carsten

2010-01-01

Cinnamoylphenethylamines are phenolic amides in which cinnamic acid provides the acid moiety and phenethylamine the amine moiety. Single ion monitoring (SIM) in LC-MS was performed on amaranth leaf extracts. Masses corresponding to sets of regioisomers, including previously reported compounds, were...

Lysosomal pH-inducible supramolecular dissociation of polyrotaxanes possessing acid-labile N-triphenylmethyl end groups and their therapeutic potential for Niemann-Pick type C disease

Science.gov (United States)

Tamura, Atsushi; Nishida, Kei; Yui, Nobuhiko

2016-01-01

Niemann-Pick type C (NPC) disease is characterized by the accumulation of cholesterol in lysosomes. We have previously reported that biocleavable polyrotaxanes (PRXs) composed of β-cyclodextrins (β-CDs) threaded onto a linear polymer capped with bulky stopper molecules via intracellularly cleavable linkers show remarkable cholesterol reducing effects in NPC disease patient-derived fibroblasts owing to the stimuli-responsive intracellular dissociation of PRXs and subsequent β-CD release from the PRXs. Herein, we describe a series of novel acid-labile 2-(2-hydroxyethoxy)ethyl group-modified PRXs (HEE-PRXs) bearing terminal N-triphenylmethyl (N-Trt) groups as a cleavable component for the treatment of NPC disease. The N-Trt end groups of the HEE-PRXs underwent acidic pH-induced cleavage and led to the dissociation of their supramolecular structure. A kinetic study revealed that the number of HEE groups on the PRX did not affect the cleavage kinetics of the N-Trt end groups of the HEE-PRXs. The effect of the number of HEE groups of the HEE-PRXs, which was modified to impart water solubility to the PRXs, on cellular internalization efficiency, lysosomal localization efficiency, and cholesterol reduction ability in NPC disease-derived fibroblasts (NPC1 fibroblasts) was also investigated. The cellular uptake and lysosomal localization efficiency were almost equivalent for HEE-PRXs with different numbers of HEE groups. However, the cholesterol reducing ability of the HEE-PRXs in NPC1 fibroblasts was affected by the number of HEE groups, and HEE-PRXs with a high number of HEE groups were unable to reduce lysosomal cholesterol accumulation. This deficiency is most likely due to the cholesterol-solubilizing ability of HEE-modified β-CDs released from the HEE-PRXs. We conclude that the N-Trt group acts as a cleavable component to induce the lysosomal dissociation of HEE-PRXs, and acid-labile HEE-PRXs with an optimal number of HEE groups (4.1 to 5.4 HEE groups per single �

Preparation and evaluation of oral multiparticulate formulations of acid-labile drugs

OpenAIRE

Huang, Fang

2017-01-01

Säure-labile Medikamente werden leicht in saurem Medium abgebaut, welche hauptsächlich als enterisch beschichtete Dosierungsformen für die orale Verabreichung formuliert wurden. Das Ziel dieser Studie war es, orale multipartikuläre Formulierungen von säure-labilen Medikamenten, mit Ilaprazol, Lansoprazol und Rabeprazol Natrium als Modellarzneistoffe vorzubereiten. Der Einfluss der Wirkstofflöslichkeit von Lansoprazol und Rabeprazol Natrium und des Kerntyps, wurde auf das Übe...

Evidence for the involvement of a labile protein in stimulation of adrenal steroidogenesis under conditions not inhibitory to protein synthesis

International Nuclear Information System (INIS)

Krueger, R.J.; Orme-Johnson, N.R.

1988-01-01

Evidence is presented to support the hypothesis that synthesis of a labile protein is required for stimulation of steroidogenesis in rat adrenocortical cells. Amino acids L-canavanine and L-S-aminoethylcysteine, at concentrations as high as 5 mM, each inhibited steroidogenesis to a much greater extent than they inhibited protein synthesis. S-Aminoethylcysteine caused a 50% decrease in the stimulated rate of corticosterone production under conditions where incorporation of [35S]methionine into protein was unchanged. Both amino acids block stimulation of steroid synthesis at a step subsequent to the formation of cAMP and before the synthesis of progesterone. The onset of this effect, after the addition of the amino acids, on corticosterone production is quite rapid. These results provide support, that is not dependent on inhibition of protein synthesis, for the hypothesis that a labile protein mediates stimulation of steroidogenesis. Reversal of canavanine and S-aminoethylcysteine inhibition of steroidogenesis by arginine and lysine, respectively, suggests that the inhibitors are functioning as amino acid analogs. S-Aminoethylcysteine inhibits the incorporation of [3H]lysine into protein as well as inhibits steroidogenesis; further, [3H]S-aminoethylcysteine is incorporated into protein that is nonstimulatory. These results suggest that lysine residues play an essential role in the function of the labile protein or that the labile protein contains a large number of lysine residues

Hydrogen isotope exchange of organic compounds in dilute acid at elevated temperatures

International Nuclear Information System (INIS)

Werstiuk, N.H.

1987-01-01

Introduction of one or more deuterium (or tritium) atoms into organic molecules can be accomplished in many ways depending on the nature of the substrate and the extent and sterochemistry of deuteriation or tritiation required. Some of the common methods include acid- and base-catalyzed exchange of carbonyl compounds, metal hydride reductions, dissolving metal reductions, catalytic reduction of double bonds, chromatographic exchange, homogeneous and heterogeneous metal-catalyzed exchange, base-catalyzed exchange of carbon acids other than carbonyl compounds and acid-catalyzed exchange via electrophilic substitution. Only the latter three methods have been used for perdeuteriation of organic compounds. A very useful compendium of labeling methods with examples has been available to chemists for some time. Although metal-catalyzed exchange has been used extensively, the method suffers from some deficiencies: irreproducibility of catalyst surfaces, catalyst poisoning, side reactions such as coupling and hydrogenolysis of labile groups and low deuterium incorporation. Usually a number of cycles are required with fresh catalyst and fresh deuterium source to achieve substantial isotope incorporation. Acid-catalyzed exchange of aromatics and alkenes, strongly acidic media such as liquid DBr, concentrated DBr, acetic acid/stannic chloride, concentrated D 3 PO 4 , concentrated DC1, D 3 PO 4 /BF 3 SO 2 , 50-80% D 2 SO 4 and DFSO 4 /SbF 5 at moderate temperatures (<100 degrees) have been used to effect exchange. The methods are not particularly suitable for large scale deuteriations because of the cost and the fact that the recovery and upgrading of the diluted deuterium pool is difficult. This paper describes the hydrogen isotope exchange of a variety of organic compounds in dilute aqueous acid (0.1-0.5 M) at elevated temperatures (150-300 degrees)

HPLC/ELSD analysis of amidated bile acids: an effective and rapid way to assist continuous flow chemistry processes.

Science.gov (United States)

Sardella, Roccaldo; Gioiello, Antimo; Ianni, Federica; Venturoni, Francesco; Natalini, Benedetto

2012-10-15

The employment of the flow N-acyl amidation of natural bile acids (BAs) required the in-line connection with suitable analytical tools enabling the determination of reaction yields as well as of the purity grade of the synthesized glyco- and tauro-conjugated derivatives. In this framework, a unique HPLC method was successfully established and validated for ursodeoxycholic (UDCA), chenodeoxycholic (CDCA), deoxycholic (DCA) and cholic (CA) acids, as well as the corresponding glyco- and tauro-conjugated forms. Because of the shared absence of relevant chromophoric moieties in the sample structure, an evaporative light scattering detector (ELSD) was profitably utilized for the analysis of such steroidal species. For each of the investigated compounds, all the runs were contemporarily carried out on the acidic free and the two relative conjugated variants. The different ELSD response of the free and the corresponding conjugated BAs, imposed to build-up separate calibration curves. In all the cases, very good precision (RSD% values ranging from 1.04 to 6.40% in the long-period) and accuracy (Recovery% values ranging from 96.03 to 111.14% in the long-period) values along with appreciably low LOD and LOQ values (the former being within the range 1-27 ng mL(-1) and the latter within the range 2-44 ng mL(-1)) turned out. Copyright © 2012 Elsevier B.V. All rights reserved.

Synthesis of ( sup 14 C)-labelled eicosa-5,8,11-triynoic acid and conversion to anti-inflammatory amides

Energy Technology Data Exchange (ETDEWEB)

Pilgrim, W R; Nedoncelle, P; Shroot, B [Centre International de Recherches Dermatologiques Galderma, Valbonne (France); Maignan, J; Restle, S [L' Oreal, Lab. de Recherches Fondamentales, Aulnay sous Bois, (France)

1991-07-01

A four step synthesis of (5,6-{sup 14}C)-eicosa-5,8,11-triynoic acid from ({sup 14}C)-labelled acetylene is described. ({sup 14}C{sub 2})-acetylene was converted to 5-chloro-(1,2-{sup 14}C)-pentyne via reaction of its monolithium salt with 3-bromo-1-chloropropane. The doubly labelled 5-chloropentyne thus obtained was transformed to (5,6-{sup 14}C)-hex-5-ynoic acid which was then coupled with 1-chloro-tetradeca-2,5-diyne to give the title compound. Using 2-(2-aminoethoxy)ethanol and 1-(2-hydroxyethyl)piperazine, amides which had previously been found to be potent inhibitors of the 5-lipoxygenase enzyme, were prepared from ({sup 14}C)-labelled eicosatriynoic acid by way of acylimidazole chemistry. (author).

Synthesis, Antifungal Activity and QSAR of Some Novel Carboxylic Acid Amides

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Shijie Du

2015-03-01

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

Influence of fast pyrolysis temperature on biochar labile fraction and short-term carbon loss in a loamy soil

DEFF Research Database (Denmark)

Bruun, Esben; Hauggaard-Nielsen, Henrik; Ibrahim, Norazana

2011-01-01

Production of bio-oil, gas and biochar from pyrolysis of biomass is considered a promising technology for combined production of bioenergy and recalcitrant carbon (C) suitable for sequestration in soil. Using a fast pyrolysis centrifuge reactor (PCR) the present study investigated the relation...... between fast pyrolysis of wheat straw at different reactor temperatures and the short-term degradability of biochar in soil. After 115 days incubation 3–12% of the added biochar-C had been emitted as CO2. On average, 90% of the total biochar-C loss occurred within the first 20 days of the experiment......, emphasizing the importance of knowing the biochar labile fraction when evaluating a specific biochars C sequestration potential. The pyrolysis temperature influenced the outputs of biochar, bio-oil and syngas significantly, as well as the stability of the biochar produced. Contrary to slow pyrolysis a fast...

Abscisic acid regulates seed germination of Vellozia species in response to temperature.

Science.gov (United States)

Vieira, B C; Bicalho, E M; Munné-Bosch, S; Garcia, Q S

2017-03-01

The relationship between the phytohormones, gibberellin (GA) and abscisic acid (ABA) and light and temperature on seed germination is still not well understood. We aimed to investigate the role of the ABA and GA on seed germination of Vellozia caruncularis, V. intermedia and V. alutacea in response to light/dark conditions on different temperature. Seeds were incubated in GA (GA 3 or GA 4 ) or ABA and their respective biosynthesis inhibitors (paclobutrazol - PAC, and fluridone - FLU) solutions at two contrasting temperatures (25 and 40 °C). Furthermore, endogenous concentrations of active GAs and those of ABA were measured in seeds of V. intermedia and V. alutacea during imbibition/germination. Exogenous ABA inhibited the germination of Vellozia species under all conditions tested. GA, FLU and FLU + GA 3 stimulated germination in the dark at 25 °C (GA 4 being more effective than GA 3 ). PAC reduced seed germination in V. caruncularis and V. alutacea, but did not affect germination of V. intermedia at 40 °C either under light or dark conditions. During imbibition in the dark, levels of active GAs decreased in the seeds of V. intermedia, but were not altered in those of V. alutacea. Incubation at 40 °C decreased ABA levels during imbibition in both V. caruncularis and V. alutacea. We conclude that the seeds of Vellozia species studied here require light or high temperature to germinate and ABA has a major role in the regulation of Vellozia seed germination in response to light and temperature. © 2016 German Botanical Society and The Royal Botanical Society of the Netherlands.

Development of analytical method used for the estimation of potassium amide in liquid ammonia at HWP (Tuticorin)

International Nuclear Information System (INIS)

Ramanathan, A.V.

2007-01-01

Potassium amide in liquid ammonia is used as a homogeneous catalyst in mono-thermal ammonia-hydrogen isotopic chemical exchange process employed for the manufacture of heavy water. Estimation of concentration of potassium amide in liquid ammonia is vital for checking whether it is sufficient for catalysis in isotopic exchange towers or for purification in purifiers in the Heavy Water Plants. This estimation was carried out earlier by the conventional method involving evaporation of ammonia, decomposition of potassium amide with water and titration of liberated ammonia with sulphuric acid. This method has been replaced by a newly developed method involving direct titration of potassium amide in ammonia with ammonium bromide. This new method is based on the principle that ammonium bromide and potassium amide act as acid and base respectively in the non-aqueous solvent medium, liquid ammonia. This method has not only proved to be an alternative method of estimation of potassium amide in liquid ammonia but also has been serving as a developed analytical method, because it is faster (with fewer steps), more accurate, safer (as it excludes the use of corrosive sulphuric acid needed for the conventional method) and more convenient (as it doesn't need specially designed apparatus and inert gas like dry nitrogen used in the conventional method). (author)

Unconventional Passerini Reaction toward α-Aminoxy-amides

NARCIS (Netherlands)

Chandgude, Ajay L; Dömling, Alexander

2016-01-01

The Passerini multicomponent reaction (P-3CR) toward the one-step synthesis of α-aminoxy-amide, by employing for the first time a N-hydroxamic acid component, has been reported. The sonication-accelerated, catalyst-free, simple, fast, and highly efficient Passerini reaction is used for the synthesis

Sequential backbone assignment based on dipolar amide-to-amide correlation experiments

Energy Technology Data Exchange (ETDEWEB)

Xiang, ShengQi; Grohe, Kristof; Rovó, Petra; Vasa, Suresh Kumar; Giller, Karin; Becker, Stefan; Linser, Rasmus, E-mail: rali@nmr.mpibpc.mpg.de [Max Planck Institute for Biophysical Chemistry, Department for NMR-Based Structural Biology (Germany)

2015-07-15

Proton detection in solid-state NMR has seen a tremendous increase in popularity in the last years. New experimental techniques allow to exploit protons as an additional source of information on structure, dynamics, and protein interactions with their surroundings. In addition, sensitivity is mostly improved and ambiguity in assignment experiments reduced. We show here that, in the solid state, sequential amide-to-amide correlations turn out to be an excellent, complementary way to exploit amide shifts for unambiguous backbone assignment. For a general assessment, we compare amide-to-amide experiments with the more common {sup 13}C-shift-based methods. Exploiting efficient CP magnetization transfers rather than less efficient INEPT periods, our results suggest that the approach is very feasible for solid-state NMR.

Sequential backbone assignment based on dipolar amide-to-amide correlation experiments

International Nuclear Information System (INIS)

Xiang, ShengQi; Grohe, Kristof; Rovó, Petra; Vasa, Suresh Kumar; Giller, Karin; Becker, Stefan; Linser, Rasmus

2015-01-01

Proton detection in solid-state NMR has seen a tremendous increase in popularity in the last years. New experimental techniques allow to exploit protons as an additional source of information on structure, dynamics, and protein interactions with their surroundings. In addition, sensitivity is mostly improved and ambiguity in assignment experiments reduced. We show here that, in the solid state, sequential amide-to-amide correlations turn out to be an excellent, complementary way to exploit amide shifts for unambiguous backbone assignment. For a general assessment, we compare amide-to-amide experiments with the more common 13 C-shift-based methods. Exploiting efficient CP magnetization transfers rather than less efficient INEPT periods, our results suggest that the approach is very feasible for solid-state NMR

A new phenylethyl alkyl amide from the Ambrostoma quadriimpressum Motschulsky

Directory of Open Access Journals (Sweden)

Guolei Zhao

2011-09-01

Full Text Available A new phenylethyl alkyl amide, (10R-10-hydroxy-N-phenethyloctadecanamide (1, was isolated from the beetle Ambrostoma quadriimpressum Motschulsky. The structure of the amide was determined by NMR and MS. The absolute configuration of compound 1 was confirmed by an asymmetric total synthesis, which was started from L-glutamic acid. The construction of the aliphatic chain was accomplished by the selective protection of the hydroxy groups and two-time implementation of the Wittig olefination reaction.

GLP-1-(9-36) amide reduces blood glucose in anesthetized pigs by a mechanism that does not involve insulin secretion

DEFF Research Database (Denmark)

Deacon, Carolyn F; Plamboeck, Astrid; Møller, Søren

2002-01-01

impossible to assess its true efficacy in vivo. In chloralose-anesthetized pigs given valine-pyrrolidide (to block endogenous DPP IV activity), the independent effects of GLP-1-(7-36) amide on glucose and insulin responses to intravenous glucose were assessed, and the metabolite generated by DPP IV, GLP-1......-(9-36) amide, was investigated for any ability to influence these responses. GLP-1-(7-36) amide enhanced insulin secretion (P amide was without effect, either alone or when coinfused with GLP-1-(7-36) amide. In contrast, GLP-1-(9-36) amide did affect glucose responses (P...... amide (73 +/- 19 mmol x l(-1) x min; P amide (62 +/- 13 mmol x l(-1) x min; P amide + GLP-1-(9-36) amide (50 +/-13 mmol x l(-1) x min; P

Ester-Mediated Amide Bond Formation Driven by Wet-Dry Cycles: A Possible Path to Polypeptides on the Prebiotic Earth.

Science.gov (United States)

Forsythe, Jay G; Yu, Sheng-Sheng; Mamajanov, Irena; Grover, Martha A; Krishnamurthy, Ramanarayanan; Fernández, Facundo M; Hud, Nicholas V

2015-08-17

Although it is generally accepted that amino acids were present on the prebiotic Earth, the mechanism by which α-amino acids were condensed into polypeptides before the emergence of enzymes remains unsolved. Here, we demonstrate a prebiotically plausible mechanism for peptide (amide) bond formation that is enabled by α-hydroxy acids, which were likely present along with amino acids on the early Earth. Together, α-hydroxy acids and α-amino acids form depsipeptides-oligomers with a combination of ester and amide linkages-in model prebiotic reactions that are driven by wet-cool/dry-hot cycles. Through a combination of ester-amide bond exchange and ester bond hydrolysis, depsipeptides are enriched with amino acids over time. These results support a long-standing hypothesis that peptides might have arisen from ester-based precursors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Complexation of di-amides of dipicolinic acid with neodymium

Energy Technology Data Exchange (ETDEWEB)

Lapka, J.L.; Paulenova, A. [Department of Chemistry, Oregon State University: 100 Radiation Center, Corvallis, OR 97331 (United States)

2013-07-01

Di-amides have undergone significant studies as possible ligands for use in the partitioning of trivalent minor actinides and lanthanides. The binding affinities of three isomeric ligands with neodymium in acetonitrile solution have been investigated. The stability constants of the metal-ligand complexes formed between different isomers of N,N'-diethyl-N,N'- ditolyl-di-picolinamide (EtTDPA) and trivalent neodymium in acetonitrile have been determined by spectrophotometric and calorimetric methods. Each isomer of EtTDPA has been found to be capable of forming three complexes with trivalent neodymium, Nd(EtTDPA), Nd(EtTDPA){sub 2}, and Nd(EtTDPA){sub 3}. Values from spectrophotometric and calorimetric titrations are within reasonable agreement with each other. The order of stability constants for each metal:ligand complex decreases in the order Et(m)TDPA > Et(p)TDPA > Et(o)TDPA. The obtained values are comparable to other di-amidic ligands obtained under similar system conditions and mirror previously obtained solvent extraction data for EtTDPA at low ionic strengths. (authors.

Roles of head group architecture and side chain length on colorimetric response of polydiacetylene vesicles to temperature, ethanol and pH.

Science.gov (United States)

Charoenthai, Nipaphat; Pattanatornchai, Thanutpon; Wacharasindhu, Sumrit; Sukwattanasinitt, Mongkol; Traiphol, Rakchart

2011-08-15

In this contribution, we report the relationship between molecular structures of polydiacetylene (PDA) vesicles, fabricated by using three monomers, 10,12-tricosadiynoic acid (TCDA), 10,12-pentacosadiynoic acid (PCDA) and N-(2-aminoethyl)pentacosa-10,12-diynamide (AEPCDA), and their color-transition behaviors. The modification of side chain length and head group of the PDA vesicles strongly affects the colorimetric response to temperature, ethanol and pH. A shorter side chain of poly(TCDA) yields weaker inter- and intra-chain dispersion interactions in the bilayers compared to the system of poly(PCDA), which in turn results in a faster color transition upon exposure to all stimuli. A change of head group in poly(AEPCDA) slightly reduces the transition temperature. Interestingly, the colorimetric response of poly(AEPCDA) vesicles to the addition of ethanol is found to occur in a two-step fashion while the response of poly(PCDA) vesicles takes place in a one-step process. The amount of ethanol required for inducing complete color-transition of poly(AEPCDA) vesicles is also much higher, about 87% v/v. The increase of pH to ~9 and ~10 causes a color-transition of poly(TCDA) and poly(PCDA) vesicles, respectively. The poly(AEPCDA) vesicles, on the other hand, change color upon decreasing pH to ~0. The colorimetric response also occurs in a multi-step fashion. These discrepancies are attributed to the architecture of surface layers of poly(AEPCDA), constituting amine and amide groups separated by ethyl linkers. Copyright © 2011 Elsevier Inc. All rights reserved.

Comparative synergistic (technetium-actinide) extraction chemistry by tributylphosphate and some amide extractants

International Nuclear Information System (INIS)

Condamines, N.; Musikas, C.

1993-01-01

In nuclear fuel reprocessing, technetium (TcO 4 - ) leads to bad interferences in the extractions, being synergistically co-extracted with different actinide cations as Uranium (VI), Plutonium (IV) and Zirconium (IV). It destroys the hydrazine in the reductive partition of U and Pu, it decreases the decontamination of U and Pu from fission products. Thus, its extraction behaviour with new extractants as N,N-diakylamides is useful to be known. TcO 4 - extraction in nitric acid media is compared for TBP and different amides. The influence of nitric acidity is related to the amides formula

Glucagon-like peptide-1 7-36 amide and peptide YY from the L-cell of the ileal mucosa are potent inhibitors of vagally induced gastric acid secretion in man

DEFF Research Database (Denmark)

Wettergren, A; Petersen, H; Orskov, C

1994-01-01

BACKGROUND: Glucagon-like peptide (GLP-1) 7-36 amide and peptide YY (PYY) from the L-cell of the ileal mucosa are potent inhibitors of gastric acid secretion in man. It is not clear, however, by which mechanism(s) they inhibit acid secretion. In dogs the inhibitory effect of PYY on acid secretion...

Equilibrium studies on liquid ammonia-potassium amide-hydrogen system at high pressures and temperatures (Preprint No. CA-10)

International Nuclear Information System (INIS)

Donde, M.M.; Srinivasa, K.; Raman, S.

1989-04-01

Insoluble deposits were observed to form during the operation of Heavy Water Plant at Talcher, based on ammonia-hydrogen exchange process with potassium amide as catalyst. Experiments were undertaken to investigate this phenomenon under controlled conditions in the laboratory employing high pressures and elevated temperatures. It was observed that deposit formation was very minimal in the autoclave and no visible deposit was left on the strainer-filter, in all the experiments. Deposit analysis showed the presence of potassium hydroxide monohydrate as major component and alpha-potassium hydroxide and potassium azide as minor components. It is suggested that the presence of hydroxide may be due to the reaction of amide with the residual moisture in the system during the experiment and any ingress of moisture while opening for collection of deposit. Azide formation is explained by following reactions occurring during the experiments. NH 3 +KNH 2 →NH 2 -NH 2 +KH; NH 2 -NH 2 +KNH 2 →KN 3 +3H 2 . (author). 1 fig

Photo-lability of deep ocean dissolved black carbon

Directory of Open Access Journals (Sweden)

A. Stubbins

2012-05-01

Full Text Available Dissolved black carbon (DBC, defined here as condensed aromatics isolated from seawater via PPL solid phase extraction and quantified as benzenepolycarboxylic acid (BPCA oxidation products, is a significant component of the oceanic dissolved organic carbon (DOC pool. These condensed aromatics are widely distributed in the open ocean and appear to be tens of thousands of years old. As such DBC is regarded as highly refractory. In the current study, the photo-lability of DBC, DOC and coloured dissolved organic matter (CDOM; ultraviolet-visible absorbance were determined over the course of a 28 day irradiation of North Atlantic Deep Water under a solar simulator. During the irradiation DBC fell from 1044 ± 164 nM-C to 55 ± 15 nM-C, a 20-fold decrease in concentration. Dissolved black carbon photo-degradation was more rapid and more extensive than for bulk CDOM and DOC. The concentration of DBC correlated with CDOM absorbance and the quality of DBC indicated by the ratios of different BPCAs correlated with CDOM absorbance spectral slope, suggesting the optical properties of CDOM may provide a proxy for both DBC concentrations and quality in natural waters. Further, the photo-lability of components of the DBC pool increased with their degree of aromatic condensation. These trends indicate that a continuum of compounds of varying photo-lability exists within the marine DOC pool. In this continuum, photo-lability scales with aromatic character, specifically the degree of condensation. Scaling the rapid photo-degradation of DBC to rates of DOC photo-mineralisation for the global ocean leads to an estimated photo-chemical half-life for oceanic DBC of less than 800 years. This is more than an order of magnitude shorter than the apparent age of DBC in the ocean. Consequently, photo-degradation is posited as the primary sink for oceanic DBC and the apparent survival of DBC molecules in the oceans for millennia appears to be facilitated not by their

Synthesis of a-amino amides via a-amino imidoylbenzotriazoles

Directory of Open Access Journals (Sweden)

ALAN R. KATRITZKY

2005-03-01

Full Text Available Reactions of isonitriles 11a-c with N-(a-aminoalkylbenzotriazoles 10a-k afford N-(a-aminoimidoylbenzotriazoles 12a-q which on hydrolysis by dilute hydrochloric acid gave a-amino amides 14a-j.

Benzoic Acid Production with Respect to Starter Culture and Incubation Temperature during Yogurt Fermentation using Response Surface Methodology.

Science.gov (United States)

Yu, Hyung-Seok; Lee, Na-Kyoung; Jeon, Hye-Lin; Eom, Su Jin; Yoo, Mi-Young; Lim, Sang-Dong; Paik, Hyun-Dong

2016-01-01

Benzoic acid is occasionally used as a raw material supplement in food products and is sometimes generated during the fermentation process. In this study, the production of naturally occurring yogurt preservatives was investigated for various starter cultures and incubation temperatures, and considered food regulations. Streptococcus thermophilus, Lactobacillus acidophilus, Lactobacillus delbrueckii subsp. bulgaricus, Lactobacillus rhamnosus, Lactobacillus casei, Lactobacillus paracasei, Lactobacillus reuteri, Lactobacillus plantarum, Bifidobacterium longum, Bifidobacterium lactis, Bifidobacterium bifidum, Bifidobacterium infantis, and Bifidobacterium breve were used as yogurt starter cultures in commercial starters. Among these strains, L. rhamnosus and L. paracasei showed the highest production of benzoic acid. Therefore, the use of L. rhamnosus, L. paracasei, S. thermophilus, and different incubation temperatures were examined to optimize benzoic acid production. Response surface methodology (RSM) based on a central composite design was performed for various incubation temperatures (35-44℃) and starter culture inoculum ratios (0-0.04%) in a commercial range of dairy fermentation processes. The optimum conditions were 0.04% L. rhamnosus, 0.01% L. paracasei, 0.02% S. thermophilus, and 38.12℃, and the predicted and estimated concentrations of benzoic acid were 13.31 and 13.94 mg/kg, respectively. These conditions maximized naturally occurring benzoic acid production during the yogurt fermentation process, and the observed production levels satisfied regulatory guidelines for benzoic acid in dairy products.

Conversion of amides to esters by the nickel-catalysed activation of amide C-N bonds.

Science.gov (United States)

Hie, Liana; Fine Nathel, Noah F; Shah, Tejas K; Baker, Emma L; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K N; Garg, Neil K

2015-08-06

Amides are common functional groups that have been studied for more than a century. They are the key building blocks of proteins and are present in a broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to the resonance stability of the amide bond. Although amides can readily be cleaved by enzymes such as proteases, it is difficult to selectively break the carbon-nitrogen bond of an amide using synthetic chemistry. Here we demonstrate that amide carbon-nitrogen bonds can be activated and cleaved using nickel catalysts. We use this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory calculations provide insight into the thermodynamics and catalytic cycle of the amide-to-ester transformation. Our results provide a way to harness amide functional groups as synthetic building blocks and are expected to lead to the further use of amides in the construction of carbon-heteroatom or carbon-carbon bonds using non-precious-metal catalysis.

LABILE IRON IN CELLS AND BODY FLUIDS . Physiology, Pathology and Pharmacology

Directory of Open Access Journals (Sweden)

Zvi Ioav Cabantchik

2014-03-01

Full Text Available In living systems iron appears predominantly associated with proteins, but can also be detected in forms referred as labile iron, which denotes the combined redox properties of iron and its amenability to exchange between ligands, including chelators. The labile cell iron (LCI composition varies with metal concentration and substances with chelating groups but also with pH and the redox potential. Although physiologically in the lower µM range, LCI plays a key role in cell iron economy as cross-roads of metabolic pathways. LCI levels are continually regulated by an iron-responsive machinery that balances iron uptake versus deposition into ferritin. However, LCI rises aberrantly in some cell types due to faulty cell utilization pathways or infiltration by pathological iron forms that are found in hemosiderotic plasma. As LCI attains pathological levels, it can catalyze reactive O species (ROS formation that, at particular threshold, can surpass cellular anti-oxidant capacities and seriously damage its constituents. While in normal plasma and interstitial fluids, virtually all iron is securely carried by circulating transferrin (that renders iron essentially non-labile, in systemic iron overload (IO, the total plasma iron binding capacity is often surpassed by a massive iron influx from hyperabsorptive gut or from erythrocyte overburdened spleen and/or liver. As plasma transferrin approaches iron saturation, labile plasma iron (LPI emerges in forms that can infiltrate cells by unregulated routes and raise LCI to toxic levels. Despite the limited knowledge available on LPI speciation in different types and degrees of iron overload, LPI measurements can be and are in fact used for identifying systemic IO and for initiating/adjusting chelation regimens to attain full-day LPI protection. A recent application of labile iron assay is the detection of labile components in iv iron formulations per se as well as in plasma (LPI following parenteral iron

Cross-Coupling of Amides with Alkylboranes via Nickel-Catalyzed C–N Bond Cleavage

KAUST Repository

Liu, Xiangqian; Hsiao, Chien-Chi; Guo, Lin; Rueping, Magnus

2018-01-01

A protocol for the nickel-catalyzed alkylation of amides was established. The use of alkylboranes as nucleophilic partners allowed the use of mild reaction conditions and compatibility of various functional groups with respect to both coupling partners. The catalytic alkylation proceeded selectively at the amides in the presence of other functional groups as well as other carboxylic acid derived moieties.

Cross-Coupling of Amides with Alkylboranes via Nickel-Catalyzed C–N Bond Cleavage

KAUST Repository

Liu, Xiangqian

2018-05-09

A protocol for the nickel-catalyzed alkylation of amides was established. The use of alkylboranes as nucleophilic partners allowed the use of mild reaction conditions and compatibility of various functional groups with respect to both coupling partners. The catalytic alkylation proceeded selectively at the amides in the presence of other functional groups as well as other carboxylic acid derived moieties.

N-Hydroxyimide Ugi Reaction toward α-Hydrazino Amides

NARCIS (Netherlands)

Chandgude, Ajay L; Dömling, Alexander

2017-01-01

The Ugi four-component reaction (U-4CR) with N-hydroxyimides as a novel carboxylic acid isostere has been reported. This reaction provides straightforward access to α-hydrazino amides. A broad range of aldehydes, amines, isocyanides and N-hydroxyimides were employed to give products in moderate to

Preparation and surface active properties of oxypropylated diol monoesters of fatty acids with an amide oxime terminal group

Directory of Open Access Journals (Sweden)

Eissa, A. M.F.

1994-10-01

Full Text Available Locally produced non-edible oil, namely, rice bran oil (R.B.O. was utilized as starting materials for preparing new nonionic surfactant. Oxypropylated diol monoesters of linoleic and rice bran oil fatty acids were prepared. Also amide oxime derivatives were obtained. Surface active properties of these compounds were measured. Under neutral condition amide eximes served as nonionic surfactants and their properties were similar to other oxypropylated monoesters.

Se ha utilizado un aceite no comestible de producción local, denominado, aceite de salvado de arroz (R.B.O. como materia prima para la preparación de nuevos tensioactivos no iónicos. Se prepararon diol monoésteres oxipropilados de ácido linoleico y ácidos grasos de aceite de salvado de arroz. También se obtuvieron los derivados de amido oxima. Se midieron las propiedades de tensión superficial de estos compuestos. Bajo condiciones neutras las amido eximas sirvieron como tensioactivos no iónicos y sus propiedades fueron similares a los de otros monoésteres oxipropilados.

Dissecting Hofmeister Effects: Direct Anion-Amide Interactions Are Weaker than Cation-Amide Binding.

Science.gov (United States)

Balos, Vasileios; Kim, Heejae; Bonn, Mischa; Hunger, Johannes

2016-07-04

Whereas there is increasing evidence for ion-induced protein destabilization through direct ion-protein interactions, the strength of the binding of anions to proteins relative to cation-protein binding has remained elusive. In this work, the rotational mobility of a model amide in aqueous solution was used as a reporter for the interactions of different anions with the amide group. Protein-stabilizing salts such as KCl and KNO3 do not affect the rotational mobility of the amide. Conversely, protein denaturants such as KSCN and KI markedly reduce the orientational freedom of the amide group. Thus these results provide evidence for a direct denaturation mechanism through ion-protein interactions. Comparing the present findings with results for cations shows that in contrast to common belief, anion-amide binding is weaker than cation-amide binding. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of ester and amide derivatives of titanium(IV) carboxymethylphosphonate

International Nuclear Information System (INIS)

Melánová, Klára; Beneš, Ludvík; Trchová, Miroslava; Svoboda, Jan; Zima, Vítězslav

2013-01-01

A set of layered ester and amide derivatives of titanium(IV) carboxymethylphosphonate was prepared by solvothermal treatment of amorphous titanium(IV) carboxymethylphosphonate with corresponding 1-alkanols, 1,ω-alkanediols, 1-aminoalkanes, 1,ω-diaminoalkanes and 1,ω-amino alcohols and characterized by powder X-ray diffraction, IR spectroscopy and thermogravimetric analysis. Whereas alkyl chains with one functional group form bilayers tilted to the layers, 1,ω-diaminoalkanes and most of 1,ω-alkanediols form bridges connecting the adjacent layers. In the case of amino alcohols, the alkyl chains form bilayer and either hydroxyl or amino group is used for bonding. This simple method for the synthesis of ester and amide derivatives does not require preparation of acid chloride derivative as a precursor or pre-intercalation with alkylamines and can be used also for the preparation of ester and amide derivatives of titanium carboxyethylphosphonate and zirconium carboxymethylphosphonate. - Graphical abstract: Ester and amide derivatives of layered titanium carboxymethylphosphonate were prepared by solvothermal treatment of amorphous solid with alkanol or alkylamine. - Highlights: • Ester and amide derivatives of titanium carboxymethylphosphonate. • Solvothermal treatment of amorphous solid with alkanol or alkylamine. • Ester and amide formation confirmed by IR spectroscopy

Reversible Twisting of Primary Amides via Ground State N-C(O) Destabilization: Highly Twisted Rotationally Inverted Acyclic Amides.

Science.gov (United States)

Meng, Guangrong; Shi, Shicheng; Lalancette, Roger; Szostak, Roman; Szostak, Michal

2018-01-17

Since the seminal studies by Pauling in 1930s, planarity has become the defining characteristic of the amide bond. Planarity of amides has central implications for the reactivity and chemical properties of amides of relevance to a range of chemical disciplines. While the vast majority of amides are planar, nonplanarity has a profound effect on the properties of the amide bond, with the most common method to restrict the amide bond relying on the incorporation of the amide function into a rigid cyclic ring system. In a major departure from this concept, here, we report the first class of acyclic twisted amides that can be prepared, reversibly, from common primary amides in a single, operationally trivial step. Di-tert-butoxycarbonylation of the amide nitrogen atom yields twisted amides in which the amide bond exhibits nearly perpendicular twist. Full structural characterization of a range of electronically diverse compounds from this new class of twisted amides is reported. Through reactivity studies we demonstrate unusual properties of the amide bond, wherein selective cleavage of the amide bond can be achieved by a judicious choice of the reaction conditions. Through computational studies we evaluate structural and energetic details pertaining to the amide bond deformation. The ability to selectively twist common primary amides, in a reversible manner, has important implications for the design and application of the amide bond nonplanarity in structural chemistry, biochemistry and organic synthesis.

Chemoselective reductive nucleophilic addition to tertiary amides, secondary amides, and N-methoxyamides.

Science.gov (United States)

Nakajima, Minami; Oda, Yukiko; Wada, Takamasa; Minamikawa, Ryo; Shirokane, Kenji; Sato, Takaaki; Chida, Noritaka

2014-12-22

As the complexity of targeted molecules increases in modern organic synthesis, chemoselectivity is recognized as an important factor in the development of new methodologies. Chemoselective nucleophilic addition to amide carbonyl centers is a challenge because classical methods require harsh reaction conditions to overcome the poor electrophilicity of the amide carbonyl group. We have successfully developed a reductive nucleophilic addition of mild nucleophiles to tertiary amides, secondary amides, and N-methoxyamides that uses the Schwartz reagent [Cp2 ZrHCl]. The reaction took place in a highly chemoselective fashion in the presence of a variety of sensitive functional groups, such as methyl esters, which conventionally require protection prior to nucleophilic addition. The reaction will be applicable to the concise synthesis of complex natural alkaloids from readily available amide groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lipoxygenase in Caragana jubata responds to low temperature, abscisic acid, methyl jasmonate and salicylic acid.

Science.gov (United States)

Bhardwaj, Pardeep Kumar; Kaur, Jagdeep; Sobti, Ranbir Chander; Ahuja, Paramvir Singh; Kumar, Sanjay

2011-09-01

Lipoxygenase (LOX) catalyses oxygenation of free polyunsaturated fatty acids into oxylipins, and is a critical enzyme of the jasmonate signaling pathway. LOX has been shown to be associated with biotic and abiotic stress responses in diverse plant species, though limited data is available with respect to low temperature and the associated cues. Using rapid amplification of cDNA ends, a full-length cDNA (CjLOX) encoding lipoxygenase was cloned from apical buds of Caragana jubata, a temperate plant species that grows under extreme cold. The cDNA obtained was 2952bp long consisting of an open reading frame of 2610bp encoding 869 amino acids protein. Multiple alignment of the deduced amino acid sequence with those of other plants demonstrated putative LH2/ PLAT domain, lipoxygenase iron binding catalytic domain and lipoxygenase_2 signature sequences. CjLOX exhibited up- and down-regulation of gene expression pattern in response to low temperature (LT), abscisic acid (ABA), methyl jasmonate (MJ) and salicylic acid (SA). Among all the treatments, a strong up-regulation was observed in response to MJ. Data suggests an important role of jasmonate signaling pathway in response to LT in C. jubata. Copyright © 2011 Elsevier B.V. All rights reserved.

Arachidonic Acid and Eicosapentaenoic Acid Metabolism in Juvenile Atlantic Salmon as Affected by Water Temperature.

Science.gov (United States)

Norambuena, Fernando; Morais, Sofia; Emery, James A; Turchini, Giovanni M

2015-01-01

Salmons raised in aquaculture farms around the world are increasingly subjected to sub-optimal environmental conditions, such as high water temperatures during summer seasons. Aerobic scope increases and lipid metabolism changes are known plasticity responses of fish for a better acclimation to high water temperature. The present study aimed at investigating the effect of high water temperature on the regulation of fatty acid metabolism in juvenile Atlantic salmon fed different dietary ARA/EPA ratios (arachidonic acid, 20:4n-6/ eicosapentaenoic acid, 20:5n-3), with particular focus on apparent in vivo enzyme activities and gene expression of lipid metabolism pathways. Three experimental diets were formulated to be identical, except for the ratio EPA/ARA, and fed to triplicate groups of Atlantic salmon (Salmo salar) kept either at 10°C or 20°C. Results showed that fatty acid metabolic utilisation, and likely also their dietary requirements for optimal performance, can be affected by changes in their relative levels and by environmental temperature in Atlantic salmon. Thus, the increase in temperature, independently from dietary treatment, had a significant effect on the β-oxidation of a fatty acid including EPA, as observed by the apparent in vivo enzyme activity and mRNA expression of pparα -transcription factor in lipid metabolism, including β-oxidation genes- and cpt1 -key enzyme responsible for the movement of LC-PUFA from the cytosol into the mitochondria for β-oxidation-, were both increased at the higher water temperature. An interesting interaction was observed in the transcription and in vivo enzyme activity of Δ5fad-time-limiting enzyme in the biosynthesis pathway of EPA and ARA. Such, at lower temperature, the highest mRNA expression and enzyme activity was recorded in fish with limited supply of dietary EPA, whereas at higher temperature these were recorded in fish with limited ARA supply. In consideration that fish at higher water temperature

Lack of effect of synthetic human gastric inhibitory polypeptide and glucagon-like peptide 1 [7-36 amide] infused at near-physiological concentrations on pentagastrin-stimulated gastric acid secretion in normal human subjects

DEFF Research Database (Denmark)

Nauck, M A; Bartels, E; Orskov, C

1992-01-01

-stimulated (0.1 micrograms/kg/h from -90 to 120 min) gastric volume, acid and chloride output, on separate occasions, synthetic human GIP (1 pmol/kg/min) and/or GLP-1 [7-36 amide] (0.3 pmol/kg/min) or placebo (0.9% NaCl with 1% albumin) were infused intravenously (from -30 to 120 min) in 9 healthy volunteers...... secretion). In conclusion, (penta)gastrin-stimulated gastric acid secretion is not inhibited by physiological circulating concentrations of GIP or GLP-1 [7-36 amide]. Therefore, the insulinotropic action of these intestinal hormones is physiologically more important than their possible role...

Synthesis, characterization and pharmacological evaluation of amide prodrugs of Flurbiprofen

International Nuclear Information System (INIS)

Mishra, Ashutosh; Veerasamy, Ravichandran; Jain, Prateek Kumar; Dixit, Vinod Kumar; Agrawal, Ram Kishor

2008-01-01

Flurbiprofen (FB) suffers from the general side effects of NSAIDs, owing to presence of free carboxylic acid group. The study was aimed to retard the adverse effects of gastrointestinal origin. Ten prodrugs of FB were synthesized by amidation with ethyl esters of amino acids, namely, glycine, L-phenylalanine, L-tryptophan, L-valine, L-isoleucine, L-alanine, L-leucine, L-glutamic acid, L-aspartic acid and β alanine. Purified synthesized prodrugs were characterized by m.p., TLC, solubility, partition coefficients, elemental analyses, UV, FTIR, NMR and MS. Synthesized prodrugs were subjected for bioavailability studies, analgesic, anti-inflammatory activities and ulcerogenic index. Marked reduction of ulcerogenic index and comparable analgesic, antiinflammatory activities were obtained in all cases as compared to FB. Among synthesized prodrugs AR-9, AR-10 and AR-2 showing excellent pharmacological response and encouraging hydrolysis rate both in (Simulated Intestinal Fluid) SIF and in 80% human plasma. Prodrugs with increased aliphatic side chain length or introduction of aromatic substituent resulted in enhanced partition coefficient but diminished dissolution and hydrolysis rate. Such prodrugs can be considered for sustained release purpose. (author)

Synthesis, characterization and pharmacological evaluation of amide prodrugs of Flurbiprofen

Energy Technology Data Exchange (ETDEWEB)

Mishra, Ashutosh; Veerasamy, Ravichandran; Jain, Prateek Kumar; Dixit, Vinod Kumar; Agrawal, Ram Kishor [Dr. H. S. Gour Vishwavidyalaya, Sagar (India). Dept. of Pharmaceutical Sciences. Pharmaceutical Chemistry Research Lab.]. E-mail: dragrawal2001@yahoo.co.in

2008-07-01

Flurbiprofen (FB) suffers from the general side effects of NSAIDs, owing to presence of free carboxylic acid group. The study was aimed to retard the adverse effects of gastrointestinal origin. Ten prodrugs of FB were synthesized by amidation with ethyl esters of amino acids, namely, glycine, L-phenylalanine, L-tryptophan, L-valine, L-isoleucine, L-alanine, L-leucine, L-glutamic acid, L-aspartic acid and {beta} alanine. Purified synthesized prodrugs were characterized by m.p., TLC, solubility, partition coefficients, elemental analyses, UV, FTIR, NMR and MS. Synthesized prodrugs were subjected for bioavailability studies, analgesic, anti-inflammatory activities and ulcerogenic index. Marked reduction of ulcerogenic index and comparable analgesic, antiinflammatory activities were obtained in all cases as compared to FB. Among synthesized prodrugs AR-9, AR-10 and AR-2 showing excellent pharmacological response and encouraging hydrolysis rate both in (Simulated Intestinal Fluid) SIF and in 80% human plasma. Prodrugs with increased aliphatic side chain length or introduction of aromatic substituent resulted in enhanced partition coefficient but diminished dissolution and hydrolysis rate. Such prodrugs can be considered for sustained release purpose. (author)

Evaluation of an amide-based stationary phase for supercritical fluid chromatography

Science.gov (United States)

Borges-Muñoz, Amaris C.; Colón, Luis A.

2017-01-01

A relatively new stationary phase containing a polar group embedded in a hydrophobic backbone (i.e., ACE® C18-amide) was evaluated for use in supercritical fluid chromatography. The amide-based column was compared with columns packed with bare silica, C18 silica, and a terminal-amide silica phase. The system was held at supercritical pressure and temperature with a mobile phase composition of CO2 and methanol as cosolvent. The linear solvation energy relationship model was used to evaluate the behavior of these stationary phases, relating the retention factor of selected probes to specific chromatographic interactions. A five-component test mixture, consisting of a group of drug-like molecules was separated isocratically. The results show that the C18-amide stationary phase provided a combination of interactions contributing to the retention of the probe compounds. The hydrophobic interactions are favorable; however, the electron donating ability of the embedded amide group shows a large positive interaction. Under the chromatographic conditions used, the C18-amide column was able to provide baseline resolution of all the drug-like probe compounds in a text mixture, while the other columns tested did not. PMID:27396487

Simultaneous Inhibition of Fatty Acid Amide Hydrolase and Monoacylglycerol Lipase Shares Discriminative Stimulus Effects with Δ9-Tetrahydrocannabinol in Mice

OpenAIRE

Hruba, Lenka; Seillier, Alexandre; Zaki, Armia; Cravatt, Benjamin F.; Lichtman, Aron H.; Giuffrida, Andrea; McMahon, Lance R.

2015-01-01

Monoacylglycerol lipase (MAGL) and fatty acid amide hydrolase (FAAH) inhibitors exert preclinical effects indicative of therapeutic potential (i.e., analgesia). However, the extent to which MAGL and FAAH inhibitors produce unwanted effects remains unclear. Here, FAAH and MAGL inhibition was examined separately and together in a Δ9-tetrahydrocannabinol (Δ9-THC; 5.6 mg/kg i.p.) discrimination assay predictive of subjective effects associated with cannabis use, and the relative contribution of N...

Effects of temperature, packaging and electron beam irradiation processing conditions on the property behaviour of Poly (ether-block-amide) blends

Energy Technology Data Exchange (ETDEWEB)

Murray, Kieran A., E-mail: kmurray@research.ait.ie [Materials Research Institute, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland); Kennedy, James E., E-mail: jkennedy@ait.ie [Materials Research Institute, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland); McEvoy, Brian, E-mail: Brian.Mcevoy@synergyhealthplc.com [Synergy Health, IDA Business and Technology Park, Sragh, Tullamore, Co. Offaly (Ireland); Vrain, Olivier, E-mail: Olivier.Vrain@synergyhealthplc.com [Synergy Health, IDA Business and Technology Park, Sragh, Tullamore, Co. Offaly (Ireland); Ryan, Damien, E-mail: Damien.Ryan@synergyhealthplc.com [Synergy Health, IDA Business and Technology Park, Sragh, Tullamore, Co. Offaly (Ireland); Cowman, Richard, E-mail: Richard.Cowman@synergyhealthplc.com [Synergy Health, IDA Business and Technology Park, Sragh, Tullamore, Co. Offaly (Ireland); Higginbotham, Clement L., E-mail: chigginbotham@ait.ie [Materials Research Institute, Athlone Institute of Technology, Dublin Road, Athlone, Co. Westmeath (Ireland)

2014-06-01

The radiation stability of Poly (ether-block-amide) (PEBA) blended with a multifunctional phenolic antioxidant and a hindered amide light stabiliser was examined under various temperatures, packaging and electron beam processing conditions. FTIR revealed that there were slight alterations to the PEBA before irradiation; however, these became more pronounced following irradiation. The effect of varying the temperature, packaging and processing conditions on the resultant PEBA properties was apparent. For example, rheology demonstrated that the structural properties could be enhanced by manipulating the aforementioned criteria. Mechanical testing exhibited less radiation resistance when the PEBA samples were vacuum packed and exposed to irradiation. MFI and AFM confirmed that the melting strength and surface topography could be reduced/increased depending on the conditions employed. From this study it was concluded that virgin PEBA submerged in dry ice with non-vacuum packaging during the irradiation process, provided excellent radiation resistance (20.9% improvement) in contrast to the traditional method. - Highlights: • PEBA was melt blended with Irganox 565 and Tinuvin 783. • All virgin and blended PEBA samples were exposed to electron beam irradiation. • Virgin and blended PEBA was exposed to different temperatures during irradiation. • Non-vacuum and vacuum packed PEBA samples were compared following irradiation. • Virgin PEBA with non-vacuum packaging in dry ice improved the radiation resistance.

Effects of temperature, packaging and electron beam irradiation processing conditions on the property behaviour of Poly (ether-block-amide) blends

International Nuclear Information System (INIS)

Murray, Kieran A.; Kennedy, James E.; McEvoy, Brian; Vrain, Olivier; Ryan, Damien; Cowman, Richard; Higginbotham, Clement L.

2014-01-01

The radiation stability of Poly (ether-block-amide) (PEBA) blended with a multifunctional phenolic antioxidant and a hindered amide light stabiliser was examined under various temperatures, packaging and electron beam processing conditions. FTIR revealed that there were slight alterations to the PEBA before irradiation; however, these became more pronounced following irradiation. The effect of varying the temperature, packaging and processing conditions on the resultant PEBA properties was apparent. For example, rheology demonstrated that the structural properties could be enhanced by manipulating the aforementioned criteria. Mechanical testing exhibited less radiation resistance when the PEBA samples were vacuum packed and exposed to irradiation. MFI and AFM confirmed that the melting strength and surface topography could be reduced/increased depending on the conditions employed. From this study it was concluded that virgin PEBA submerged in dry ice with non-vacuum packaging during the irradiation process, provided excellent radiation resistance (20.9% improvement) in contrast to the traditional method. - Highlights: • PEBA was melt blended with Irganox 565 and Tinuvin 783. • All virgin and blended PEBA samples were exposed to electron beam irradiation. • Virgin and blended PEBA was exposed to different temperatures during irradiation. • Non-vacuum and vacuum packed PEBA samples were compared following irradiation. • Virgin PEBA with non-vacuum packaging in dry ice improved the radiation resistance

Amide-induced phase separation of hexafluoroisopropanol-water mixtures depending on the hydrophobicity of amides.

Science.gov (United States)

Takamuku, Toshiyuki; Wada, Hiroshi; Kawatoko, Chiemi; Shimomura, Takuya; Kanzaki, Ryo; Takeuchi, Munetaka

2012-06-21

Amide-induced phase separation of hexafluoro-2-propanol (HFIP)-water mixtures has been investigated to elucidate solvation properties of the mixtures by means of small-angle neutron scattering (SANS), (1)H and (13)C NMR, and molecular dynamics (MD) simulation. The amides included N-methylformamide (NMF), N-methylacetamide (NMA), and N-methylpropionamide (NMP). The phase diagrams of amide-HFIP-water ternary systems at 298 K showed that phase separation occurs in a closed-loop area of compositions as well as an N,N-dimethylformamide (DMF) system previously reported. The phase separation area becomes wider as the hydrophobicity of amides increases in the order of NMF amides due to the hydrophobic interaction gives rise to phase separation of the mixtures. In contrast, the disruption of HFIP clusters causes the recovery of the homogeneity of the ternary systems. The present results showed that HFIP clusters are evolved with increasing amide content to the lower phase separation concentration in the same mechanism among the four amide systems. However, the disruption of HFIP clusters in the NMP and DMF systems with further increasing amide content to the upper phase separation concentration occurs in a different way from those in the NMF and NMA systems.

Hemodynamic changes in systolic and diastolic function during isoproterenol challenge predicts symptomatic response to myectomy in hypertrophic cardiomyopathy with labile obstruction.

Science.gov (United States)

Prasad, Megha; Geske, Jeffrey B; Sorajja, Paul; Ommen, Steve R; Schaff, Hartzell V; Gersh, Bernard J; Nishimura, Rick A

2016-11-15

We aimed to assess the utility of changes in systolic and diastolic function by isoproterenol challenge in predicting symptom resolution post-myectomy in selected patients with hypertrophic cardiomyopathy (HCM) and labile obstruction. In a subset of symptomatic HCM patients without resting/provocable obstruction on noninvasive assessment, isoproterenol challenge during hemodynamic catheterization may elicit labile left ventricular outflow tract (LVOT) obstruction, and demonstrate the effect of obstruction on diastolic function. These changes may determine whether patients achieve complete symptom resolution post-myectomy. Between February 2003 and April 2009, 18 symptomatic HCM patients without LVOT obstruction on noninvasive testing underwent isoproterenol provocation and septal myectomy due to presence of provocable gradient and were followed for 4 (IQR 3-7) years. Thirteen (72.2%) had complete symptom resolution, while 5 (27.8%) had improved, but persistent symptoms. Those with provoked gradient >100 mm Hg or increase in left atrial pressure (LAP) with isoproterenol had symptom resolution. Symptomatic HCM patients without LVOT gradient on noninvasive testing may demonstrate labile obstruction with isoproterenol. With isoproterenol, patients with high LVOT gradient or increase in LAP concomitant with an increase in gradient achieved complete symptom resolution post-myectomy. Thus, improved diastolic filling as well as outflow gradient production in patients with HCM may predict symptom response to myectomy. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Conversion of Amides to Esters by the Nickel-Catalyzed Activation of Amide C–N Bonds

Science.gov (United States)

Hie, Liana; Fine Nathel, Noah F.; Shah, Tejas K.; Baker, Emma L.; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K. N.; Garg, Neil K.

2015-01-01

Amides are common functional groups that have been well studied for more than a century.1 They serve as the key building blocks of proteins and are present in an broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to resonance stability of the amide bond.1,2 Whereas Nature can easily cleave amides through the action of enzymes, such as proteases,3 the ability to selectively break the C–N bond of an amide using synthetic chemistry is quite difficult. In this manuscript, we demonstrate that amide C–N bonds can be activated and cleaved using nickel catalysts. We have used this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory (DFT) calculations provide insight into the thermodynamics and catalytic cycle of this unusual transformation. Our results provide a new strategy to harness amide functional groups as synthons and are expected fuel the further use of amides for the construction of carbon–heteroatom or carbon–carbon bonds using non-precious metal catalysis. PMID:26200342

Formation and hydrolysis of amide bonds by lipase A from Candida antarctica; exceptional features.

Science.gov (United States)

Liljeblad, Arto; Kallio, Pauli; Vainio, Marita; Niemi, Jarmo; Kanerva, Liisa T

2010-02-21

Various commercial lyophilized and immobilized preparations of lipase A from Candida antarctica (CAL-A) were studied for their ability to catalyze the hydrolysis of amide bonds in N-acylated alpha-amino acids, 3-butanamidobutanoic acid (beta-amino acid) and its ethyl ester. The activity toward amide bonds is highly untypical of lipases, despite the close mechanistic analogy to amidases which normally catalyze the corresponding reactions. Most CAL-A preparations cleaved amide bonds of various substrates with high enantioselectivity, although high variations in substrate selectivity and catalytic rates were detected. The possible role of contaminant protein species on the hydrolytic activity toward these bonds was studied by fractionation and analysis of the commercial lyophilized preparation of CAL-A (Cat#ICR-112, Codexis). In addition to minor impurities, two equally abundant proteins were detected, migrating on SDS-PAGE a few kDa apart around the calculated size of CAL-A. Based on peptide fragment analysis and sequence comparison both bands shared substantial sequence coverage with CAL-A. However, peptides at the C-terminal end constituting a motile domain described as an active-site flap were not identified in the smaller fragment. Separated gel filtration fractions of the two forms of CAL-A both catalyzed the amide bond hydrolysis of ethyl 3-butanamidobutanoate as well as the N-acylation of methyl pipecolinate. Hydrolytic activity towards N-acetylmethionine was, however, solely confined to the fractions containing the truncated form of CAL-A. These fractions were also found to contain a trace enzyme impurity identified in sequence analysis as a serine carboxypeptidase. The possible role of catalytic impurities versus the function of CAL-A in amide bond hydrolysis is further discussed in the paper.

Amides in Nature and Biocatalysis.

Science.gov (United States)

Pitzer, Julia; Steiner, Kerstin

2016-10-10

Amides are widespread in biologically active compounds with a broad range of applications in biotechnology, agriculture and medicine. Therefore, as alternative to chemical synthesis the biocatalytic amide synthesis is a very interesting field of research. As usual, Nature can serve as guide in the quest for novel biocatalysts. Several mechanisms for carboxylate activation involving mainly acyl-adenylate, acyl-phosphate or acyl-enzyme intermediates have been discovered, but also completely different pathways to amides are found. In addition to ribosomes, selected enzymes of almost all main enzyme classes are able to synthesize amides. In this review we give an overview about amide synthesis in Nature, as well as biotechnological applications of these enzymes. Moreover, several examples of biocatalytic amide synthesis are given. Copyright © 2016 Elsevier B.V. All rights reserved.

Metal cation dependence of interactions with amino acids: bond dissociation energies of Rb(+) and Cs(+) to the acidic amino acids and their amide derivatives.

Science.gov (United States)

Armentrout, P B; Yang, Bo; Rodgers, M T

2014-04-24

Metal cation-amino acid interactions are key components controlling the secondary structure and biological function of proteins, enzymes, and macromolecular complexes comprising these species. Determination of pairwise interactions of alkali metal cations with amino acids provides a thermodynamic vocabulary that begins to quantify these fundamental processes. In the present work, we expand a systematic study of such interactions by examining rubidium and cesium cations binding with the acidic amino acids (AA), aspartic acid (Asp) and glutamic acid (Glu), and their amide derivatives, asparagine (Asn) and glutamine (Gln). These eight complexes are formed using electrospray ionization and their bond dissociation energies (BDEs) are determined experimentally using threshold collision-induced dissociation with xenon in a guided ion beam tandem mass spectrometer. Analyses of the energy-dependent cross sections include consideration of unimolecular decay rates, internal energy of the reactant ions, and multiple ion-neutral collisions. Quantum chemical calculations are conducted at the B3LYP, MP2(full), and M06 levels of theory using def2-TZVPPD basis sets, with results showing reasonable agreement with experiment. At 0 and 298 K, most levels of theory predict that the ground-state conformers for M(+)(Asp) and M(+)(Asn) involve tridentate binding of the metal cation to the backbone carbonyl, amino, and side-chain carbonyl groups, although tridentate binding to the carboxylic acid group and side-chain carbonyl is competitive for M(+)(Asn). For the two longer side-chain amino acids, Glu and Gln, multiple structures are competitive. A comparison of these results to those for the smaller alkali cations, Na(+) and K(+), provides insight into the trends in binding energies associated with the molecular polarizability and dipole moment of the side chain. For all four metal cations, the BDEs are inversely correlated with the size of the metal cation and follow the order Asp < Glu

Expression and purification of antimicrobial peptide adenoregulin with C-amidated terminus in Escherichia coli.

Science.gov (United States)

Cao, Wei; Zhou, Yuxun; Ma, Yushu; Luo, Qingping; Wei, Dongzhi

2005-04-01

Adenoregulin is a 33 amino acid antimicrobial peptide isolated from the skin of the arboreal frog Phyllomedusa bicolor. Natural adenoregulin is synthesized with an amidated valine residue at C-terminus and shows lethal effects against filamentous fungi, as well as a broad spectrum of pathogenic microorganisms. A synthetic gene for adenoregulin (ADR) with an additional amino acid glutamine at C-terminus was cloned into pET32a vector to allow expression of ADR as a Trx fusion protein in Escherichia coli BL21(DE3). The resulting expression level of the fusion protein could reach up to 20% of the total cell proteins. The fusion protein could be purified effectively by Ni2+-chelating chromatography. Released from the fusion protein by enterokinase cleavage and purified to homogeneity, the recombinant ADR displayed antimicrobial activity similar to that of the synthetic ADR reported earlier. Comparing the antimicrobial activities of the recombinant adenoregulin with C-amidated terminus to that without an amidated C-terminus, we found that the amide of glutamine at C-terminus of ADR improved its potency on certain microorganisms such as Tritirachium album and Saccharomyces cerevisiae.

N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage.

Science.gov (United States)

Meng, Guangrong; Lalancette, Roger; Szostak, Roman; Szostak, Michal

2017-09-01

Despite recent progress in catalytic cross-coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled n N → π Ar conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating acyl-metal intermediates from unactivated primary and secondary amides.

Arachidonic Acid and Eicosapentaenoic Acid Metabolism in Juvenile Atlantic Salmon as Affected by Water Temperature.

Directory of Open Access Journals (Sweden)

Fernando Norambuena

Full Text Available Salmons raised in aquaculture farms around the world are increasingly subjected to sub-optimal environmental conditions, such as high water temperatures during summer seasons. Aerobic scope increases and lipid metabolism changes are known plasticity responses of fish for a better acclimation to high water temperature. The present study aimed at investigating the effect of high water temperature on the regulation of fatty acid metabolism in juvenile Atlantic salmon fed different dietary ARA/EPA ratios (arachidonic acid, 20:4n-6/ eicosapentaenoic acid, 20:5n-3, with particular focus on apparent in vivo enzyme activities and gene expression of lipid metabolism pathways. Three experimental diets were formulated to be identical, except for the ratio EPA/ARA, and fed to triplicate groups of Atlantic salmon (Salmo salar kept either at 10°C or 20°C. Results showed that fatty acid metabolic utilisation, and likely also their dietary requirements for optimal performance, can be affected by changes in their relative levels and by environmental temperature in Atlantic salmon. Thus, the increase in temperature, independently from dietary treatment, had a significant effect on the β-oxidation of a fatty acid including EPA, as observed by the apparent in vivo enzyme activity and mRNA expression of pparα -transcription factor in lipid metabolism, including β-oxidation genes- and cpt1 -key enzyme responsible for the movement of LC-PUFA from the cytosol into the mitochondria for β-oxidation-, were both increased at the higher water temperature. An interesting interaction was observed in the transcription and in vivo enzyme activity of Δ5fad-time-limiting enzyme in the biosynthesis pathway of EPA and ARA. Such, at lower temperature, the highest mRNA expression and enzyme activity was recorded in fish with limited supply of dietary EPA, whereas at higher temperature these were recorded in fish with limited ARA supply. In consideration that fish at higher

Barbier Continuous Flow Preparation and Reactions of Carbamoyllithiums for Nucleophilic Amidation.

Science.gov (United States)

Ganiek, Maximilian A; Becker, Matthias R; Berionni, Guillaume; Zipse, Hendrik; Knochel, Paul

2017-08-01

An ambient temperature continuous flow method for nucleophilic amidation and thioamidation is described. Deprotonation of formamides by lithium diisopropylamine (LDA) affords carbamoyllithium intermediates that are quenched in situ with various electrophiles such as ketones, allyl bromides, Weinreb and morpholino amides. The nature of the reactive lithium intermediates and the thermodynamics of the metalation were further investigated by ab initio calculations and kinetic experiments. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of new optically active poly(amide ...

African Journals Online (AJOL)

Synthesis and characterization of new optically active poly(amide-imide)s based on N -trimellitimido- ... Bulletin of the Chemical Society of Ethiopia ... (DMAc), dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) at room temperature.

Synthesis, Antifungal Evaluation and In Silico Study of N-(4-Halobenzyl)amides.

Science.gov (United States)

Montes, Ricardo Carneiro; Perez, Ana Luiza A L; Medeiros, Cássio Ilan S; Araújo, Marianna Oliveira de; Lima, Edeltrudes de Oliveira; Scotti, Marcus Tullius; Sousa, Damião Pergentino de

2016-12-13

A collection of 32 structurally related N -(4-halobenzyl)amides were synthesized from cinnamic and benzoic acids through coupling reactions with 4-halobenzylamines, using (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP) as a coupling agent. The compounds were identified by spectroscopic methods such as infrared, ¹H- and 13 C- Nuclear Magnetic Resonance (NMR) and high-resolution mass spectrometry. The compounds were then submitted to antimicrobial tests by the minimum inhibitory concentration method (MIC) and nystatin was used as a control in the antifungal assays. The purpose of the tests was to evaluate the influence of structural changes in the cinnamic and benzoic acid substructures on the inhibitory activity against strains of Candida albicans , Candida tropicalis , and Candida krusei . A quantitative structure-activity relationship (QSAR) study with KNIME v. 3.1.0 and Volsurf v. 1.0.7 softwares were realized, showing that descriptors DRDRDR, DRDRAC, L4LgS, IW4 and DD2 influence the antifungal activity of the haloamides. In general, 10 benzamides revealed fungal sensitivity, especially a vanillic amide which enjoyed the lowest MIC. The results demonstrate that a hydroxyl group in the para position, and a methoxyl at the meta position enhance antifungal activity for the amide skeletal structure. In addition, the double bond as a spacer group appears to be important for the activity of amide structures.

Supercritical fluid extraction of uranium and thorium employing dialkyl amides

International Nuclear Information System (INIS)

Rao, Ankita; Kumar, Pradeep

2014-01-01

Extraction and purification of actinides from different matrices is of utmost importance to the nuclear industry. In recent decades, supercritical fluid extraction (SFE) has emerged as a promising alternative to solvent extraction owing to its inherent potential of minimization of liquid waste generation. N,N-dialkyl aliphatic amides have been proposed to be an alternative to TBP in the reprocessing of spent nuclear fuel due to several attractive features like innocuous nature of degradation products (mainly carboxylic acids/ amines), possibility of complete incineration of the used extractant leading to reduction in volume of secondary waste. Also, physico-chemical properties of this class of extractants can be tuned by the judicious choice of alkyl groups. In the present work, N,N-dialkyl aliphatic amides with varying alkyl groups viz. N,N-dibutyl-2-ethylhexanamide (DBEHA), N,N-dibutyl-3,3-dimethylbutanamide (DBDMBA), N,N-dihexyloctanamide (DHOA), N,N-disecbutylpentamide (DBPA), N,N-dibutyloctanamide (DBOA), have been evaluated for supercritical fluid extraction (SFE) of uranium and thorium from nitric acid medium as well as tissue paper matrix. Amides were obtained from Department of Chemistry, Delhi University and were used as such. This fact could be exploited for separation of thorium and uranium

Food emulsions with amidated pectin from celery (Apium graveolens var. rapaceum D.C. tubers

Directory of Open Access Journals (Sweden)

Iv. Petrova

2017-09-01

Full Text Available Abstract. Hydrocolloids, especially polysaccharides from traditional plant sources and their derivatives possessed significant emulsifying properties. Pectin was isolated from celery tubers by accelerated “green” method for extraction based on ultrasonic irradiation. Further chemical modification of celery pectin was performed with 4 mol/L NH The amidated celery pectin was obtained with the following characteristics: the degree of esterification (DE 31%, the degree of 3. amidation (DA 16%, degree of acetylation (DAc 2% and anhydrouronic acid content (AUAC 68%. This modified pectin was incorporated in preparation of model 30, 40 and 50% oil-in-water emulsions. The effect of amidation of celery pectin on the stability of emulsions was investigated. The results showed that amidation increased the emulsifying properties of pectic polysaccharides. It affected also the rheological characteristics of model emulsion. The current study demonstrated preparation of emulsion with low-caloric amidated pectin as proper alternative to the traditional emulsifiers.

Vibrational lifetimes of protein amide modes

International Nuclear Information System (INIS)

Peterson, K.A.; Rella, C.A.

1995-01-01

Measurement of the lifetimes of vibrational modes in proteins has been achieved with a single frequency infrared pump-probe technique using the Stanford Picosecond Free-electron Laser, These are the first direct measurements of vibrational dynamics in the polyamide structure of proteins. In this study, modes associated with the protein backbone are investigated. Results for the amide I band, which consists mainly of the stretching motion of the carbonyl unit of the amide linkage, show that relaxation from the first vibrational excited level (v=1) to the vibrational ground state (v=0) occurs within 1.5 picoseconds with apparent first order kinetics. Comparison of lifetimes for myoglobin and azurin, which have differing secondary structures, show a small but significant difference. The lifetime for the amide I band of myoglobin is 300 femtoseconds shorter than for azurin. Further measurements are in progress on other backbone vibrational modes and on the temperature dependence of the lifetimes. Comparison of vibrational dynamics for proteins with differing secondary structure and for different vibrational modes within a protein will lead to a greater understanding of energy transfer and dissipation in biological systems. In addition, these results have relevance to tissue ablation studies which have been conducted with pulsed infrared lasers. Vibrational lifetimes are necessary for calculating the rate at which the energy from absorbed infrared photons is converted to equilibrium thermal energy within the irradiated volume. The very fast vibrational lifetimes measured here indicate that mechanisms which involve direct vibrational up-pumping of the amide modes with consecutive laser pulses, leading to bond breakage or weakening, are not valid

Designing of molecular architecture, synthesis and properties of the next generation of state-of-the-art high-performance thermoplastic fluoro-poly(ether amide)s, (6F-PEA), fluoro-poly(ether amide-imide)s (6F-PEAI), and their co-polymers

International Nuclear Information System (INIS)

Vora, Rohitkumar H.

2010-01-01

-copoly(ether amide-imide-(ether imide))s (6F-co(PEAI-PEI)) were also designed and synthesized using 2,2'-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydrides (6FDA). Solution, thermal, electrical, chemical resistance, thermo-oxidative and hydrolytic stabilities, etc., properties of two series of polymers and co-polymers were analyzed. These 6F-polymers possess moderate to high glass transition temperature (T g ). The T g values of co-polymers were re-confirmed by the Fox-Vora equation. These polymers showed excellent resistance toward thermo-oxidative degradation in isothermal heating at temperature 300 deg. C for 300 h. Most of these 6F-PEAI, 6F-PEAI, 6F-co(PEA-PEI), 6F-co(PEA-PEAI) and 6F-co(PEA-PEAI) polymers also shown to have low moisture uptake at 100% relative humidity at 50 deg. C over 100 h. The dielectric constant (ε') of these polymers in addition to experimentally measuring, were also estimated by the additive group contribution calculation using mathematical equations defined by the Lorentz-Lorenz's theory and the Vogel's theory, and by Vora-Wang equations, respectively. Their dielectric constants (ε' H and Upilex S . The amorphous nature of these designed 6F-polymers renders them readily processable into films, sheets, etc., molded articles.

A protocol for amide bond formation with electron deficient amines and sterically hindered substrates

DEFF Research Database (Denmark)

Due-Hansen, Maria E; Pandey, Sunil K; Christiansen, Elisabeth

2016-01-01

A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed.......A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed....

Mechanistic insight into benzenethiol catalyzed amide bond formations from thioesters and primary amines

DEFF Research Database (Denmark)

Stuhr-Hansen, Nicolai; Bork, Nicolai; Strømgaard, Kristian

2014-01-01

The influence of arylthiols on cysteine-free ligation, i.e. the reaction between an alkyl thioester and a primary amine forming an amide bond, was studied in a polar aprotic solvent. We reacted the ethylthioester of hippuric acid with cyclohexylamine in the absence or presence of various quantities...... of thiophenol (PhSH) in a slurry of disodium hydrogen phosphate in dry DMF. Quantitative conversions into the resulting amide were observed within a few hours in the presence of equimolar amounts of thiophenol. Ab initio calculations showed that the reaction mechanism in DMF is similar to the well-known aqueous...... reaction mechanism. The energy barrier of the catalyzed amidation reaction is approximately 40 kJ mol(-1) lower than the non-catalyzed amidation reaction. At least partially this can be explained by a hydrogen bond from the amine to the π-electrons of the thiophenol, stabilizing the transition state...

PURIFICATION AND CHARACTERIZATION OF AN OXYGEN-LABILE, NAD-DEPENDENT ALCOHOL-DEHYDROGENASE FROM DESULFOVIBRIO-GIGAS

NARCIS (Netherlands)

HENSGENS, CMH; VONCK, J; VANBEEUMEN, J; VANBRUGGEN, EFJ; HANSEN, TA

A NAD-dependent, oxygen-labile alcohol dehydrogenase was purified from Desulfovibrio gigas. It was decameric, with subunits of M(r) 43,000. The best substrates were ethanol (K(m), 0.15 mM) and 1-propanol (K(m), 0.28 mM). N-terminal amino acid sequence analysis showed that the enzyme belongs to the

Evaluation of unsaturated alkanoic acid amides as maskers of epigallocatechin gallate astringency.

Science.gov (United States)

Obst, Katja; Paetz, Susanne; Backes, Michael; Reichelt, Katharina V; Ley, Jakob P; Engel, Karl-Heinz

2013-05-08

Some foods, beverages, and food ingredients show characteristic long-lasting aftertastes. The sweet, lingering taste of high intensity sweeteners or the astringency of tea catechins are typical examples. Epigallocatechin-3-gallate (EGCG), the most abundant catechin in green tea, causes a long-lasting astringency and bitterness. These sensations are mostly perceived as aversive and are only accepted in a few foods (e.g., tea and red wine). For the evaluation of the aftertaste of such constituents over a certain period of time, Intensity Variation Descriptive Methodology (IVDM) was used. The approach allows the measurement of different descriptors in parallel in one panel session. IVDM was evaluated concerning the inter- and intraindividual differences of panelists for bitterness and astringency of EGCG. Subsequently, the test method was used as a screening tool for the identification of potential modality-selective masking compounds. In particular, the intensity of the astringency of EGCG (750 mg kg(-1)) could be significantly lowered by 18-33% during the time course by adding the trigeminal-active compound trans-pellitorine (2E,4E-decadienoic acid N-isobutyl amide 1, 5 mg kg(-1)) without significantly affecting bitterness perception. Further, structurally related compounds were evaluated on EGCG to gain evidence for possible structure-activity relationships. A more polar derivative of 1, (2S)-2-[[(2E,4E)-deca-2,4-dienoyl]amino]propanoic acid 9, was also able to reduce the astringency of EGCG similar to trans-pellitorine but without showing the strong tingling effect.

Electrode reactions of ruthenium–bipyridine complex in amide-type ionic liquids

International Nuclear Information System (INIS)

Toshimitsu, Yuichi; Katayama, Yasushi; Miura, Takashi

2012-01-01

The electrode kinetics of [Ru(bpy) 3 ] 3+ /[Ru(bpy) 3 ] 2+ (bpy = 2,2′-bipyridine) on a platinum electrode was investigated in room-temperature ionic liquids, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMITFSA), and 1-butyl-1-methylpyrrolidinium bis(perfluoroethylsulfonyl)amide (BMPBETA) over the temperature range from 25 to 45 °C. The diffusion coefficients of [Ru(bpy) 3 ] 2+ and [Ru(bpy) 3 ] 3+ were found to be affected not only by the viscosity of ionic liquids but also by the charge density of the complex. The activation energy for the diffusion coefficients of these complexes in the ionic liquids were close to that for the viscosity of the ionic liquids. The standard rate constants of [Ru(bpy) 3 ] 3+ /[Ru(bpy) 3 ] 2+ in BMPTFSA, EMITFSA and BMPBETA were estimated by electrochemical impedance spectroscopy. The standard rate constants in the ionic liquids were estimated to be smaller than those in aqueous and organic electrolytes, probably due to the slow dynamics of the ionic liquids.

Isentropic compressibilities of (amide + water) mixtures: A comparative study

International Nuclear Information System (INIS)

Papamatthaiakis, Dimitris; Aroni, Fryni; Havredaki, Vasiliki

2008-01-01

The density and ultrasonic velocity of aqueous solutions of formamide (FA), N-methylformamide (NMF), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), pyrrolidin-2-one (PYR), N-methyl-2-pyrrolidinone (NMP), and their pure phases have been measured at 298.15 K and atmospheric pressure. Densities and ultrasonic velocities in pure amides have been also measured at the temperature range 288.15 K to 308.15 K for the computation of their thermal expansivities. Isentropic compressibility, intermolecular free length, relative association, apparent molar compressibility, as well as the excess quantities, ultrasonic velocity, isentropic compressibility, intermolecular free length, have been evaluated and fitted to the Redlich-Kister type equation. The deviation from ideal mixing law in ultrasonic velocity is positive while the deviations in isentropic compressibility and intermolecular free length are negative for all (amide + water) mixtures. This behavior reveals the nature and the magnitude of intermolecular interactions between the amide-water molecules. The sequence of superimposed curves of various ultrasonic parameters vs. the amide mole fraction is related to the strength of interactions between the unlike molecules and the role of -CH 3 substitution in amides. The comparison of ultrasonic to volumetric properties reveals differences on the position of the extrema and their relation with the degree of substitution while the interpretation of these differences is discussed. Two different approaches on the computation of excess functions, applied in this work, brought out a difference in the magnitude of deviations and a partial reversion to the sequence of amides curves suggesting a different estimation in terms of deviations from ideal mixing law and therefore of the relative molecular interactions

Identification and characterization of carprofen as a multitarget fatty acid amide hydrolase/cyclooxygenase inhibitor.

Science.gov (United States)

Favia, Angelo D; Habrant, Damien; Scarpelli, Rita; Migliore, Marco; Albani, Clara; Bertozzi, Sine Mandrup; Dionisi, Mauro; Tarozzo, Glauco; Piomelli, Daniele; Cavalli, Andrea; De Vivo, Marco

2012-10-25

Pain and inflammation are major therapeutic areas for drug discovery. Current drugs for these pathologies have limited efficacy, however, and often cause a number of unwanted side effects. In the present study, we identify the nonsteroidal anti-inflammatory drug carprofen as a multitarget-directed ligand that simultaneously inhibits cyclooxygenase-1 (COX-1), COX-2, and fatty acid amide hydrolase (FAAH). Additionally, we synthesized and tested several derivatives of carprofen, sharing this multitarget activity. This may result in improved analgesic efficacy and reduced side effects (Naidu et al. J. Pharmacol. Exp. Ther.2009, 329, 48-56; Fowler, C. J.; et al. J. Enzyme Inhib. Med. Chem.2012, in press; Sasso et al. Pharmacol. Res.2012, 65, 553). The new compounds are among the most potent multitarget FAAH/COX inhibitors reported so far in the literature and thus may represent promising starting points for the discovery of new analgesic and anti-inflammatory drugs.

Picolinamide-Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability.

Science.gov (United States)

Kanega, Ryoichi; Onishi, Naoya; Wang, Lin; Murata, Kazuhisa; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

2018-03-01

To develop highly efficient catalysts for dehydrogenation of formic acid in water, we investigated several Cp*Ir catalysts with various amide ligands. The catalyst with an N-phenylpicolinamide ligand exhibited a TOF of 118 000 h -1 at 60 °C. A constant rate (TOF>35 000 h -1 ) was maintained for six hours, and a TON of 1 000 000 was achieved at 50 °C. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles: Specific characteristics of the condensed phases.

Science.gov (United States)

Vollhardt, D

2015-08-01

For understanding the role of amide containing amphiphiles in inherently complex biological processes, monolayers at the air-water interface are used as simple biomimetic model systems. The specific characteristics of the condensed phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles are surveyed to highlight the effect of the chemical structure of the amide amphiphiles on the interfacial interactions in model monolayers. The mesoscopic topography and/or two-dimensional lattice structures of selected amino acid amphiphiles, amphiphilic N-alkylaldonamide, amide amphiphiles with specific tailored headgroups, such as amide amphiphiles based on derivatized ethanolamine, e.g. acylethanolamines (NAEs) and N-,O-diacylethanolamines (DAEs) are presented. Special attention is devoted the dominance of N,O-diacylated ethanolamine in mixed amphiphilic acid amide monolayers. The evidence that a first order phase transition can occur in adsorption layers and that condensed phase domains of mesoscopic scale can be formed in adsorption layers was first obtained on the basis of the experimental characteristics of a tailored amide amphiphile. New thermodynamic and kinetic concepts for the theoretical description of the characteristics of amide amphiphile's monolayers were developed. In particular, the equation of state for Langmuir monolayers generalized for the case that one, two or more phase transitions occur, and the new theory for phase transition in adsorbed monolayers are experimentally confirmed at first by amide amphiphile monolayers. Despite the significant progress made towards the understanding the model systems, these model studies are still limited to transfer the gained knowledge to biological systems where the fundamental physical principles are operative in the same way. The study of biomimetic systems, as described in this review, is only a first step in this direction. Copyright © 2014 Elsevier B.V. All rights reserved.

The effect of the conditions of amidoximation on the adsorptive characteristics of amide oxime resin for uranium recovery from seawater

International Nuclear Information System (INIS)

Hori, Takahiro; Furusaki, Shintaro; Sugo, Takanobu; Okamoto, Jiro.

1987-01-01

A hollow-fiber type chelating resin containing the amide oxime group for the recovery of uranium from seawater was synthesized by radiation-induced graft polymerization. The effect of the conditions of amidoximation on the amount and/or distribution of the functional groups and on the durability to the recycle adsorption was investigated. The amount of adsorbed copper on the resin increased with the reaction time of the amidoximation, but that of adsorbed hydrochloric acid gradually decreased after reaching the maximum. From the results of elemental analysis, infrared adsorption spectra, visible light and ultraviolet adsorption spectra and the observation of coloration of the resin by alkaline treatment, the amidoximation was found to be a consecutive reaction. The results also suggested that, after the introduction of the amide oxime group, the acidic amide, hydroxamic acid and/or cyclic functional groups were formed. From the measurement of the distribution of adsorbed copper by X-ray microanalyzer, it was confirmed that the amidoximation occured uniformly across the resin. An experiment was carried out on the recycle adsorption of the amide oxime resin using natural seawater, and the sufficient durability was recognized for the case that the resin was taken out from the hydroxylamine solution at the time when the amount of adsorbed hydrochloric acid reached the maximum. In this case the resin contained the largest amount of the amide oxime group and least amount of the by-products formed from the secondary reactions. (author)

Overexpression of fatty acid amide hydrolase induces early flowering in Arabidopsis thaliana

Directory of Open Access Journals (Sweden)

Neal D. Teaster

2012-02-01

Full Text Available N-Acylethanolamines (NAEs are bioactive lipids derived from the hydrolysis of the membrane phospholipid N-acylphosphatidylethanolamine (NAPE. In animal systems this reaction is part of the endocannabinoid signaling pathway, which regulates a variety of physiological processes. The signaling function of NAE is terminated by fatty acid amide hydrolase (FAAH, which hydrolyzes NAE to ethanolamine and free fatty acid. Our previous work in Arabidopsis thaliana showed that overexpression of AtFAAH (At5g64440 lowered endogenous levels of NAEs in seeds, consistent with its role in NAE signal termination. Reduced NAE levels were accompanied by an accelerated growth phenotype, increased sensitivity to abscisic acid (ABA, enhanced susceptibility to bacterial pathogens, and early flowering. Here we investigated the nature of the early flowering phenotype of AtFAAH overexpression. AtFAAH overexpressors flowered several days earlier than wild type and AtFAAH knockouts under both non-inductive short day (SD and inductive long day (LD conditions. Microarray analysis revealed that the FLOWERING LOCUS T (FT gene, which plays a major role in regulating flowering time, and one target MADS box transcription factor, SEPATALLA3 (SEP3, were elevated in AtFAAH overexpressors. Furthermore, AtFAAH overexpressors, with the early flowering phenotype had lower endogenous NAE levels in leaves compared to wild type prior to flowering. Exogenous application of NAE 12:0, which was reduced by up to 30% in AtFAAH overexpressors, delayed the onset of flowering in wild type plants. We conclude that the early flowering phenotype of AtFAAH overexpressors is, in part, explained by elevated FT gene expression resulting from the enhanced NAE hydrolase activity of AtFAAH, suggesting that NAE metabolism may participate in floral signaling pathways.

Twisted Amides: From Obscurity to Broadly Useful Transition-Metal-Catalyzed Reactions by N-C Amide Bond Activation.

Science.gov (United States)

Liu, Chengwei; Szostak, Michal

2017-05-29

The concept of using amide bond distortion to modulate amidic resonance has been known for more than 75 years. Two classic twisted amides (bridged lactams) ingeniously designed and synthesized by Kirby and Stoltz to feature fully perpendicular amide bonds, and as a consequence emanate amino-ketone-like reactivity, are now routinely recognized in all organic chemistry textbooks. However, only recently the use of amide bond twist (distortion) has advanced to the general organic chemistry mainstream enabling a host of highly attractive N-C amide bond cross-coupling reactions of broad synthetic relevance. In this Minireview, we discuss recent progress in this area and present a detailed overview of the prominent role of amide bond destabilization as a driving force in the development of transition-metal-catalyzed cross-coupling reactions by N-C bond activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amide-N-oxide heterosynthon and amide dimer homosynthon in cocrystals of carboxamide drugs and pyridine N-oxides.

Science.gov (United States)

Babu, N Jagadeesh; Reddy, L Sreenivas; Nangia, Ashwini

2007-01-01

The carboxamide-pyridine N-oxide heterosynthon is sustained by syn(amide)N-H...O-(oxide) hydrogen bond and auxiliary (N-oxide)C-H...O(amide) interaction (Reddy, L. S.; Babu, N. J.; Nangia, A. Chem. Commun. 2006, 1369). We evaluate the scope and utility of this heterosynthon in amide-containing molecules and drugs (active pharmaceutical ingredients, APIs) with pyridine N-oxide cocrystal former molecules (CCFs). Out of 10 cocrystals in this study and 7 complexes from previous work, amide-N-oxide heterosynthon is present in 12 structures and amide dimer homosynthon occurs in 5 structures. The amide dimer is favored over amide-N-oxide synthon in cocrystals when there is competition from another H-bonding functional group, e.g., 4-hydroxybenzamide, or because of steric factors, as in carbamazepine API. The molecular organization in carbamazepine.quinoxaline N,N'-dioxide 1:1 cocrystal structure is directed by amide homodimer and anti(amide)N-H...O-(oxide) hydrogen bond. Its X-ray crystal structure matches with the third lowest energy frame calculated in Polymorph Predictor (Cerius(2), COMPASS force field). Apart from generating new and diverse supramolecular structures, hydration is controlled in one substance. 4-Picoline N-oxide deliquesces within a day, but its cocrystal with barbital does not absorb moisture at 50% RH and 30 degrees C up to four weeks. Amide-N-oxide heterosynthon has potential utility in both amide and N-oxide type drug molecules with complementary CCFs. Its occurrence probability in the Cambridge Structural Database is 87% among 27 structures without competing acceptors and 78% in 41 structures containing OH, NH, H(2)O functional groups.

Emotional lability and affective synchrony in borderline personality disorder.

Science.gov (United States)

Schoenleber, Michelle; Berghoff, Christopher R; Tull, Matthew T; DiLillo, David; Messman-Moore, Terri; Gratz, Kim L

2016-07-01

Extant research on emotional lability in borderline personality disorder (BPD) has focused almost exclusively on lability of individual emotions or emotion types, with limited research considering how different types of emotions shift together over time. Thus, this study examined the temporal dynamics of emotion in BPD at the level of both individual emotions (i.e., self-conscious emotions [SCE], anger, and anxiety) and mixed emotions (i.e., synchrony between emotions). One hundred forty-four women from the community completed a diagnostic interview and laboratory study involving 5 emotion induction tasks (each of which was preceded and followed by a 5-min resting period or neutral task). State ratings of SCE, anger, and anxiety were provided at 14 time points (before and after each laboratory task and resting period). Hierarchical linear modeling results indicate that women with BPD reported greater mean levels of SCE and Anxiety (but not Anger), and greater lability of Anxiety. Women with BPD also exhibited greater variability in lability of all 3 emotions (suggestive of within-group differences in the relevance of lability to BPD). Results also revealed synchrony (i.e., positive relations) between each possible pair of emotions, regardless of BPD status. Follow-up regression analyses suggest the importance of accounting for lability when examining the role of synchrony in BPD, as the relation of SCE-Anger synchrony to BPD symptom severity was moderated by Anger and SCE lability. Specifically, synchronous changes in SCE and Anger were associated with greater BPD symptom severity when large shifts in SCE were paired with minor shifts in Anger. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

(Amino acid + silica) adsorption thermodynamics: Effects of temperature

International Nuclear Information System (INIS)

Sebben, Damien; Pendleton, Phillip

2015-01-01

Highlights: • High resolution, low concentration Gly, Lys and Glu solution adsorption isotherms. • All isotherms fitted with Langmuir–Freundlich isotherm model. • Gly, Lys and Glu show exothermic adsorption processes. • Isosteric heat analyses reveal changes in interaction strength with surface coverage. - Abstract: A thorough understanding of amino acid adsorption by mineral and oxide surfaces has a major impact on a variety of industrial and biomedical applications. Little information currently exists regarding temperature effects on most of these adsorption processes. Deeper thermodynamic analyses of their multiple temperature adsorption isotherms would aid the interpretation of the interfacial interactions. Low solution concentration adsorption isotherms for glycine, lysine and glutamic acid on a silica adsorbent were generated for T = (291, 298 and 310) K. Data analysis via the Clausius–Clapeyron method yielded the isosteric heat of adsorption as a function of fractional monolayer coverage for each adsorptive. Each amino acid showed an exothermic adsorption response. Glycine and lysine experienced a greater negative effect of increased temperature compared with glutamic acid, indicating a greater number of adsorbed molecules than glutamic acid, with the former undergoing intermolecular clustering within the adsorbed phase. Isosteric heat analyses suggest ionic interactions for lysine and hydrogen bonding for glutamic acid, both weakening with increased coverage. In contrast, initial hydrogen bonding led to ionic bonding for glycine with increasing coverage

Phenethyl ester and amide of Ferulic Acids: Synthesis and bioactivity against P388 Leukemia Murine Cells

Science.gov (United States)

Firdaus; Soekamto, N. H.; Seniwati; Islam, M. F.; Sultan

2018-03-01

Bioactivity of a compound is closely related to the molecular structure of the compound concerned, its strength being the quantitative relation of the strength of the activity of the group it possesses. The combining of moieties of the active compounds will produce more active compounds. Most phenolic compounds as well as compounds containing moiety phenethyl groups have potential activity as anticancer. Combining phenolic groups and phenethyl groups in a compound will result in compounds having strong anticancer bioactivity. This study aims to combine the feruloyl and phenethyl groups to form esters and amides by synthesize of phenethyl trans-3-(4-hydroxy-3-methoxyphenyl)acrylate (5) and trans-3-(4- hydroxy-3-methoxyphenyl)-N-phenethylacrylamide (6) from ferulic acid with phenethyl alcohol and phenethylamine, and to study their bioactivity as anticancer. The synthesis of both compounds was conducted via indirect reaction, including acetylation, chlorination, esterfication/amidation, and deacetylation. Structures of products were characterized by FTIR and NMR data, and their bioactivity assay of the compounds against P388 Leukemia Murine Cells was conducted by an MTT method. Results showed that the compound 5 was obtained as a yellow gel with the IC50 of 10.79 μg/mL (36.21 μΜ), and the compound 6 was a yellowish solid with a melting point of 118-120°C and the IC50 of 29.14 μg/mL (97.79 μΜ). These compounds were more active than the analog compounds.

Functionalities of chitosan conjugated with stearic acid and gallic acid and application of the modified chitosan in stabilizing labile aroma compounds in an oil-in-water emulsion.

Science.gov (United States)

Yang, Tsung-Shi; Liu, Tai-Ti; Lin, I-Hwa

2017-08-01

The aims of this research were to conjugate chitosan (CT) with stearic acid (SA) and gallic acid (GA), and apply the modified chitosan to stabilize labile aroma compounds such as allyl isothiocyanate (AITC) and limonene in oil-in-water emulsions. Generally, the antioxidant activity of CT-SA-GA increased as the GA content in the conjugate increased. In most assays, GA had a lower IC 50 value than that of CT-SA-GA; however, CT-SA-GA exhibited better performance than GA in the Fe 2+ -chelating activity. In accelerated tests (heating or illumination) for evaluating the chemical stability of AITC and limonene during storage, CT-SA and CT-SA-GA were used to prepare AITC and limonene O/W emulsions, respectively. Tween 80 and Span 80 (T-S-80), an emulsifier mixture, were used as a control in both emulsions for comparison. The results show that CT-SA or CT-SA-GA could protect AITC or limonene from degradation or oxidation more effectively than T-S-80. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mass Spectra Analyses of Amides and Amide Dimers of Steviol, Isosteviol, and Steviolbioside

Directory of Open Access Journals (Sweden)

Lin-Wen Lee

2012-01-01

Full Text Available The mass spectra of a series of stevioside analogues including the amide and dimer compounds of steviol, isosteviol, and steviolbioside were examined. Positive ion mass spectral fragmentation of new steviol, isosteviol, and steviolbioside amides and the amide dimers are reported and discussed. The techniques included their synthesis procedures, fast-atom bombardment (FAB, and LC/MS/MS mass spectra. Intense [M+H]+ and [M+Na]+ ion peaks were observed on the FAB and ESI spectra. LC/MS/MS also yielded ES+ and ES− ion peaks that fairly agreed with the results of the FAB and ESI studies. Mass spectral analysis of compounds 4p-q, 5a-g, 6, and 7 revealed the different cleavage pathway patterns that can help in identifying the structures of steviolbioside and its amide derivatives.

Polyvinylpolypyrrolidone-Supported Boron Trifluoride; Highly Efficient Catalyst for the Synthesis of N-tert-Butyl Amides

Directory of Open Access Journals (Sweden)

Masoud Mokhtary

2012-01-01

Full Text Available Highly efficient method for the preparation of N-tert-butyl amides by reaction of nitriles with tert-butyl acetate is described using polyvinylpolypyrrolidone-supported boron trifluoride (PVPP-BF3 at 70°C in good to excellent yields. Selective amidation of benzonitrile in the presence of acetonitrile was also achieved. polyvinylpolypyrrolidone-boron trifluoride complex shows non-corrosive and stable solid catalyst elevated Lewis acid property.

Biologically active and C-amidated hinnavinII-38-Asn produced from a Trx fusion construct in Escherichia coli.

Science.gov (United States)

Kang, Chang Soo; Son, Seung-Yeol; Bang, In Seok

2008-12-01

The cabbage butterfly (Artogeia rapae) antimicrobial peptide hinnavinII as a member of cecropin family is synthesized as 37 residues in size with an amidated lysine at C-terminus and shows the humoral immune response to a bacterial invasion. In this work, a synthetic gene for hinnavinII-38-Asn (HIN) with an additional amino acid asparagine residue containing amide group at C-terminus was cloned into pET-32a(+) vector to allow expression of HIN as a Trx fusion protein in Escherichia coli strain BL21 (DE3) pLysS. The resulting expression level of the fusion protein Trx-HIN could reach 15-20% of the total cell proteins and more than 70% of the target proteins were in soluble form. The fusion protein could be purified successfully by HiTrap Chelating HP column and a high yield of 15 mg purified fusion protein was obtained from 80 ml E. coli culture. Recombinant HIN was readily obtained by enterokinase cleavage of the fusion protein followed by FPLC chromatography, and 3.18 mg pure active recombinant HIN was obtained from 80 ml culture. The molecular mass of recombinant HIN determined by MALDI-TOF mass spectrometer is 4252.084 Da which matches the theoretical mass (4252.0 Da) of HIN. Comparing the antimicrobial activities of the recombinant hinnavinII with C-amidated terminus to that without an amidated C-terminus, we found that the amide of asparagine at C-terminus of hinnavinII improved its potency on certain microorganism such as E. coli, Enterobacter cloacae, Bacillus megaterium, and Staphylococcus aureus.

Improving release completeness from PLGA-based implants for the acid-labile model protein ovalbumin.

Science.gov (United States)

Duque, Luisa; Körber, Martin; Bodmeier, Roland

2018-03-01

The objectives of this study were to assess the feasibility of hot melt extrusion (HME) for the preparation of PLGA-based ovalbumin-loaded implants as well as to characterize and improve protein release from the implants. Ovalbumin (OVA) was stable during extrusion, which was attributed to a protective effect of the biodegradable matrix. OVA release was characterized by a low burst, a slow release up to day 21, which plateaued thereafter resulting in incomplete release for all evaluated protein loadings. Release incompleteness was accompanied by the formation of an insoluble residual mass. Further characterization of this mass indicated that it consisted of non-covalent protein aggregates and polymer, where ovalbumin was ionically bound as the pH inside the degrading matrix decreased below the pI of the protein. Although higher protein release was obtained with the inclusion of weak bases because of their neutralizing effect, OVA aggregation and release incompleteness were not fully avoided. With the use of shellac, a well-known enteric and biocompatible polymer, as protective excipient, a distinct late release phase occurred and release completeness was increased to more than 75% cumulative release. Shellac apparently protected the protein against the acidic microclimate due to its low solubility at low pH. Protected OVA was thus released once the pH increased due to a declining PLGA-oligomer formation. The result was a triphasic release profile consisting of an initial burst, a slow diffusion phase over about 7 weeks, and an erosion-controlled dissolution phase over the next 3 weeks. An acid-labile protein like OVA was thus feasibly protected from interactions with PLGA and its degradation products, resulting in a controlled delivery of more than 85% of the original payload. Copyright © 2018 Elsevier B.V. All rights reserved.

Preparation and study of novel poly(sulfone-ester-amide)s

Energy Technology Data Exchange (ETDEWEB)

Bruma, M. [Institute of Macromolecular Chemistry, Isai (Romania)], Mercer, F. [Raychem Corporation, Menlo Park, CA (United States); Gronewald, S. [Southwest Texas State Univ., San Marcos, TX (United States)] [and others

1995-12-31

A series of novel poly(ester-amide)s containing sulfone groups in the main chain have been prepared and compared with related polymers which do not have sulfone bridges. Incorporation of sulfone moieties into the polymer backbone improved the solubility of these polymers without significant loss of their high thermal stability, and provided a large {open_quotes}window{close_quotes} between T{sub g} and decomposition temperature. Solutions of poly(sulfone-ester-amide)s in NMP have been cast into flexible films, having low dielectric constant. The synthesis and characterization of these new polymers will be presented.

Application of nanoparticles for oral delivery of acid-labile lansoprazole in the treatment of gastric ulcer: in vitro and in vivo evaluations.

Science.gov (United States)

Alai, Milind; Lin, Wen Jen

2015-01-01

The aim of this study was to develop nanoparticles for oral delivery of an acid-labile drug, lansoprazole (LPZ), for gastric ulcer therapy. LPZ-loaded positively charged Eudragit(®) RS100 nanoparticles (ERSNPs-LPZ) and negatively charged poly(lactic-co-glycolic acid) nanoparticles (PLGANPs-LPZ) were prepared. The effect of charge on nanoparticle deposition in ulcerated and non-ulcerated regions of the stomach was investigated. The cellular uptake of nanoparticles in the intestine was evaluated in a Caco-2 cell model. The pharmacokinetic performance and ulcer healing response of LPZ-loaded nanoparticles following oral administration were evaluated in Wistar rats with induced ulcers. The prepared drug-loaded ERSNPs-LPZ and PLGANPs-LPZ possessed opposite surface charge (+38.5±0.3 mV versus -27.3±0.3 mV, respectively) and the particle size was around 200 nm with a narrow size distribution. The negatively charged PLGANPs adhered more readily to the ulcerated region (7.22%±1.21% per cm(2)), whereas the positively charged ERSNPs preferentially distributed in the non-ulcerated region (8.29%±0.35% per cm(2)). Both ERSNPs and PLGANPs were prominent uptake in Caco-2 cells, too. The nanoparticles sustained and prolonged LPZ concentrations up to 24 hours, and the half-life and mean residence time of LPZ were prolonged by 3.5-fold and 4.5-fold, respectively, as compared with LPZ solution. Oral administration of LPZ-loaded nanoparticles healed 92.6%-95.7% of gastric ulcers in Wistar rats within 7 days.

Dianthosaponins G-I, triterpene saponins, an anthranilic acid amide glucoside and a flavonoid glycoside from the aerial parts of Dianthus japonicus and their cytotoxicity.

Science.gov (United States)

Kanehira, Yuka; Kawakami, Susumu; Sugimoto, Sachiko; Matsunami, Katsuyoshi; Otsuka, Hideaki

2016-10-01

Extensive isolation work on the 1-BuOH-soluble fraction of a MeOH extract of the aerial parts of Dianthus japonicus afforded three further triterpene glycosyl estsers, termed dianthosaponins G-I, an anthranilic acid amide glucoside and a C-glycosyl flavonoid along with one known triterpene saponin. Their structures were elucidated from spectroscopic evidence. The cytotoxicity of the isolated compounds toward A549 cells was evaluated.

Structural Characterization of N-Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N-C Cleavage.

Science.gov (United States)

Hu, Feng; Lalancette, Roger; Szostak, Michal

2016-04-11

Herein, we describe the first structural characterization of N-alkylated twisted amides prepared directly by N-alkylation of the corresponding non-planar lactams. This study provides the first experimental evidence that N-alkylation results in a dramatic increase of non-planarity around the amide N-C(O) bond. Moreover, we report a rare example of a molecular wire supported by the same amide C=O-Ag bonds. Reactivity studies demonstrate rapid nucleophilic addition to the N-C(O) moiety of N-alkylated amides, indicating the lack of n(N) to π*(C=O) conjugation. Most crucially, we demonstrate that N-alkylation activates the otherwise unreactive amide bond towards σ N-C cleavage by switchable coordination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lability of nanoparticulate metal complexes in electrochemical speciation analysis

DEFF Research Database (Denmark)

van Leeuwen, Herman P.; Town, Raewyn M.

2016-01-01

Lability concepts are elaborated for metal complexes with soft (3D) and hard (2D) aqueous nanoparticles. In the presence of a non-equilibrium sensor, e.g. a voltammetric electrode, the notion of lability for nanoparticulate metal complexes, M-NP, reflects the ability of the M-NP to maintain...... equilibrium with the reduced concentration of the electroactive free M2+ in its diffusion layer. Since the metal ion binding sites are confined to the NP body, the conventional reaction layer in the form of a layer adjacent to the electrode surface is immaterial. Instead an intraparticulate reaction zone may...... of the electrochemical technique is crucial in the lability towards the electrode surface. In contrast, for nanoparticulate complexes it is the dynamics of the exchange of the electroactive metal ion with the surrounding medium that governs the effective lability towards the electrode surface....

Pharmacological ascorbate and ionizing radiation (IR increase labile iron in pancreatic cancer

Directory of Open Access Journals (Sweden)

Justin C. Moser

2014-01-01

Full Text Available Labile iron, i.e. iron that is weakly bound and is relatively unrestricted in its redox activity, has been implicated in both the pathogenesis as well as treatment of cancer. Two cancer treatments where labile iron may contribute to their mechanism of action are pharmacological ascorbate and ionizing radiation (IR. Pharmacological ascorbate has been shown to have tumor-specific toxic effects due to the formation of hydrogen peroxide. By catalyzing the oxidation of ascorbate, labile iron can enhance the rate of formation of hydrogen peroxide; labile iron can also react with hydrogen peroxide. Here we have investigated the magnitude of the labile iron pool in tumor and normal tissue. We also examined the ability of pharmacological ascorbate and IR to change the size of the labile iron pool. Although a significant amount of labile iron was seen in tumors (MIA PaCa-2 cells in athymic nude mice, higher levels were seen in murine tissues that were not susceptible to pharmacological ascorbate. Pharmacological ascorbate and irradiation were shown to increase the labile iron in tumor homogenates from this murine model of pancreatic cancer. As both IR and pharmacological ascorbate may rely on labile iron for their effects on tumor tissues, our data suggest that pharmacological ascorbate could be used as a radio-sensitizing agent for some radio-resistant tumors.

Use of UHPLC-TripleQ with synthetic standards to profile anti-inflammatory hydroxycinnamic acid amides in root barks and leaves of Lycium barbarum

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Siyu Wang

2018-04-01

Full Text Available Hydroxycinnamic acid amides (HCAA are the secondary metabolites ubiquitously exist in flowering plants, formed by condensation between hydroxycinnamates and mono or polyamines. HCAA species not only serve multiple functions in plant growth and development, but also exert significant positive effects on human health. In this study, we combined organic synthesis and UPHLC-TripleQ-MS/MS specifically targeting at HCAA species. The method was fully validated with respect to specificity, linearity, intra- and inter-day precision and accuracy, limit of detection (LOD, limit of quantification (LOQ, recovery, and reproducibility. We applied this method to identify and quantify HCAAs from the root barks and leaves of Lycium barbarum. HCAA species were reported in leaves for the first time, and 10 new HCAA species were further identified in root barks in addition to the ones reported in the literature. We also examine anti-inflammatory properties of identified HCAAs species. Seven HCAA compounds had a potent NO inhibitory effect with IC50 as low as 2.381 μM (trans-N-caffeoyl phenethylamine. Our developed method largely improved analytical sensitivity of HCAAs species that potentially contributes to plant metabolomics studies. Keywords: Hydroxycinnamic acid amide, Lycium barbarum, UHPLC-MS/MS, Quantification, Anti-inflammatory

Preparation and characterization of molecularly-imprinted polymers for extraction of sanshool acid amide compounds followed by their separation from pepper oil resin derived from Chinese prickly ash (Zanthoxylum bungeanum).

Science.gov (United States)

Chen, Xiaolong; Jin, Xinkai; Li, Yao; Chen, Guangjing; Chen, Kewei; Kan, Jianquan

2018-01-01

Molecularly imprinted polymers were prepared using the molecular structure analogs of sanshool as template molecule, 2-vinylpyridine and β-cyclodextrin as double functional monomers, ethylene dimethacrylate as cross linker, and azobisisobutyronitrile as initiator. The structural characteristics of the polymers were determined by Fourier-transform infrared spectroscopy and scanning electron microscopy. Dynamic adsorption and isothermal adsorption were also investigated. The molecularly imprinted polymers were used to prepare a molecularly imprinted solid-phase extraction column in order to separate acid amide components from pepper oil resin derived from Chinese prickly ash (Zanthoxylum bungeanum). After eluting, the percentage of acid amide components was enhanced to 92.40 ± 1.41% compared with 23.34 ± 1.21% in the initial pepper oil resin, indicating good properties of purification of molecularly imprinted polymers and potential industrial application. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduced-Amide Inhibitor of Pin1 Binds in a Conformation Resembling a Twisted-Amide Transition State†

Science.gov (United States)

Xu, Guoyan G.; Zhang, Yan; Mercedes-Camacho, Ana Y.; Etzkorn, Felicia A.

2011-01-01

The mechanism of the cell cycle regulatory peptidyl prolyl isomerase (PPIase), Pin1, was investigated using reduced-amide inhibitors designed to mimic the twisted-amide transition state. Inhibitors, R–pSer–Ψ[CH2N]–Pro–2-(indol-3-yl)-ethylamine, 1 (R = fluorenylmethoxycarbonyl, Fmoc), and 2 (R = Ac), of Pin1 were synthesized and bioassayed. Inhibitor 1 had an IC50 value of 6.3 μM, which is 4.5-fold better inhibition for Pin1 than our comparable ground state analogue, a cis-amide alkene isostere containing inhibitor. The change of Fmoc to Ac in 2 improved aqueous solubility for structural determination, and resulted in an IC50 value of 12 μM. The X-ray structure of the complex of 2 bound to Pin1 was determined to 1.76 Å resolution. The structure revealed that the reduced amide adopted a conformation similar to the proposed twisted-amide transition state of Pin1, with a trans-pyrrolidine conformation of the prolyl ring. A similar conformation of substrate would be destabilized relative to the planar amide conformation. Three additional reduced amides, with Thr replacing Ser, and l- or d-pipecolate (Pip) replacing Pro, were slightly weaker inhibitors of Pin1. PMID:21980916

Fine structure of the amide i band in acetanilide

Science.gov (United States)

Careri, G.; Gratton, E.; Shyamsunder, E.

1988-05-01

Their absorption spectrum of both single crystals and powdered samples of acetanilide (a model system for proteins) has been studied in the amide i region, where a narrow band has been identified as a highly trapped soliton state. The powder-sample spectra have been decomposed using four Lorentzian bands. A strong temperature dependence has been found for the intensity of two of the subbands, which also show a complementary behavior. Polarization studies performed on thin crystals have shown that the subbands have the same polarization. Low-temperature spectra of partially deuterated samples show the presence of the subbands at the same absorption frequencies found using the fitting procedure in the spectra of nondeuterated samples. The soliton model currently proposed to explain the origin of the anomalous amide i component at 1650 cm-1 still holds, but some modification of the model is required to account for the new features revealed by this study.

Chemical constituents from red algae Bostrychia radicans (Rhodomelaceae): new amides and phenolic compounds

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Ana Ligia Leandrini de; Silva, Denise B. da; Lopes, Norberto P.; Debonsi, Hosana M. [Universidade de Sao Paulo (FCFRP/USP), Ribeirao Preto, SP (Brazil). Fac. de Ciencias Farmaceuticas de Ribeirao Preto. Dept. de Quimica e Fisica; Yokoya, Nair S., E-mail: hosana@fcfrp.usp.br [Instituto de Botanica, Sao Paulo, SP (Brazil). Secao de Ficologia

2012-07-01

This study describes the isolation and structural determination of two amides, isolated for the first time: N,4-dihydroxy-N-(2'-hydroxyethyl)-benzamide (0.019%) and N,4-dihydroxy-N-(2'-hydroxyethyl)-benzeneacetamide (0.023%). These amides, produced by the red macroalgae Bostrychia radicans, had their structures assigned by NMR spectral data and MS analyses. In addition, this chemical study led to the isolation of cholesterol, heptadecane, squalene, trans-phytol, neophytadiene, tetradecanoic and hexadecanoic acids, methyl hexadecanoate and methyl 9-octadecenoate, 4-(methoxymethyl)-phenol, 4-hydroxybenzaldehyde, methyl 4-hydroxybenzeneacetate, methyl 2-hydroxy-3-(4-hydroxyphenyl)-propanoate, hydroquinone, methyl 4-hydroxymandelate, methyl 4-hydroxybenzoate, 4-hydroxybenzeneacetic acid and (4-hydroxyphenyl)-oxo-acetaldehyde. This is the first report concerning these compounds in B. radicans, contributing by illustrating the chemical diversity within the Rhodomelaceae family. (author)

Chemical constituents from red algae Bostrychia radicans (Rhodomelaceae: new amides and phenolic compounds

Directory of Open Access Journals (Sweden)

Ana Lígia Leandrini de Oliveira

2012-01-01

Full Text Available This study describes the isolation and structural determination of two amides, isolated for the first time: N,4-dihydroxy-N-(2'-hydroxyethyl-benzamide (0.019% and N,4-dihydroxy-N-(2'-hydroxyethyl-benzeneacetamide (0.023%. These amides, produced by the red macroalgae Bostrychia radicans, had their structures assigned by NMR spectral data and MS analyses. In addition, this chemical study led to the isolation of cholesterol, heptadecane, squalene, trans-phytol, neophytadiene, tetradecanoic and hexadecanoic acids, methyl hexadecanoate and methyl 9-octadecenoate, 4-(methoxymethyl-phenol, 4-hydroxybenzaldehyde, methyl 4-hydroxybenzeneacetate, methyl 2-hydroxy-3-(4-hydroxyphenyl-propanoate, hydroquinone, methyl 4-hydroxymandelate, methyl 4-hydroxybenzoate, 4-hydroxybenzeneacetic acid and (4-hydroxyphenyl-oxo-acetaldehyde. This is the first report concerning these compounds in B. radicans, contributing by illustrating the chemical diversity within the Rhodomelaceae family.

Understanding Chemistry and Unique NMR Characters of Novel Amide and Ester Leflunomide Analogues

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Morkos A. Henen

2017-12-01

Full Text Available A series of diverse substituted 5-methyl-isoxazole-4-carboxylic acid amides, imide and esters in which the benzene ring is mono or disubstituted was prepared. Spectroscopic and conformational examination was investigated and a new insight involving steric interference and interesting downfield deviation due to additional diamagnetic anisotropic effect of the amidic carbonyl group and the methine protons in 2,6-diisopropyl-aryl derivative (2 as conformationaly restricted analogues Leflunomide was discussed. Individual substituent electronic effects through π resonance of p-substituents and most stable conformation of compound (2 are discussed.

Backbone amide linker strategy

DEFF Research Database (Denmark)

Shelton, Anne Pernille Tofteng; Jensen, Knud Jørgen

2013-01-01

In the backbone amide linker (BAL) strategy, the peptide is anchored not at the C-terminus but through a backbone amide, which leaves the C-terminal available for various modifications. This is thus a very general strategy for the introduction of C-terminal modifications. The BAL strategy...

VCD Robustness of the Amide-I and Amide-II Vibrational Modes of Small Peptide Models.

Science.gov (United States)

Góbi, Sándor; Magyarfalvi, Gábor; Tarczay, György

2015-09-01

The rotational strengths and the robustness values of amide-I and amide-II vibrational modes of For(AA)n NHMe (where AA is Val, Asn, Asp, or Cys, n = 1-5 for Val and Asn; n = 1 for Asp and Cys) model peptides with α-helix and β-sheet backbone conformations were computed by density functional methods. The robustness results verify empirical rules drawn from experiments and from computed rotational strengths linking amide-I and amide-II patterns in the vibrational circular dichroism (VCD) spectra of peptides with their backbone structures. For peptides with at least three residues (n ≥ 3) these characteristic patterns from coupled amide vibrational modes have robust signatures. For shorter peptide models many vibrational modes are nonrobust, and the robust modes can be dependent on the residues or on their side chain conformations in addition to backbone conformations. These robust VCD bands, however, provide information for the detailed structural analysis of these smaller systems. © 2015 Wiley Periodicals, Inc.

Alkali-labile sites and post-irradiation effects in single-stranded DNA induced by H radicals

International Nuclear Information System (INIS)

Lafleur, M.V.M.; Heuvel, N. van; Woldhuis, J.; Loman, H.

1978-01-01

Single-stranded phiX174 DNA in aqueous solutions has been irradiated in the absence of oxygen, under conditions in which H radicals react with the DNA. It was shown that H radical reactions result in breaks, which contribute approximately 10 per cent inactivation. Further, two types of alkali-labile sites were formed. One was lethal and gave rise to single-strand breaks by alkali and was most probably identical with post-irradiation heat damage and contributed about 33 per cent to the inactivation mentioned above. The other consisted of non-lethal damage, partly dihydropyrimidine derivatives, and was converted to lethal damage by alkali. This followed from experiments in which the DNA was treated with osmium-tetroxide, which oxidized thymine to 5,6-dihydroxydihydrothymine. Treatment with alkali of this DNA gave the same temperature dependence as found for the non-lethal alkali-labile sites in irradiated DNA. A similar temperature dependence was found for dihydrothymine and irradiated pyrimidines with alkali. (author)

Synthetic polyspermine imidazole-4, 5-amide as an efficient and cytotoxicity-free gene delivery system

Directory of Open Access Journals (Sweden)

Duan S

2012-07-01

Full Text Available Shi-Yue Duan, Xue-Mei Ge, Nan Lu, Fei Wu, Weien Yuan, Tuo JinSchool of Pharmacy, Shanghai Jiao Tong University, Shanghai, 200240, People's Republic of ChinaAbstract: A chemically dynamic spermine-based polymer: polyspermine imidazole-4, 5-amide (PSIA, Mw > 7 kDa was designed, synthesized, and evaluated in terms of its ability to deliver nucleic acids. This polymer was made from an endogenous monomer professionally condensing genes in sperms, spermine, and a known safety drug metabolite, imidazole-4, 5-dicarboxylic acid, through a bis-amide bond conjugated with the imidazole ring. This polymer can condense pDNA at a W/W ratio above 10 to form polyplexes (100–200 nm in diameter, which is consistent with the observation by transmission electron microscopy (TEM, and the zeta potential was in the range of 10–20 mV. The pDNA packaged polymer was stable in phosphate buffer solution (PBS at pH 7.4 (simulated body fluid while the polyplexes were releasing pDNA into the solution at pH 5.8 (simulated endo-lysosomes due to the degradation of the bis-amide linkages in response to changes in pH values. PSIA-polyplexes were able to achieve efficient cellular uptake and luciferase gene silencing by co-transfection of pDNA and siRNA in COS-7 cells and HepG2 cells with negligible cytotoxicity. Biodistribution of Rhodamine B-labeled PSIA-polyplexes after being systemically injected in BALB/c nude-mice showed that the polyplexes circulated throughout the body, accumulated mainly in the kidney at 4 hours of sample administration, and moved to the liver and spleen after 24 hours. All the results suggested that PSIA offered a promising example to balance the transfection efficiency and toxicity of a synthetic carrier system for the delivery of therapeutic nucleic acids.Keywords: gene delivery, polyspermine, cytotoxicity, transfection efficiency, biodistribution

[Synthetic transformations of higher terpenoids. XXX. Synthesis and cytotoxic activity of betulonic acid amides with a piperidine or pyrrolidine nitroxide moiety].

Science.gov (United States)

Antimonova, A N; Petrenko, N I; Shults, E E; Polienko, Iu F; Shakirov, M M; Irtegova, I G; Pokrovskiĭ, M A; Sherman, K M; Grigor'ev, I A; Pokrovskiĭ, A G; Tolstikov, G A

2013-01-01

The reaction of betulonic acid chloride with 4-amino-2,2,6,6-tetramethylpeperidine-1-oxyl, 3-amino-2,2,5,5-tetramethylpyrrolidine-1-oxyl and 3-aminomethyl-2,2,5,5-tetramethylpyrrolidine-1-oxyl gave corresponding triterpenoid amides. It was found that new derivatives exhibit cytotoxic activity against tumor cells CEM-13, U-937, MT-4. CCID50 value for most activity compound--N-[3-oxolup-20(29)-en-30-yl]-(2,2,6,6-tetramethylpiperidine-4-yl)-1-oxyl--was 5.7-33.1 microM.

Increasing human Th17 differentiation through activation of orphan nuclear receptor retinoid acid-related orphan receptor γ (RORγ) by a class of aryl amide compounds.

Science.gov (United States)

Zhang, Wei; Zhang, Jing; Fang, Leiping; Zhou, Ling; Wang, Shuai; Xiang, Zhijun; Li, Yuan; Wisely, Bruce; Zhang, Guifeng; An, Gang; Wang, Yonghui; Leung, Stewart; Zhong, Zhong

2012-10-01

In a screen for small-molecule inhibitors of retinoid acid-related orphan receptor γ (RORγ), we fortuitously discovered that a class of aryl amide compounds behaved as functional activators of the interleukin 17 (IL-17) reporter in Jurkat cells. Three of these compounds were selected for further analysis and found to activate the IL-17 reporter with potencies of ∼0.1 μM measured by EC₅₀. These compounds were shown to directly bind to RORγ by circular dichroism-based thermal stability experiments. Furthermore, they can enhance an in vitro Th17 differentiation process in human primary T cells. As RORγ remains an orphan nuclear receptor, discovery of these aryl amide compounds as functional agonists will now provide pharmacological tools for us to dissect functions of RORγ and facilitate drug discovery efforts for immune-modulating therapies.

40 CFR 721.3720 - Fatty amide.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty amide. 721.3720 Section 721.3720... Fatty amide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a fatty amide (PMN P-91-87) is subject to reporting under this section...

40 CFR 721.2120 - Cyclic amide.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Cyclic amide. 721.2120 Section 721... Cyclic amide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a cyclic amide (PMN P-92-131) is subject to reporting under this section for the...

Inhibitors of HIV-1 maturation: Development of structure-activity relationship for C-28 amides based on C-3 benzoic acid-modified triterpenoids.

Science.gov (United States)

Swidorski, Jacob J; Liu, Zheng; Sit, Sing-Yuen; Chen, Jie; Chen, Yan; Sin, Ny; Venables, Brian L; Parker, Dawn D; Nowicka-Sans, Beata; Terry, Brian J; Protack, Tricia; Rahematpura, Sandhya; Hanumegowda, Umesh; Jenkins, Susan; Krystal, Mark; Dicker, Ira B; Meanwell, Nicholas A; Regueiro-Ren, Alicia

2016-04-15

We have recently reported on the discovery of a C-3 benzoic acid (1) as a suitable replacement for the dimethyl succinate side chain of bevirimat (2), an HIV-1 maturation inhibitor that reached Phase II clinical trials before being discontinued. Recent SAR studies aimed at improving the antiviral properties of 2 have shown that the benzoic acid moiety conferred topographical constraint to the pharmacophore and was associated with a lower shift in potency in the presence of human serum albumin. In this manuscript, we describe efforts to improve the polymorphic coverage of the C-3 benzoic acid chemotype through modifications at the C-28 position of the triterpenoid core. The dimethylaminoethyl amides 17 and 23 delivered improved potency toward bevirimat-resistant viruses while increasing C24 in rat oral PK studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Two novel zinc(II) coordination polymers constructed from in situ amidation ligands

Science.gov (United States)

Yu, Xiao-Yang; Fu, Yao; Fu, Jian-Tao; Xu, Jia-Ning; Luo, Ya-Nan; Yang, Yan-Yan; Qu, Xiao-Shu; Zhang, Jing; Lu, Shu-Lai

2018-04-01

Two novel coordination compounds, [Zn(Hbimh) (H2O)]·H2O (1) and [Zn(Hbimh)]·(4,4ʹ-bpy)0.5 (2) (H3bimh = benzimidazole-5,6-hydrazide, 4,4ʹ-bpy = 4,4ʹ-bipyridine), have been prepared from the hydrothermal in situ amidation cyclization reactions of H3bimdc (H3bimdc = benzimidazole-5,6-dicarboxylic acid) and hydrazine hydrate (N2H4·H2O). Compound 1 exhibits a one-dimensional (1D) hexagon channel structure. Compound 2 is a three-dimensional (3D) framework structure, with 4,4ʹ-bpy fill the channels. We also obtained the ligand H3bimh. The compounds were characterized by IR, PXRD, TGA and elemental analysis. The fluorescence properties in the solid state at room temperature were also investigated.

Discovery of competing anaerobic and aerobic pathways in umpolung amide synthesis allows for site-selective amide 18O-labeling

Science.gov (United States)

Shackleford, Jessica P.; Shen, Bo; Johnston, Jeffrey N.

2012-01-01

The mechanism of umpolung amide synthesis was probed by interrogating potential sources for the oxygen of the product amide carbonyl that emanates from the α-bromo nitroalkane substrate. Using a series of 18O-labeled substrates and reagents, evidence is gathered to advance two pathways from the putative tetrahedral intermediate. Under anaerobic conditions, a nitro-nitrite isomerization delivers the amide oxygen from nitro oxygen. The same homolytic nitro-carbon fragmentation can be diverted by capture of the carbon radical intermediate with oxygen gas (O2) to deliver the amide oxygen from O2. This understanding was used to develop a straightforward protocol for the preparation of 18O-labeled amides in peptides by simply performing the umpolung amide synthesis reaction under an atmosphere of . PMID:22184227

A reduced-amide inhibitor of Pin1 binds in a conformation resembling a twisted-amide transition state.

Science.gov (United States)

Xu, Guoyan G; Zhang, Yan; Mercedes-Camacho, Ana Y; Etzkorn, Felicia A

2011-11-08

The mechanism of the cell cycle regulatory peptidyl prolyl isomerase (PPIase), Pin1, was investigated using reduced-amide inhibitors designed to mimic the twisted-amide transition state. Inhibitors, R-pSer-Ψ[CH(2)N]-Pro-2-(indol-3-yl)ethylamine, 1 [R = fluorenylmethoxycarbonyl (Fmoc)] and 2 (R = Ac), of Pin1 were synthesized and bioassayed. Inhibitor 1 had an IC(50) value of 6.3 μM, which is 4.5-fold better for Pin1 than our comparable ground-state analogue, a cis-amide alkene isostere-containing inhibitor. The change of Fmoc to Ac in 2 improved aqueous solubility for structural determination and resulted in an IC(50) value of 12 μM. The X-ray structure of the complex of 2 bound to Pin1 was determined to 1.76 Å resolution. The structure revealed that the reduced amide adopted a conformation similar to the proposed twisted-amide transition state of Pin1, with a trans-pyrrolidine conformation of the prolyl ring. A similar conformation of substrate would be destabilized relative to the planar amide conformation. Three additional reduced amides, with Thr replacing Ser and l- or d-pipecolate (Pip) replacing Pro, were slightly weaker inhibitors of Pin1.

Experimental and theoretical understanding of the gas phase oxidation of atmospheric amides with OH radicals: kinetics, products, and mechanisms.

Science.gov (United States)

Borduas, Nadine; da Silva, Gabriel; Murphy, Jennifer G; Abbatt, Jonathan P D

2015-05-14

Atmospheric amides have primary and secondary sources and are present in ambient air at low pptv levels. To better assess the fate of amides in the atmosphere, the room temperature (298 ± 3 K) rate coefficients of five different amides with OH radicals were determined in a 1 m(3) smog chamber using online proton-transfer-reaction mass spectrometry (PTR-MS). Formamide, the simplest amide, has a rate coefficient of (4.44 ± 0.46) × 10(-12) cm(3) molec(-1) s(-1) against OH, translating to an atmospheric lifetime of ∼1 day. N-methylformamide, N-methylacetamide and propanamide, alkyl versions of formamide, have rate coefficients of (10.1 ± 0.6) × 10(-12), (5.42 ± 0.19) × 10(-12), and (1.78 ± 0.43) × 10(-12) cm(3) molec(-1) s(-1), respectively. Acetamide was also investigated, but due to its slow oxidation kinetics, we report a range of (0.4-1.1) × 10(-12) cm(3) molec(-1) s(-1) for its rate coefficient with OH radicals. Oxidation products were monitored and quantified and their time traces were fitted using a simple kinetic box model. To further probe the mechanism, ab initio calculations are used to identify the initial radical products of the amide reactions with OH. Our results indicate that N-H abstractions are negligible in all cases, in contrast to what is predicted by structure-activity relationships. Instead, the reactions proceed via C-H abstraction from alkyl groups and from formyl C(O)-H bonds when available. The latter process leads to radicals that can readily react with O2 to form isocyanates, explaining the detection of toxic compounds such as isocyanic acid (HNCO) and methyl isocyanate (CH3NCO). These contaminants of significant interest are primary oxidation products in the photochemical oxidation of formamide and N-methylformamide, respectively.

Multicomponent ternary cocrystals of the sulfonamide group with pyridine-amides and lactams.

Science.gov (United States)

Bolla, Geetha; Nangia, Ashwini

2015-11-04

SMBA was selected as a bifunctional sulfa drug to design ternary cocrystals with pyridine amides and lactam coformers. Supramolecular assembly of five ternary cocrystals of p-sulfonamide benzoic acid with nicotinamide and 2-pyridone is demonstrated and reproducible heterosynthons are identified for crystal engineering.

Visible-light-promoted redox neutral C-H amidation of heteroarenes with hydroxylamine derivatives.

Science.gov (United States)

Qin, Qixue; Yu, Shouyun

2014-07-03

A room temperature redox neutral direct C-H amidation of heteroarenes has been achieved. Hydroxylamine derivatives, which are easily accessed, have been employed as tunable nitrogen sources. These reactions were enabled by a visible-light-promoted single-electron transfer pathway without a directing group. A variety of heteroarenes, such as indoles, pyrroles, and furans, could go through this amidation with high yields (up to 98%). These reactions are highly regioselective, and all the products were isolated as a single regioisomer.

Measurement of labile copper in wine by medium exchange stripping potentiometry utilising screen printed carbon electrodes.

Science.gov (United States)

Clark, Andrew C; Kontoudakis, Nikolaos; Barril, Celia; Schmidtke, Leigh M; Scollary, Geoffrey R

2016-07-01

The presence of copper in wine is known to impact the reductive, oxidative and colloidal stability of wine, and techniques enabling measurement of different forms of copper in wine are of particular interest in understanding these spoilage processes. Electrochemical stripping techniques developed to date require significant pretreatment of wine, potentially disturbing the copper binding equilibria. A thin mercury film on a screen printed carbon electrode was utilised in a flow system for the direct analysis of labile copper in red and white wine by constant current stripping potentiometry with medium exchange. Under the optimised conditions, including an enrichment time of 500s and constant current of 1.0μA, the response range was linear from 0.015 to 0.200mg/L. The analysis of 52 red and white wines showed that this technique generally provided lower labile copper concentrations than reported for batch measurement by related techniques. Studies in a model system and in finished wines showed that the copper sulfide was not measured as labile copper, and that loss of hydrogen sulfide via volatilisation induced an increase in labile copper within the model wine system. Copyright © 2016 Elsevier B.V. All rights reserved.

Amide-conjugated indole-3-acetic acid and adventitious root formation in mung bean cuttings

International Nuclear Information System (INIS)

Norcini, J.G.

1986-01-01

The purpose of this research was to investigate further the relationship between amide-conjugated auxin and adventitious root formation. Indoleacetylaspartic acid (IAA-aspartate) was positively identified as the predominant conjugate isolated from mung bean cuttings after the cuttings has been treated with 10 -3 M IAA. In cuttings treated with [1- 14 C]IAA immediately after excision (0 hr), the percent of extractable 14 C in IAA-aspartate in the hypocotyl sharply increased until 36 hr, then steadily declined. [ 14 C]IAA was completely metabolized between 12 and 24 hr. The rooting activities of IAA-L-aspartate, IAA-L-alanine, and IAA-glycine were determined at various stages of root formation; some cuttings were pretreated with 10 -3 M IAA at 0 hr. Pretreated cuttings that were treated with IAA-glycine at 12, 24, 36 hr exhibited the greatest consistency between replications, the greatest number of long roots, and the longest roots. The conjugates did not stimulate rooting as effectively as IAA, yet like IAA, generally enhanced rooting the greatest when applied before the first cell division (24 hr)

Phenotypic assessment of THC discriminative stimulus properties in fatty acid amide hydrolase knockout and wildtype mice.

Science.gov (United States)

Walentiny, D Matthew; Vann, Robert E; Wiley, Jenny L

2015-06-01

A number of studies have examined the ability of the endogenous cannabinoid anandamide to elicit Δ(9)-tetrahydrocannabinol (THC)-like subjective effects, as modeled through the THC discrimination paradigm. In the present study, we compared transgenic mice lacking fatty acid amide hydrolase (FAAH), the enzyme primarily responsible for anandamide catabolism, to wildtype counterparts in a THC discrimination procedure. THC (5.6 mg/kg) served as a discriminative stimulus in both genotypes, with similar THC dose-response curves between groups. Anandamide fully substituted for THC in FAAH knockout, but not wildtype, mice. Conversely, the metabolically stable anandamide analog O-1812 fully substituted in both groups, but was more potent in knockouts. The CB1 receptor antagonist rimonabant dose-dependently attenuated THC generalization in both groups and anandamide substitution in FAAH knockouts. Pharmacological inhibition of monoacylglycerol lipase (MAGL), the primary catabolic enzyme for the endocannabinoid 2-arachidonoylglycerol (2-AG), with JZL184 resulted in full substitution for THC in FAAH knockout mice and nearly full substitution in wildtypes. Quantification of brain endocannabinoid levels revealed expected elevations in anandamide in FAAH knockout mice compared to wildtypes and equipotent dose-dependent elevations in 2-AG following JZL184 administration. Dual inhibition of FAAH and MAGL with JZL195 resulted in roughly equipotent increases in THC-appropriate responding in both groups. While the notable similarity in THC's discriminative stimulus effects across genotype suggests that the increased baseline brain anandamide levels (as seen in FAAH knockout mice) do not alter THC's subjective effects, FAAH knockout mice are more sensitive to the THC-like effects of pharmacologically induced increases in anandamide and MAGL inhibition (e.g., JZL184). Copyright © 2015 Elsevier Ltd. All rights reserved.

Radiation initiated telomerization of ethylene with formamide and dimethylformamide

International Nuclear Information System (INIS)

Dederichs, B.; Saus, A.

1977-01-01

The radiation initiated telomerization of ethylene with formic acid amide and dimethylformamide under pressure was studied in detail. With formamide, homologous odd numbered linear alkane carbonic acid amides are obtained as the main products. Dimethylformamide gives homologous N,N-dimethyl alkane carbonic acid amides and N-methyl-N-alkyl-formic acid amides with a molar ratio of 1:1. The distribution of the homologous amides corresponds to a geometrical progression. The yield of telomers is proportional to the absorbed dose. The influence of the dose rate is given by the following equation: G = K x Isup(a-1). The exponent a was found to be 0.6. The reaction is pressure and temperature dependent. With increasing pressure the distribution of telomers is shifted to longer chain acid amides. Increasing temperature favours the yield of acid amides. The results are discussed from the radiation chemical point of view. (author)

Specific amino acids responsible for the cold adaptedness of Micrococcus antarcticus β-glucosidase BglU.

Science.gov (United States)

Miao, Li-Li; Fan, Hong-Xia; Qu, Jie; Liu, Ying; Liu, Zhi-Pei

2017-03-01

Psychrophilic enzymes display efficient activity at moderate or low temperatures (4-25 °C) and are therefore of great interest in biotechnological industries. We previously examined the crystal structure of BglU, a psychrophilic β-glucosidase from the bacterium Micrococcus antarcticus, at 2.2 Å resolution. In structural comparison and sequence alignment with mesophilic (BglB) and thermophilic (GlyTn) counterpart enzymes, BglU showed much lower contents of Pro residue and of charged amino acids (particularly positively charged) on the accessible surface area. In the present study, we investigated the roles of specific amino acid residues in the cold adaptedness of BglU. Mutagenesis assays showed that the mutations G261R and Q448P increased optimal temperature (from 25 to 40-45 °C) at the expense of low-temperature activity, but had no notable effects on maximal activity or heat lability. Mutations A368P, T383P, and A389E significantly increased optimal temperature (from 25 to 35-40 °C) and maximal activity (~1.5-fold relative to BglU). Thermostability of A368P and A389E increased slightly at 30 °C. Mutations K163P, N228P, and H301A greatly reduced enzymatic activity-almost completely in the case of H301A. Low contents of Pro, Arg, and Glu are important factors contributing to BglU's psychrophilic properties. Our findings will be useful in structure-based engineering of psychrophilic enzymes and in production of mutants suitable for a variety of industrial processes (e.g., food production, sewage treatment) at cold or moderate temperatures.

Acidity of hydroxamic acids and amides

Czech Academy of Sciences Publication Activity Database

Böhm, S.; Exner, Otto

2003-01-01

Roč. 1, č. 7 (2003), s. 1176-1180 ISSN 1477-0520 R&D Projects: GA AV ČR IAA4072005 Institutional research plan: CEZ:AV0Z4055905 Keywords : hydroxamic acids * DFT calculations * isodesmic reactions Subject RIV: CC - Organic Chemistry

Amides of non-steroidal anti-inflammatory drugs with thiomorpholine can yield hypolipidemic agents with improved anti-inflammatory activity.

Science.gov (United States)

Theodosis-Nobelos, Panagiotis; Kourti, Malamati; Gavalas, Antonios; Rekka, Eleni A

2016-02-01

Novel amides of non steroidal anti-inflammatory drugs (NSAIDs), α-lipoic acid and indole-3-acetic acid with thiomorpholine were synthesised by a simple method and at high yields (60-92%). All the NSAID derivatives highly decreased lipidemic indices in the plasma of Triton treated hyperlipidemic rats. The most potent compound was the indomethacin derivative, which decreased total cholesterol, triglycerides and LDL cholesterol by 73%, 80% and 83%, respectively. They reduced acute inflammation equally or more than most parent acids. Hence, it could be concluded that amides of common NSAIDs with thiomorpholine acquire considerable hypolipidemic potency, while they preserve or augment their anti-inflammatory activity, thus addressing significant risk factors for atherogenesis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hepatoprotective amide constituents from the fruit of Piper chaba: Structural requirements, mode of action, and new amides.

Science.gov (United States)

Matsuda, Hisashi; Ninomiya, Kiyofumi; Morikawa, Toshio; Yasuda, Daisuke; Yamaguchi, Itadaki; Yoshikawa, Masayuki

2009-10-15

The 80% aqueous acetone extract from the fruit of Piper chaba (Piperaceae) was found to have hepatoprotective effects on D-galactosamine (D-GalN)/lipopolysaccharide-induced liver injury in mice. From the ethyl acetate-soluble fraction, three new amides, piperchabamides E, G, and H, 33 amides, and four aromatic constituents were isolated. Among the isolates, several amide constituents inhibited D-GalN/tumor necrosis factor-alpha (TNF-alpha)-induced death of hepatocytes, and the following structural requirements were suggested: (i) the amide moiety is essential for potent activity; and (ii) the 1,9-decadiene structure between the benzene ring and the amide moiety tended to enhance the activity. Moreover, a principal constituent, piperine, exhibited strong in vivo hepatoprotective effects at doses of 5 and 10 mg/kg, po and its mode of action was suggested to depend on the reduced sensitivity of hepatocytes to TNF-alpha.

Acid tolerance in Salmonella typhimurium induced by culturing in the presence of organic acids at different growth temperatures.

Science.gov (United States)

Alvarez-Ordóñez, Avelino; Fernández, Ana; Bernardo, Ana; López, Mercedes

2010-02-01

The influence of growth temperature and acidification of the culture medium up to pH 4.25 with acetic, citric, lactic and hydrochloric acids on the growth and subsequent acid resistance at pH 3.0 of Salmonella typhimurium CECT 443 was studied. The minimum pH value which allowed for S. typhimurium growth within the temperature range of 25-37 degrees C was 4.5 when the pH was reduced using citric and hydrochloric acids, and 5.4 and 6.4 when lactic acid and acetic acid were used, respectively. At high (45 degrees C) or low (10 degrees C) temperatures, the growth pH boundary was increased about 1 pH unit. The growth temperature markedly modified the acid resistance of the resulting cells. In all cases, D-values were lower for cells grown at 10 degrees C and significantly increased with increasing growth temperature up to 37 degrees C, at which D-values obtained were up to 10 times higher. Cells grown at 45 degrees C showed D-values similar to those found for cells grown at 25 degrees C. The growth of cells in acidified media, regardless of the pH value, caused an increase in their acid resistance at the four incubation temperatures, although the magnitude of the Acid Tolerance Response (ATR) observed depended on the growth temperature. Acid adapted cultures at 10 degrees C showed D-values ranging from 5.75 to 6.91 min, which turned out to be about 2 times higher than those corresponding to non-acid adapted cultures, while higher temperatures induced an increase in D-values of at least 3.5 times. Another finding was that, while at 10 and 45 degrees C no significant differences among the effect of the different acids tested in inducing an ATR were observed, when cells were grown at 25 and 37 degrees C citric acid generally turned out to be the acid which induced the strongest ATR. Results obtained in this study show that growth temperature is an important factor affecting S. typhimurium acid resistance and could contribute to find new strategies based on intelligent

Amides in Nature and Biocatalysis

NARCIS (Netherlands)

Pitzer, J.; Steiner, K.

2016-01-01

Amides are widespread in biologically active compounds with a broad range of applications in biotechnology, agriculture and medicine. Therefore, as alternative to chemical synthesis the biocatalytic amide synthesis is a very interesting field of research. As usual, Nature can serve as guide in the

N-(3-Methylphenylsuccinamic acid

Directory of Open Access Journals (Sweden)

B. Thimme Gowda

2010-02-01

Full Text Available In the crystal structure of the title compound, C11H13NO3, the conformations of the N—H and C=O bonds in the amide segment are anti to each other, and that of the amide H atom is anti to the meta-methyl group in the benzene ring. Furthermore, the conformations of the amide oxygen and the carbonyl O atom of the acid segment are also anti to the adjacent –CH2 groups. The C=O and O—H bonds of the acid group are syn to each other. In the crystal, the molecules are packed into infinite chains through intermolecular N—H...O and O—H...O hydrogen bonds.

Amides are excellent mimics of phosphate internucleoside linkages and are well tolerated in short interfering RNAs.

Science.gov (United States)

Mutisya, Daniel; Selvam, Chelliah; Lunstad, Benjamin D; Pallan, Pradeep S; Haas, Amanda; Leake, Devin; Egli, Martin; Rozners, Eriks

2014-06-01

RNA interference (RNAi) has become an important tool in functional genomics and has an intriguing therapeutic potential. However, the current design of short interfering RNAs (siRNAs) is not optimal for in vivo applications. Non-ionic phosphate backbone modifications may have the potential to improve the properties of siRNAs, but are little explored in RNAi technologies. Using X-ray crystallography and RNAi activity assays, the present study demonstrates that 3'-CH2-CO-NH-5' amides are excellent replacements for phosphodiester internucleoside linkages in RNA. The crystal structure shows that amide-modified RNA forms a typical A-form duplex. The amide carbonyl group points into the major groove and assumes an orientation that is similar to the P-OP2 bond in the phosphate linkage. Amide linkages are well hydrated by tandem waters linking the carbonyl group and adjacent phosphate oxygens. Amides are tolerated at internal positions of both the guide and passenger strand of siRNAs and may increase the silencing activity when placed near the 5'-end of the passenger strand. As a result, an siRNA containing eight amide linkages is more active than the unmodified control. The results suggest that RNAi may tolerate even more extensive amide modification, which may be useful for optimization of siRNAs for in vivo applications. © The Author(s) 2014. Published by Oxford University Press on behalf of Nucleic Acids Research.

Fate and lability of silver in soils: Effect of ageing

Science.gov (United States)

The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the 110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectrosco...

A systematic analysis of backbone amide assignments achieved via combinatorial selective labelling of amino acids

Energy Technology Data Exchange (ETDEWEB)

Jeremy Craven, C. [University of Sheffield, Department of Biotechnology and Molecular Biology (United Kingdom); Al-Owais, Moza; Parker, Martin J. [University of Leeds, Astbury Centre for Structural Molecular Biology, Institute of Molecular and Cellular Biology (United Kingdom)], E-mail: m.j.parker@leeds.ac.uk

2007-06-15

With the advent of high-yield cell-free expressions systems, many researchers are exploiting selective isotope labelling of amino acids to increase the efficiency and accuracy of the NMR assignment process. We developed recently a combinatorial selective labelling (CSL) method capable of yielding large numbers of residue-type and sequence-specific backbone amide assignments, which involves comparing cross-peak intensities in {sup 1}H-{sup 15}N HSQC and 2D {sup 1}H-{sup 15}N HNCO spectra collected for five samples containing different combinations of {sup 13}C- and {sup 15}N-labelled amino acids [Parker MJ, Aulton-Jones M, Hounslow A, Craven C J (2004) J Am Chem Soc 126:5020-5021]. In this paper we develop a robust method for establishing the reliability of these assignments. We have performed a detailed statistical analysis of the CSL data collected for a model system (the B1 domain of protein G from Streptococcus), developing a scoring method which allows the confidence in assignments to be assessed, and which enables the effects of overlap on assignment fidelity to be predicted. To further test the scoring method and also to assess the performance of CSL in relation to sample quality, we have applied the method to the CSL data collected for GFP in our previous study.

Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides.

Science.gov (United States)

Hoang, G L; Zhang, S; Takacs, J M

2018-05-08

γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.

Synthesis and proapoptotic activity of oleanolic acid derived amides.

Science.gov (United States)

Heller, Lucie; Knorrscheidt, Anja; Flemming, Franziska; Wiemann, Jana; Sommerwerk, Sven; Pavel, Ioana Z; Al-Harrasi, Ahmed; Csuk, René

2016-10-01

Thirty-one different 3-O-acetyl-OA derived amides have been prepared and screened for their cytotoxic activity. In the SRB assays nearly all the carboxamides displayed good cytotoxicity in the low μM range for several human tumor cell lines. Low EC50 values were obtained especially for the picolinylamides 14-16, for a N-[2-(dimethylamino)-ethyl] derivative 27 and a N-[2-(pyrrolinyl)-ethyl] carboxamide 28. These compounds were submitted to an extensive biological testing and proved compound 15 to act mainly by an arrest of the tumor cells in the S phase of the cell cycle. Cell death occurred by autophagy while compounds 27 and 28 triggered apoptosis. Copyright © 2016 Elsevier Inc. All rights reserved.

Protein Topology Determines Cysteine Oxidation Fate: The Case of Sulfenyl Amide Formation among Protein Families

Science.gov (United States)

Defelipe, Lucas A.; Lanzarotti, Esteban; Gauto, Diego; Marti, Marcelo A.; Turjanski, Adrián G.

2015-01-01

Cysteine residues have a rich chemistry and play a critical role in the catalytic activity of a plethora of enzymes. However, cysteines are susceptible to oxidation by Reactive Oxygen and Nitrogen Species, leading to a loss of their catalytic function. Therefore, cysteine oxidation is emerging as a relevant physiological regulatory mechanism. Formation of a cyclic sulfenyl amide residue at the active site of redox-regulated proteins has been proposed as a protection mechanism against irreversible oxidation as the sulfenyl amide intermediate has been identified in several proteins. However, how and why only some specific cysteine residues in particular proteins react to form this intermediate is still unknown. In the present work using in-silico based tools, we have identified a constrained conformation that accelerates sulfenyl amide formation. By means of combined MD and QM/MM calculation we show that this conformation positions the NH backbone towards the sulfenic acid and promotes the reaction to yield the sulfenyl amide intermediate, in one step with the concomitant release of a water molecule. Moreover, in a large subset of the proteins we found a conserved beta sheet-loop-helix motif, which is present across different protein folds, that is key for sulfenyl amide production as it promotes the previous formation of sulfenic acid. For catalytic activity, in several cases, proteins need the Cysteine to be in the cysteinate form, i.e. a low pKa Cys. We found that the conserved motif stabilizes the cysteinate by hydrogen bonding to several NH backbone moieties. As cysteinate is also more reactive toward ROS we propose that the sheet-loop-helix motif and the constraint conformation have been selected by evolution for proteins that need a reactive Cys protected from irreversible oxidation. Our results also highlight how fold conservation can be correlated to redox chemistry regulation of protein function. PMID:25741692

Synthesis, Crystal Structures and Properties of Ferrocenyl Bis-Amide Derivatives Yielded via the Ugi Four-Component Reaction.

Science.gov (United States)

Zhao, Mei; Shao, Guang-Kui; Huang, Dan-Dan; Lv, Xue-Xin; Guo, Dian-Shun

2017-05-04

Ten ferrocenyl bis-amide derivatives were successfully synthesized via the Ugi four-component reaction by treating ferrocenecarboxylic acid with diverse aldehydes, amines, and isocyanides in methanol solution. Their chemical structures were fully characterized by IR, NMR, HR-MS, and X-ray diffraction analyses. They feature unique molecular morphologies and create a 14-membered ring motif in the centro-symmetric dimers generated in the solid state. Moreover, the electrochemical behavior of these ferrocenyl bis-amides was assessed by cyclic voltammetry.

Biodegradable gadolinium-chelated cationic poly(urethane amide) copolymers for gene transfection and magnetic resonance imaging

Energy Technology Data Exchange (ETDEWEB)

Gao, Xiaolong [Department of Radiology, Tongji Hospital, Tongji University School of Medicine, Shanghai 200065 (China); Wang, Gangmin [Department of Urology, Huashan Hospital, Fudan University, Shanghai 200040 (China); Shi, Ting [The Institute for Translational Nanomedicine, Shanghai East Hospital, Institute for Biomedical Engineering and Nanoscience, Tongji University School of Medicine, Shanghai 200092 (China); Shao, Zhihong [Department of Radiology, Tongji Hospital, Tongji University School of Medicine, Shanghai 200065 (China); Zhao, Peng; Shi, Donglu [The Institute for Translational Nanomedicine, Shanghai East Hospital, Institute for Biomedical Engineering and Nanoscience, Tongji University School of Medicine, Shanghai 200092 (China); Ren, Jie [Institute of Nano and Biopolymeric Materials, School of Materials Science and Engineering, Tongji University, 4800 Caoan Road, Shanghai 201804 (China); Lin, Chao, E-mail: chaolin@tongji.edu.cn [The Institute for Translational Nanomedicine, Shanghai East Hospital, Institute for Biomedical Engineering and Nanoscience, Tongji University School of Medicine, Shanghai 200092 (China); Wang, Peijun, E-mail: tjpjwang@sina.com [Department of Radiology, Tongji Hospital, Tongji University School of Medicine, Shanghai 200065 (China)

2016-08-01

Theranostic nano-polyplexes containing gene and imaging agents hold a great promise for tumor diagnosis and therapy. In this work, we develop a group of new gadolinium (Gd)-chelated cationic poly(urethane amide)s for gene delivery and T{sub 1}-weighted magnetic resonance (MR) imaging. Cationic poly(urethane amide)s (denoted as CPUAs) having multiple disulfide bonds, urethane and amide linkages were synthesized by stepwise polycondensation reaction between 1,4-bis(3-aminopropyl)piperazine and a mixture of di(4-nitrophenyl)-2, 2′-dithiodiethanocarbonate (DTDE-PNC) and diethylenetriaminepentaacetic acid (DTPA) dianhydride at varied molar ratios. Then, Gd-chelated CPUAs (denoted as GdCPUAs) were produced by chelating Gd(III) ions with DTPA residues of CPUAs. These GdCPUAs could condense gene into nanosized and positively-charged polyplexes in a physiological condition and, however, liberated gene in an intracellular reductive environment. In vitro transfection experiments revealed that the GdCPUA at a DTDE-PNC/DTPA residue molar ratio of 85/15 induced the highest transfection efficiency in different cancer cells. This efficiency was higher than that yielded with 25 kDa branched polyethylenimine as a positive control. GdCPUAs and their polyplexes exhibited low cytotoxicity when an optimal transfection activity was detected. Moreover, GdCPUAs may serve as contrast agents for T{sub 1}-weighted magnetic resonance imaging. The results of this work indicate that biodegradable Gd-chelated cationic poly(urethane amide) copolymers have high potential for tumor theranostics. - Highlights: • Novel cationic gadolinium-chelated poly(urethane amide)s (GdCPUAs) are prepared. • GdCPUAs can induce a high transfection efficacy in different cancer cells. • GdCPUAs reveal good cyto-compatibility against cancer cells. • GdCPUAs may be applied as T{sub 1}-contrast agents for magnetic resonance imaging. • GdCPUAs hold high potential for cancer theranostics.

Biodegradable gadolinium-chelated cationic poly(urethane amide) copolymers for gene transfection and magnetic resonance imaging

International Nuclear Information System (INIS)

Gao, Xiaolong; Wang, Gangmin; Shi, Ting; Shao, Zhihong; Zhao, Peng; Shi, Donglu; Ren, Jie; Lin, Chao; Wang, Peijun

2016-01-01

Theranostic nano-polyplexes containing gene and imaging agents hold a great promise for tumor diagnosis and therapy. In this work, we develop a group of new gadolinium (Gd)-chelated cationic poly(urethane amide)s for gene delivery and T 1 -weighted magnetic resonance (MR) imaging. Cationic poly(urethane amide)s (denoted as CPUAs) having multiple disulfide bonds, urethane and amide linkages were synthesized by stepwise polycondensation reaction between 1,4-bis(3-aminopropyl)piperazine and a mixture of di(4-nitrophenyl)-2, 2′-dithiodiethanocarbonate (DTDE-PNC) and diethylenetriaminepentaacetic acid (DTPA) dianhydride at varied molar ratios. Then, Gd-chelated CPUAs (denoted as GdCPUAs) were produced by chelating Gd(III) ions with DTPA residues of CPUAs. These GdCPUAs could condense gene into nanosized and positively-charged polyplexes in a physiological condition and, however, liberated gene in an intracellular reductive environment. In vitro transfection experiments revealed that the GdCPUA at a DTDE-PNC/DTPA residue molar ratio of 85/15 induced the highest transfection efficiency in different cancer cells. This efficiency was higher than that yielded with 25 kDa branched polyethylenimine as a positive control. GdCPUAs and their polyplexes exhibited low cytotoxicity when an optimal transfection activity was detected. Moreover, GdCPUAs may serve as contrast agents for T 1 -weighted magnetic resonance imaging. The results of this work indicate that biodegradable Gd-chelated cationic poly(urethane amide) copolymers have high potential for tumor theranostics. - Highlights: • Novel cationic gadolinium-chelated poly(urethane amide)s (GdCPUAs) are prepared. • GdCPUAs can induce a high transfection efficacy in different cancer cells. • GdCPUAs reveal good cyto-compatibility against cancer cells. • GdCPUAs may be applied as T 1 -contrast agents for magnetic resonance imaging. • GdCPUAs hold high potential for cancer theranostics.

Tris(2-aminoethyl)amine-based α-branched fatty acid amides - Synthesis of lipids and comparative study of transfection efficiency of their lipid formulations.

Science.gov (United States)

Erdmann, Nicole; Wölk, Christian; Schulze, Ingo; Janich, Christopher; Folz, Manuela; Drescher, Simon; Dittrich, Matthias; Meister, Annette; Vogel, Jürgen; Groth, Thomas; Dobner, Bodo; Langner, Andreas

2015-10-01

The synthesis of a new class of cationic lipids, tris(2-aminoethyl)amine-based α-branched fatty acid amides, is described resulting in a series of lipids with specific variations in the lipophilic as well as the hydrophilic part of the lipids. In-vitro structure/transfection relationships were established by application of complexes of these lipids with plasmid DNA (pDNA) to different cell lines. The α-branched fatty acid amide bearing two tetradecyl chains and two lysine molecules (T14diLys) in mixture with the co-lipid 1,2-di-[(9Z)-octadec-9-enoyl]-sn-glycero-3-phosphoethanolamine (DOPE) (1/2, n/n) exhibits effective pDNA transfer in three different cell lines, namely Hep-G2, A549, and COS-7. The presence of 10% serum during lipoplex incubation of the cells did not affect the transfection efficiency. Based on that, detailed investigations of the complexation of pDNA with the lipid formulation T14diLys/DOPE 1/2 (n/n) were carried out with respect to particle size and charge using dynamic light scattering (DLS), ζ-potential measurements, and transmission electron microscopy (TEM). Additionally, the lipoplex uptake was investigated by confocal laser scanning microscopy (CLSM). Overall, lipoplexes prepared from T14diLys/DOPE 1/2 (n/n) offer large potential as lipid-based polynucleotide carriers and further justify advanced examinations. Copyright © 2015 Elsevier B.V. All rights reserved.

Application of nanoparticles for oral delivery of acid-labile lansoprazole in the treatment of gastric ulcer: in vitro and in vivo evaluations

Directory of Open Access Journals (Sweden)

Alai M

2015-06-01

Full Text Available Milind Alai,1 Wen Jen Lin1,2 1Graduate Institute of Pharmaceutical Sciences, School of Pharmacy, 2Drug Research Center, College of Medicine, National Taiwan University, Taipei, Taiwan Abstract: The aim of this study was to develop nanoparticles for oral delivery of an acid-labile drug, lansoprazole (LPZ, for gastric ulcer therapy. LPZ-loaded positively charged Eudragit® RS100 nanoparticles (ERSNPs-LPZ and negatively charged poly(lactic-co-glycolic acid nanoparticles (PLGANPs-LPZ were prepared. The effect of charge on nanoparticle deposition in ulcerated and non-ulcerated regions of the stomach was investigated. The cellular uptake of nanoparticles in the intestine was evaluated in a Caco-2 cell model. The pharmacokinetic performance and ulcer healing response of LPZ-loaded nanoparticles following oral administration were evaluated in Wistar rats with induced ulcers. The prepared drug-loaded ERSNPs-LPZ and PLGANPs-LPZ possessed opposite surface charge (+38.5±0.3 mV versus -27.3±0.3 mV, respectively and the particle size was around 200 nm with a narrow size distribution. The negatively charged PLGANPs adhered more readily to the ulcerated region (7.22%±1.21% per cm2, whereas the positively charged ERSNPs preferentially distributed in the non-ulcerated region (8.29%±0.35% per cm2. Both ERSNPs and PLGANPs were prominent uptake in Caco-2 cells, too. The nanoparticles sustained and prolonged LPZ concentrations up to 24 hours, and the half-life and mean residence time of LPZ were prolonged by 3.5-fold and 4.5-fold, respectively, as compared with LPZ solution. Oral administration of LPZ-loaded nanoparticles healed 92.6%–95.7% of gastric ulcers in Wistar rats within 7 days. Keywords: nanoparticles, lansoprazole, Eudragit® RS100, PLGA

T. thermophila group I introns that cleave amide bonds

Science.gov (United States)

Joyce, Gerald F. (Inventor)

1997-01-01

The present invention relates to nucleic acid enzymes or enzymatic RNA molecules that are capable of cleaving a variety of bonds, including phosphodiester bonds and amide bonds, in a variety of substrates. Thus, the disclosed enzymatic RNA molecules are capable of functioning as nucleases and/or peptidases. The present invention also relates to compositions containing the disclosed enzymatic RNA molecule and to methods of making, selecting, and using such enzymes and compositions.

The response of amino acid cycling to global change across multiple biomes: Feedbacks on soil nitrogen availability

Science.gov (United States)

Brzostek, E. R.; Finzi, A. C.

2010-12-01

The cycling of organic nitrogen (N) in soil links soil organic matter decomposition to ecosystem productivity. Amino acids are a key pool of organic N in the soil, whose cycling is sensitive to alterations in microbial demand for carbon and N. Further, the amino acids released from the breakdown of protein by proteolytic enzymes are an important source of N that supports terrestrial productivity. The objective of this study was to measure changes in amino acid cycling in response to experimental alterations of precipitation and temperature in twelve global change experiments during the 2009 growing season. The study sites ranged from arctic tundra to xeric grasslands. The treatments experimentally increased temperature, increased or decreased precipitation, or some combination of both factors. The response of amino acid cycling to temperature and precipitation manipulations tended to be site specific, but the responses could be placed into a common framework. Changes in soil moisture drove a large response in amino acid cycling. Precipitation augmentation in xeric and mesic sites increased both amino acid pool sizes and production. However, treatments that decreased precipitation drove decreases in amino acid cycling in xeric sites, but led to increases in amino acid cycling in more mesic sites. Across sites, the response to soil warming was horizon specific. Amino acid cycling in organic rich horizons responded positively to warming, while negative responses were exhibited in lower mineral soil horizons. The variable response likely reflects a higher availability of protein substrate to sustain high rates of proteolytic enzyme activity in organic rich horizons. Overall, these results suggest that soil moisture and the availability of protein substrate may be important factors that mediate the response of amino acid cycling to predicted increases in soil temperatures.

Recognition of RNA by amide modified backbone nucleic acids: molecular dynamics simulations of DNA-RNA hybrids in aqueous solution.

Science.gov (United States)

Nina, Mafalda; Fonné-Pfister, Raymonde; Beaudegnies, Renaud; Chekatt, Habiba; Jung, Pierre M J; Murphy-Kessabi, Fiona; De Mesmaeker, Alain; Wendeborn, Sebastian

2005-04-27

Thermodynamic and structural properties of a chemically modified DNA-RNA hybrid in which a phosphodiester linkage is replaced by a neutral amide-3 linkage (3'-CH(2)-CONH-5') were investigated using UV melting experiments, molecular dynamics simulations in explicit water, and continuum solvent models. van't Hoff analysis of the experimental UV melting curves suggests that the significant increase of the thermodynamic stability of a 15-mer DNA-RNA with seven alternated amide-3 modifications (+11 degrees C) is mainly due to an increased binding enthalpy. To further evaluate the origin in the observed affinities differences, the electrostatic contribution to the binding free energy was calculated by solving the Poisson-Boltzmann equation numerically. The nonelectrostatic contribution was estimated as the product of a hydrophobic surface tension coefficient and the surface area that is buried upon double strand formation. Structures were taken from 10 ns molecular dynamics simulations computed in a consistent fashion using explicit solvent, counterions, and the particle-mesh Ewald procedure. The present preliminary thermodynamic study suggests that the favorable binding free energy of the amide-3 DNA single strand to the complementary RNA is equally driven by electrostatic and nonpolar contributions to the binding compared to their natural analogues. In addition, molecular dynamics simulations in explicit water were performed on an amide-3 DNA single strand and the corresponding natural DNA. Results from the conformations cluster analysis of the simulated amide-3 DNA single strand ensembles suggest that the 25% of the population sampled within 10 ns has a pre-organized conformation where the sugar C3' endo pucker is favored at the 3'-flanking nucleotides. These structural and thermodynamic features contribute to the understanding of the observed increased affinities of the amide-3 DNA-RNA hybrids at the microscopic level.

Metabolome Integrated Analysis of High-Temperature Response in Pinus radiata

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Mónica Escandón

2018-04-01

Full Text Available The integrative omics approach is crucial to identify the molecular mechanisms underlying high-temperature response in non-model species. Based on future scenarios of heat increase, Pinus radiata plants were exposed to a temperature of 40°C for a period of 5 days, including recovered plants (30 days after last exposure to 40°C in the analysis. The analysis of the metabolome using complementary mass spectrometry techniques (GC-MS and LC-Orbitrap-MS allowed the reliable quantification of 2,287 metabolites. The analysis of identified metabolites and highlighter metabolic pathways across heat time exposure reveal the dynamism of the metabolome in relation to high-temperature response in P. radiata, identifying the existence of a turning point (on day 3 at which P. radiata plants changed from an initial stress response program (shorter-term response to an acclimation one (longer-term response. Furthermore, the integration of metabolome and physiological measurements, which cover from the photosynthetic state to hormonal profile, suggests a complex metabolic pathway interaction network related to heat-stress response. Cytokinins (CKs, fatty acid metabolism and flavonoid and terpenoid biosynthesis were revealed as the most important pathways involved in heat-stress response in P. radiata, with zeatin riboside (ZR and isopentenyl adenosine (iPA as the key hormones coordinating these multiple and complex interactions. On the other hand, the integrative approach allowed elucidation of crucial metabolic mechanisms involved in heat response in P. radiata, as well as the identification of thermotolerance metabolic biomarkers (L-phenylalanine, hexadecanoic acid, and dihydromyricetin, crucial metabolites which can reschedule the metabolic strategy to adapt to high temperature.

Assessing soil carbon lability by near infrared spectroscopy and NaOCL oxidation

DEFF Research Database (Denmark)

Thomsen, Ingrid Kaag; Bruun, Sander; Jensen, Lars Stoumann

2009-01-01

The feasibility of near infrared (NIR) spectroscopy for quantifying labile organic matter (OM) in arable soils and for predicting soil refractory OM fractions was tested on 37 soils varying in texture and soil carbon (C) content. Three sets of arable soils (0-20 cm depth) were sampled from 1) long......-term field experiments with different OM inputs, 2) individual sites with inherent with-in field gradients in soil texture and/or C content, and 3) from a range of different sites covering variations in management and geological origin. The labile OM fraction was defined by the CO2 evolved from the soils...... incubated for 34 weeks while refractory OM was obtained by NaOCl oxidation. The labile fraction of the soil C accounted for 2-12% of the total soil C content. No systematic relationship between labile C content and total soil C or clay was found, but NIR spectra could be correlated well with the labile C...

Enhanced high temperature thermoelectric response of sulphuric acid treated conducting polymer thin films

KAUST Repository

Sarath Kumar, S. R.; Kurra, Narendra; Alshareef, Husam N.

2015-01-01

We report the high temperature thermoelectric properties of solution processed pristine and sulphuric acid treated poly(3, 4-ethylenedioxythiophene):poly(4-styrenesulfonate) (or PEDOT:PSS) films. The acid treatment is shown to simultaneously enhance the electrical conductivity and Seebeck coefficient of the metal-like films, resulting in a five-fold increase in thermoelectric power factor (0.052 W/m. K ) at 460 K, compared to the pristine film. By using atomic force micrographs, Raman and impedance spectra and using a series heterogeneous model for electrical conductivity, we demonstrate that acid treatment results in the removal of PSS from the films, leading to the quenching of accumulated charge-induced energy barriers that prevent hopping conduction. The continuous removal of PSS with duration of acid treatment also alters the local band structure of PEDOT:PSS, resulting in simultaneous enhancement in Seebeck coefficient.

Enhanced high temperature thermoelectric response of sulphuric acid treated conducting polymer thin films

KAUST Repository

Sarath Kumar, S. R.

2015-11-24

We report the high temperature thermoelectric properties of solution processed pristine and sulphuric acid treated poly(3, 4-ethylenedioxythiophene):poly(4-styrenesulfonate) (or PEDOT:PSS) films. The acid treatment is shown to simultaneously enhance the electrical conductivity and Seebeck coefficient of the metal-like films, resulting in a five-fold increase in thermoelectric power factor (0.052 W/m. K ) at 460 K, compared to the pristine film. By using atomic force micrographs, Raman and impedance spectra and using a series heterogeneous model for electrical conductivity, we demonstrate that acid treatment results in the removal of PSS from the films, leading to the quenching of accumulated charge-induced energy barriers that prevent hopping conduction. The continuous removal of PSS with duration of acid treatment also alters the local band structure of PEDOT:PSS, resulting in simultaneous enhancement in Seebeck coefficient.

Determination of the equilibrium micelle-inserting position of the fusion peptide of gp41 of human immunodeficiency virus type 1 at amino acid resolution by exchange broadening of amide proton resonances

International Nuclear Information System (INIS)

Chang, D.-K.; Cheng, S.-F.

1998-01-01

The exchange broadening of backbone amide proton resonances of a 23-mer fusion peptide of the transmembrane subunit of HIV-1 envelope glycoprotein gp41, gp41-FP, was investigated at pH 5 and 7 at room temperature in perdeuterated sodium dodecyl sulfate (SDS) micellar solution. Comparison of resonance peaks for these pHs revealed an insignificant change in exchange rate between pH 5 and 7 for amide protons of residues 4 through 14, while the exchange rate increase at neutral pH was more prominent for amide protons of the remaining residues, with peaks from some protons becoming undetectable. The relative insensitivity to pH of the exchange for the amide protons of residues 4 through 14 is attributable to the drastic reduction in [OH-] in the micellar interior, leading to a decreased exchange rate. The A15-G16 segment represents a transition between these two regimes. The data are thus consistent with the notion that the peptide inserts into the hydrophobic core of a membrane-like structure and the A15-G16 dipeptide is located at the micellar-aqueous boundary

Distribution and origin of major and trace elements (particularly REE, U and Th) into labile and residual phases in an acid soil profile (Vosges Mountains, France)

Science.gov (United States)

Aubert, D.; Probst, A.; Stille, P.

2003-04-01

Physical and chemical weathering of rocks and minerals lead to soil formation and allow the removal of chemical elements from these systems to ground- or surface waters. But most of the time the determination of element concentrations in soils is not sufficient to estimate whether they are being accumulated or what is their ability to be released in the environment. Thus, the distribution and chemical binding for a given element is very important because it determines its mobility and potential bioavailability throughout a soil profile. Heavy metals and REE (Rare Earth Elements) are particularly of environmental concern because of their potential toxicity. For most of them, their chemical form strongly depends on the evolution of physico-chemical parameters like pH or redox conditions that will induce adsorption-desorption, complexation or co-precipitation phenomena in the material. The purpose of this study is to determine the distribution of several major and trace elements (especially REE, Th and U) in an acidic forested podzolic soil profile from the Vosges Mountains (France). To achieve this goal we use a 7 step sequential extraction procedure that allows determining precisely the origin and the behaviour of particular elements in the environment (Leleyter et al., 1999). In addition we performed leaching experiments using very dilute acetic and hydrochloric acid in order to establish the origin of REE in this soil. The results of the sequential extraction indicate that most of the metals, Th and U are mainly bound to Fe oxides. Organic matter appears also to be a great carrier of P, Ca, Fe and REE even if its content is very low in the deep horizons of the soil. Moreover, we show that in each soil horizon, middle REE (MREE) to heavy REE (HREE) are more labile than light REE (LREE). Leaching experiments using dilute acid solution further suggest that in the shallowest horizons REE largely derive from atmospheric deposition whereas at greater depth, weathering

Amide-transforming activity of Streptomyces: possible application to the formation of hydroxy amides and aminoalcohols.

Science.gov (United States)

Yamada, Shinya; Miyagawa, Taka-Aki; Yamada, Ren; Shiratori-Takano, Hatsumi; Sayo, Noboru; Saito, Takao; Takano, Hideaki; Beppu, Teruhiko; Ueda, Kenji

2013-07-01

To develop an efficient bioconversion process for amides, we screened our collection of Streptomyces strains, mostly obtained from soil, for effective transformers. Five strains, including the SY007 (NBRC 109343) and SY435 (NBRC 109344) of Streptomyces sp., exhibited marked conversion activities from the approximately 700 strains analyzed. These strains transformed diverse amide compounds such as N-acetyltetrahydroquinoline, N-benzoylpyrrolidine, and N-benzoylpiperidine into alcohols or N,O-acetals with high activity and regioselectivity. N,O-acetal was transformed into alcohol by serial tautomerization and reduction reactions. As such, Streptomyces spp. can potentially be used for the efficient preparation of hydroxy amides and aminoalcohols.

Synthesis and Characterization of Novel Polyurethanes Based on Vegetable Oils Amide and Ester Polyols

Directory of Open Access Journals (Sweden)

Vladimir YAKUSHIN

2014-09-01

Full Text Available Amide and ester type polyols were synthesized from rapeseed, sunflower and castor oils, and two types of ethanolamine (diethanolamine and triethanolamine at different molar ratio. Poly(urethane amides and polyester urethanes based on the synthesized polyols were prepared. The effect of the chemical structure of the obtained polyurethanes on density, glass transition temperature, thermal stability and mechanical properties was investigated. The influence of the content of OH groups in the synthesized polyols on the specified characteristics was estimated. It has been found that poly(urethane amides have better mechanical characteristics, but their thermal stability is lower than that of polyester urethanes. The chemical structure of the synthesized polyols and polyurethanes is qualitatively confirmed by IR-spectroscopy data. DOI: http://dx.doi.org/10.5755/j01.ms.20.3.4532

Cyclisation versus 1,1-Carboboration: Reactions of B(C6F5)3 with Propargyl Amides.

Science.gov (United States)

Melen, Rebecca L; Hansmann, Max M; Lough, Alan J; Hashmi, A Stephen K; Stephan, Douglas W

2013-09-02

A series of propargyl amides were prepared and their reactions with the Lewis acidic compound B(C6F5)3 were investigated. These reactions were shown to afford novel heterocycles under mild conditions. The reaction of a variety of N-substituted propargyl amides with B(C6F5)3 led to an intramolecular oxo-boration cyclisation reaction, which afforded the 5-alkylidene-4,5-dihydrooxazolium borate species. Secondary propargyl amides gave oxazoles in B(C6F5)3 mediated (catalytic) cyclisation reactions. In the special case of disubstitution adjacent to the nitrogen atom, 1,1-carboboration is favoured as a result of the increased steric hindrance (1,3-allylic strain) in the 5-alkylidene-4,5-dihydrooxazolium borate species. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ IR studies of Co and Ce doped Mn/TiO{sub 2} catalyst for low-temperature selective catalytic reduction of NO with NH{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Qiu, Lu; Pang, Dandan; Zhang, Changliang; Meng, Jiaojiao; Zhu, Rongshu; Ouyang, Feng, E-mail: ouyangfh@hit.edu.cn

2015-12-01

Highlights: • A SCR mechanistic pathway over Mn–Co–Ce/TiO{sub 2} is proposed. • The cobalt oxide produces lots of Brønsted acid sites, which favor to the adsorption of coordinated NH{sub 3} through NH{sub 3} migration. • Ce addition improves amide ions formation to reach best NO reduction selectivity. • At low-temperature coordinated NH{sub 3} reacts with NO{sub 2}{sup −}, or amide reacts with NO (ad) or NO (g) to form N{sub 2}. At high temperature, the reaction also occurs between coordinated NH{sub 3} and nitrate species. - Abstract: The Mn–Co–Ce/TiO{sub 2} catalyst was prepared by wet co-impregnation method for selective catalytic reduction of NO by NH{sub 3} in the presence of oxygen. The adsorption and co-adsorption of NH{sub 3}, NO and O{sub 2} on catalysts were investigated by in situ FTIR spectroscopy. The results suggested that addition of cobalt and cerium oxides increased the numbers of acid and redox sites. Especially, the cobalt oxide produced lots of Brønsted acid sites, which favor to the adsorption of coordinated NH{sub 3} through NH{sub 3} migration. Ce addition improved amide ions formation to reach best NO reduction selectivity. A mechanistic pathway over Mn–Co–Ce/TiO{sub 2} was proposed. At low-temperature SCR reaction, coordinated NH{sub 3} reacted with NO{sub 2}{sup −}, and amide reacted with NO (ad) or NO (g) to form N{sub 2}. NO{sub 2} was related to the formation of nitrite on Co-contained catalysts and the generation of −NH{sub 2}{sup −} on Ce-contained catalysts. At high temperature, the other branch reaction also occurred between the coordinated NH{sub 3} and nitrate species, resulting in N{sub 2}O yield increase.

How amide hydrogens exchange in native proteins.

Science.gov (United States)

Persson, Filip; Halle, Bertil

2015-08-18

Amide hydrogen exchange (HX) is widely used in protein biophysics even though our ignorance about the HX mechanism makes data interpretation imprecise. Notably, the open exchange-competent conformational state has not been identified. Based on analysis of an ultralong molecular dynamics trajectory of the protein BPTI, we propose that the open (O) states for amides that exchange by subglobal fluctuations are locally distorted conformations with two water molecules directly coordinated to the N-H group. The HX protection factors computed from the relative O-state populations agree well with experiment. The O states of different amides show little or no temporal correlation, even if adjacent residues unfold cooperatively. The mean residence time of the O state is ∼100 ps for all examined amides, so the large variation in measured HX rate must be attributed to the opening frequency. A few amides gain solvent access via tunnels or pores penetrated by water chains including native internal water molecules, but most amides access solvent by more local structural distortions. In either case, we argue that an overcoordinated N-H group is necessary for efficient proton transfer by Grotthuss-type structural diffusion.

How amide hydrogens exchange in native proteins

Science.gov (United States)

Persson, Filip; Halle, Bertil

2015-01-01

Amide hydrogen exchange (HX) is widely used in protein biophysics even though our ignorance about the HX mechanism makes data interpretation imprecise. Notably, the open exchange-competent conformational state has not been identified. Based on analysis of an ultralong molecular dynamics trajectory of the protein BPTI, we propose that the open (O) states for amides that exchange by subglobal fluctuations are locally distorted conformations with two water molecules directly coordinated to the N–H group. The HX protection factors computed from the relative O-state populations agree well with experiment. The O states of different amides show little or no temporal correlation, even if adjacent residues unfold cooperatively. The mean residence time of the O state is ∼100 ps for all examined amides, so the large variation in measured HX rate must be attributed to the opening frequency. A few amides gain solvent access via tunnels or pores penetrated by water chains including native internal water molecules, but most amides access solvent by more local structural distortions. In either case, we argue that an overcoordinated N–H group is necessary for efficient proton transfer by Grotthuss-type structural diffusion. PMID:26195754

Dual, differential isotope labeling shows the preferential movement of labile plant constituents into mineral-bonded soil organic matter.

Science.gov (United States)

Haddix, Michelle L; Paul, Eldor A; Cotrufo, M Francesca

2016-06-01

The formation and stabilization of soil organic matter (SOM) are major concerns in the context of global change for carbon sequestration and soil health. It is presently believed that lignin is not selectively preserved in soil and that chemically labile compounds bonding to minerals comprise a large fraction of the SOM. Labile plant inputs have been suggested to be the main precursor of the mineral-bonded SOM. Litter decomposition and SOM formation are expected to have temperature sensitivity varying with the lability of plant inputs. We tested this framework using dual (13) C and (15) N differentially labeled plant material to distinguish the metabolic and structural components within a single plant material. Big Bluestem (Andropogon gerardii) seedlings were grown in an enriched (13) C and (15) N environment and then prior to harvest, removed from the enriched environment and allowed to incorporate natural abundance (13) C-CO2 and (15) N fertilizer into the metabolic plant components. This enabled us to achieve a greater than one atom % difference in (13) C between the metabolic and structural components within the plant litter. This differentially labeled litter was incubated in soil at 15 and 35 °C, for 386 days with CO2 measured throughout the incubation. After 14, 28, 147, and 386 days of incubation, the soil was subsequently fractionated. There was no difference in temperature sensitivity of the metabolic and structural components with regard to how much was respired or in the amount of litter biomass stabilized. Only the metabolic litter component was found in the sand, silt, or clay fraction while the structural component was exclusively found in the light fraction. These results support the stabilization framework that labile plant components are the main precursor of mineral-associated organic matter. © 2016 John Wiley & Sons Ltd.

Relationship between the lability of sediment-bound Cd and its bioaccumulation in edible oyster.

Science.gov (United States)

Chakraborty, Parthasarathi; Ramteke, Darwin; Chakraborty, Sucharita; Chennuri, Kartheek; Bardhan, Pratirupa

2015-11-15

A linkage between Cd speciation in sediments and its bioaccumulation in edible oyster (Crassostrea sp.) from a tropical estuarine system was established. Bioaccumulation of Cd in edible oyster increased with the increasing lability and dissociation rate constants of Cd-sediment complexes in the bottom sediments. Total Cd concentration in sediment was not a good indicator of Cd-bioavailability. Increasing trace metal competition in sediments increased lability and bioavailability of Cd in the tropical estuarine sediment. Low thermodynamic stability and high bioavailability of Cd in the estuarine sediment were responsible for high bioaccumulation of Cd in edible oysters (3.2-12.2mgkg(-1)) even though the total concentration of Cd in the bottom sediment was low (0.17-0.49mgkg(-1)). Copyright © 2015 Elsevier Ltd. All rights reserved.

Poly(ester-amide)s derived from PET containing uniform bisester amide segments

OpenAIRE

Ascanio Nuñez, Yanireth

2013-01-01

Poly(ethylene terephthalate) has experienced a growth in its demand as a bottle container and food packaging material. However, in order to expand its uses, its barrier properties to gases like carbon dioxide and oxygen, have to be improved. In this way, bisester amide units have been introduced as a third component in the main chain of PET, with the aim to reduce both CO2 and O2 permeability. In this project, poly(ester-amide)s based on PET (PETxMXy) have been synthesized, according to th...

DNA lability induced by nimustine and ramustine in rat glioma cells.

Science.gov (United States)

Mineura, K; Fushimi, S; Itoh, Y; Kowada, M

1988-01-01

The DNA labile sites induced by two nitrosoureas, nimustine (ACNU) and ramustine (MCNU) synthesised in Japan, have been examined in highly reiterated DNA sequences of rat glioma cells. Reiterated fragments of 167 and 203 base pairs (bp), obtained after Hind III and Hae III restriction endonuclease digestion of rat glioma cells DNA, were used as target DNA sequences to determine the labile sites. In vitro reaction with ACNU and MCNU resulted in scission products corresponding to the locations of guanine. Subsequent piperidine hydrolysis produced more frequent breaks of the phosphodiester bonds at guanine positions, thus forming alkali-labile sites. Images PMID:3236017

Characterization and profiling of phenolic amides from Cortex Lycii by ultra-high performance liquid chromatography coupled with LTQ-Orbitrap mass spectrometry.

Science.gov (United States)

Zhang, Jingxian; Guan, Shuhong; Sun, Jianghao; Liu, Tian; Chen, Pei; Feng, Ruihong; Chen, Xin; Wu, Wanying; Yang, Min; Guo, De-An

2015-01-01

Cortex Lycii, the root bark of Lycium chinense Mill. or Lycium barbarum L., is a frequently used traditional Chinese medicine. Phytochemical studies have shown that phenolic amides are not only characteristic compounds but also abundant ones in this plant. In the present study, an effective method was developed for structural characterization of phenolic amides from Cortex Lycii by ultra-high performance liquid chromatography coupled with linear ion trap Orbitrap tandem mass spectrometry. The fragmentation of 14 compounds including six cinnamic acid amides, six neolignanamides, and two lignanamides were studied systematically for the first time. It was found that, in the positive ion mode, neutral loss of the tyramide moiety (137 Da) or N-(4-aminobutyl)acetamide moiety (130 Da) were characteristic for these compounds. At least 54 phenolic amides were detected in the extract and 48 of them were characterized, among which 14 known compounds were identified unambiguously by comparing the retention time and mass spectra with those of reference compounds, and 34 components were tentatively identified based on the fragmentation patterns, exact mass, UV spectra, as well as retention time. Fifteen compounds were characterized as potential new ones. Additionally, the developed method was applied to analyze eight batches of samples collected from the northwest of China, and it was found that cinnamic acid amides were the main type of phenolic amides in Cortex Lycii. In conclusion, the identification of these chemicals provided essential data for further phytochemical studies, metabolites identification, and the quality control of Cortex Lycii.

Response of pine hypocotyl sections to growth regulators and related substances

Directory of Open Access Journals (Sweden)

J. Zakrzewski

2015-01-01

Full Text Available Growth response of Pinus silvestris hypocotyl sections to some synthetic growth regulators and related substances was studied. Elongation of hypocotyl sections was stimulated by naphtaleneacetic acid, indole-3-acetic acid, in-dole-3-propionic acid, indole-3-butyric acid, 2,4-dichlorophenoxyacetic acid, indoleaoetic amide, indoleacetic nitrile and coumarin. Indole-3-acetic acid and naphtaleneacetic acid extended period of growth up to 16 and 24 hours, respectively. Growth was inhibited by kinetin, trans-cinnamic acid and 2,3,5-tri-iodobenzoic acid. No effect of gibberellic acid, tryptophan and biotin was observed.

Triboelectrification of active pharmaceutical ingredients: week acids and their salts.

Science.gov (United States)

Fujinuma, Kenta; Ishii, Yuji; Yashihashi, Yasuo; Yonemochi, Estuo; Sugano, Kiyohiko; Tarada, Katsuhide

2015-09-30

The effect of salt formulation on the electrostatic property of active pharmaceutical ingredients was investigated. The electrostatic property of weak acids (carboxylic acids and amide-enole type acid) and their sodium salts was evaluated by a suction-type Faraday cage meter. Free carboxylic acids showed negative chargeability, whereas their sodium salts showed more positive chargeability than the free acids. However, no such trend was observed for amide-enole type acids. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of Light and Temperature on Fatty Acid Production in Nannochloropsis Salina

Energy Technology Data Exchange (ETDEWEB)

Van Wagenen, Jonathan M.; Miller, Tyler W.; Hobbs, Samuel J.; Hook, Paul W.; Crowe, Braden J.; Huesemann, Michael H.

2012-03-12

Accurate prediction of algal biofuel yield will require empirical determination of physiological responses to the climate, particularly light and temperature. One strain of interest, Nannochloropsis salina, was subjected to ranges of light intensity (5-850 {mu}mol m{sup -2} s{sup -1}) and temperature (13-40 C); exponential growth rate, total fatty acids (TFA) and fatty acid composition were measured. The maximum acclimated growth rate was 1.3 day{sup -1} at 23 C and 250 {mu}mol m{sup -2} s{sup -1}. Fatty acids were detected by gas chromatography with flame ionization detection (GC-FID) after transesterification to corresponding fatty acid methyl esters (FAME). A sharp increase in TFA containing elevated palmitic acid (C16:0) and palmitoleic acid (C16:1) during exponential growth at high light was observed, indicating likely triacylglycerol accumulation due to photo-oxidative stress. Lower light resulted in increases in the relative abundance of unsaturated fatty acids; in thin cultures, increases were observed in palmitoleic and eicosapentaenoeic acids (C20:5{omega}3). As cultures aged and the effective light intensity per cell converged to very low levels, fatty acid profiles became more similar and there was a notable increase of oleic acid (C18:1{omega}9). The amount of unsaturated fatty acids was inversely proportional to temperature, demonstrating physiological adaptations to increase membrane fluidity. This data will improve prediction of fatty acid characteristics and yields relevant to biofuel production.

Genetic variations in insulin-like growth factor binding protein acid labile subunit gene associated with growth traits in beef cattle (Bos taurus) in China.

Science.gov (United States)

Liu, Yu; Duan, Xiaoyan; Liu, Xiaolin; Guo, Jiazhong; Wang, Hongliang; Li, Zhixiong; Yang, Jing

2014-05-01

The insulin-like growth factor binding protein acid labile subunit (IGFALS) gene encodes a serum protein that binds to IGFs and regulates growth, development, and other physiological processes. We have found that sequencing of the IGFALS gene in Chinese Qinchuan beef cattle (n=300) revealed four SNP loci in exon two of the gene (g1219: T>C, g1893: T>C, g2612: G>A, and g2696: A>G). The SNP g2696: A>G resulted in a change from asparagine to aspartic acid (p. N574D) in the leucine-rich repeat region in the carboxyl-terminal domain of IGFALS. Four SNPs were in low linkage disequilibrium, and 12 different haplotypes were identified in the population. Association analysis suggested that SNP g1219: T>C had a significant association with hip width (PG displayed a significant association with stature (Pgrowth traits of bovine, and may serve as a genetic marker for selection of beef cattle for growth traits, including stature. Copyright © 2014 Elsevier B.V. All rights reserved.

Poly(methacrylic acid-ran-2-vinylpyridine Statistical Copolymer and Derived Dual pH-Temperature Responsive Block Copolymers by Nitroxide-Mediated Polymerization

Directory of Open Access Journals (Sweden)

Milan Marić

2017-02-01

Full Text Available Nitroxide-mediated polymerization using the succinimidyl ester functional unimolecular alkoxyamine initiator (NHS-BlocBuilder was used to first copolymerize tert-butyl methacrylate/2-vinylpyridine (tBMA/2VP with low dispersity (Đ = 1.30–1.41 and controlled growth (linear number average molecular Mn versus conversion, Mn = 3.8–10.4 kg·mol−1 across a wide composition of ranges (initial mol fraction 2VP, f2VP,0 = 0.10–0.90. The resulting statistical copolymers were first de-protected to give statistical polyampholytic copolymers comprised of methacrylic acid/2VP (MAA/2VP units. These copolymers exhibited tunable water-solubility due to the different pKas of the acidic MAA and basic 2VP units; being soluble at very low pH < 3 and high pH > 8. One of the tBMA/2VP copolymers was used as a macroinitiator for a 4-acryloylmorpholine/4-acryloylpiperidine (4AM/4AP mixture, to provide a second block with thermo-responsive behavior with tunable cloud point temperature (CPT, depending on the ratio of 4AM:4AP. Dynamic light scattering of the block copolymer at various pHs (3, 7 and 10 as a function of temperature indicated a rapid increase in particle size >2000 nm at 22–27 °C, corresponding to the 4AM/4AP segment’s thermos-responsiveness followed by a leveling in particle size to about 500 nm at higher temperatures.

Tuning the bimetallic amide-imide precursor system to make paramagnetic GaMnN nanopowders

Energy Technology Data Exchange (ETDEWEB)

Drygas, Mariusz [AGH University of Science and Technology, Faculty of Energy and Fuels, Al. Mickiewicza 30, 30-059 Krakow (Poland); Janik, Jerzy F., E-mail: janikj@agh.edu.pl [AGH University of Science and Technology, Faculty of Energy and Fuels, Al. Mickiewicza 30, 30-059 Krakow (Poland); Musial, Michal [AGH University of Science and Technology, Faculty of Energy and Fuels, Al. Mickiewicza 30, 30-059 Krakow (Poland); Gosk, Jacek [Warsaw University of Technology, Faculty of Physics, Koszykowa 75, 00-662 Warszawa (Poland); Twardowski, Andrzej, E-mail: andrzej.twardowski@fuw.edu.pl [University of Warsaw, Faculty of Physics, Pasteura 5, 02-093 Warszawa (Poland)

2016-09-01

A bimetallic molecular system made of gallium (III) tris(dimethyl)amide Ga(NMe{sub 2}){sub 3} and manganese (II) bis(trimethylsilyl)amide Mn[N(SiMe{sub 3}){sub 2}]{sub 2} (Me = CH{sub 3}, fixed initial Mn-content 10 at.%) was subjected to ammonolysis in refluxing/liquid ammonia. Upon isolation at room temperature, the amide-imide mixed metal precursor was pyrolyzed at elevated temperatures under an ammonia flow by two different routes. Route 1 consisted of a direct nitridation at high temperatures of 500, 700 or 900 °C. In route 2, a low temperature pyrolysis at 150 °C was applied prior to nitridation at the same final temperatures as in route 1. All nanopowders were characterized by XRD diffraction, FT-IR spectroscopy, and SEM/EDX microscopy and analysis. Thorough magnetization measurements in function of magnetic field and temperature were carried out with a SQUID magnetometer. In all samples, the paramagnetic phase of GaMnN was accompanied by an antiferromagnetic by-product linked to a Mn-containing species from decomposition and oxidation of Mn-precursor excess. The Mn-contents in the crystalline GaMnN, i.e., Mn-incorporated in GaN crystal lattice, were of the order of 2–3 at.% mostly independent on the nitridation route whereas the latter had a pronounced effect on amounts of the antiferromagnetic by-product. - Highlights: • New bimetallic precursor system for conversion to GaN/Mn nanopowders was designed. • Two conversion routes were applied with precursor nitridation at 500, 700 or 900 °C. • Prepared nanopowders were thoroughly characterized including magnetic measurements. • The major product was the gallium nitride Mn-doped phase GaMnN with 2–3 at.% of Mn.

Immobilization of lysozyme-cellulose amide-linked conjugates on cellulose i and ii cotton nanocrystalline preparations

Science.gov (United States)

Lysozyme was attached through an amide linkage between some of the protein’s aspartate and glutamate residues to amino-glycine-cellulose (AGC), which was prepared by esterification of glycine to preparations of cotton nanocrystals (CNC). The nanocrystalline preparations were produced through acid h...

Nickel-Catalyzed Reductive Transamidation of Secondary Amides with Nitroarenes

OpenAIRE

Cheung, Chi Wai; Ploeger, Marten Leendert; Hu, Xile

2017-01-01

Transmidation is an attractive method for amide synthesis. However, transamidation of secondary amides is challenging. Here, we describe a reductive transamidation method that employs readily available nitro(hetero)arenes as the nitrogen sources, zinc or manganese as reductant, and simple nickel salt and ligand as a catalyst system. The scope of amides includes both alkyl and aryl secondary amides, with high functional group compatibility.

Non-labile Soil Nitrogen Retention beneath Three Tree Species in a Tropical Plantation

Science.gov (United States)

Jason P. Kaye; Dan Binkley; Xiaoming Zou

2002-01-01

Soil organic matter is the largest sink for N additions to forests. Species composition may affect soilNretention by altering the amount or proportion of added N stored in non-labile organic pools. We measured 15N tracer retention in labile and non-labile pools of surface (0–20 cm) mineral soils, 7 yr after the tracer was applied to a 9 yr-old Puerto Rican tree...

Synthesis, Antifungal Activity and Structure-Activity Relationships of Novel 3-(Difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic Acid Amides.

Science.gov (United States)

Du, Shijie; Tian, Zaimin; Yang, Dongyan; Li, Xiuyun; Li, Hong; Jia, Changqing; Che, Chuanliang; Wang, Mian; Qin, Zhaohai

2015-05-08

A series of novel 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid amides were synthesized and their activities were tested against seven phytopathogenic fungi by an in vitro mycelia growth inhibition assay. Most of them displayed moderate to excellent activities. Among them N-(2-(5-bromo-1H-indazol-1-yl)phenyl)-3-(difluoro-methyl)-1-methyl-1H-pyrazole-4-carboxamide (9m) exhibited higher antifungal activity against the seven phytopathogenic fungi than boscalid. Topomer CoMFA was employed to develop a three-dimensional quantitative structure-activity relationship model for the compounds. In molecular docking, the carbonyl oxygen atom of 9m could form hydrogen bonds towards the hydroxyl of TYR58 and TRP173 on SDH.

Synthesis, Antifungal Activity and Structure-Activity Relationships of Novel 3-(Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic Acid Amides

Directory of Open Access Journals (Sweden)

Shijie Du

2015-05-01

Full Text Available A series of novel 3-(difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amides were synthesized and their activities were tested against seven phytopathogenic fungi by an in vitro mycelia growth inhibition assay. Most of them displayed moderate to excellent activities. Among them N-(2-(5-bromo-1H-indazol-1-ylphenyl-3-(difluoro-methyl-1-methyl-1H-pyrazole-4-carboxamide (9m exhibited higher antifungal activity against the seven phytopathogenic fungi than boscalid. Topomer CoMFA was employed to develop a three-dimensional quantitative structure-activity relationship model for the compounds. In molecular docking, the carbonyl oxygen atom of 9m could form hydrogen bonds towards the hydroxyl of TYR58 and TRP173 on SDH.

Maternal emotion socialization differentially predicts third-grade children's emotion regulation and lability.

Science.gov (United States)

Rogers, Megan L; Halberstadt, Amy G; Castro, Vanessa L; MacCormack, Jennifer K; Garrett-Peters, Patricia

2016-03-01

Numerous parental emotion socialization factors have been implicated as direct and indirect contributors to the development of children's emotional competence. To date, however, no study has combined parents' emotion-related beliefs, behaviors, and regulation strategies in one model to assess their cumulative-as well as unique-contributions to children's emotion regulation. We considered the 2 components that have recently been distinguished: emotion regulation and emotional lability. We predicted that mothers' beliefs about the value of and contempt for children's emotions, mothers' supportive and nonsupportive reactions to their children's emotions, as well as mothers' use of cognitive reappraisal and suppression of their own emotions would each contribute unique variance to their children's emotion regulation and lability, as assessed by children's teachers. The study sample consisted of an ethnically and socioeconomically diverse group of 165 mothers and their third-grade children. Different patterns emerged for regulation and lability: Controlling for family income, child gender, and ethnicity, only mothers' lack of suppression as a regulatory strategy predicted greater emotion regulation in children, whereas mothers' valuing of children's emotions, mothers' lack of contempt for children's emotions, mothers' use of cognitive reappraisal to reinterpret events, and mothers' lack of emotional suppression predicted less lability in children. These findings support the divergence of emotion regulation and lability as constructs and indicate that, during middle childhood, children's lability may be substantially and uniquely affected by multiple forms of parental socialization. (c) 2016 APA, all rights reserved).

Tissue and plasma concentrations of amidated and glycine-extended glucagon-like peptide I in humans

DEFF Research Database (Denmark)

Orskov, C; Rabenhøj, L; Wettergren, A

1994-01-01

Using specific radioimmunoassays, we studied the occurrence of amidated and glycine-extended glucagon-like peptide I (GLP-I) molecules in the human small intestine and pancreas and in the circulation system in response to a breakfast meal. Through gel permeation chromatography of extracts...... plasma were 7 +/- 1 and 6 +/- 1 pM, respectively (n = 6). In response to a breakfast meal, the concentration of amidated GLP-I rose significantly amounting to 41 +/- 5 pM 90 min after the meal ingestion, whereas the concentration of glycine-extended GLP-I only rose slightly to a maximum of 10 +/- 1 p...

Inhibition of fatty acid amide hydrolase by kaempferol and related naturally occurring flavonoids

Science.gov (United States)

Thors, L; Belghiti, M; Fowler, C J

2008-01-01

Background and purpose: Recent studies have demonstrated that the naturally occurring isoflavone compounds genistein and daidzein inhibit the hydrolysis of anandamide by fatty acid amide hydrolase (FAAH) in the low micromolar concentration range. The purpose of the present study was to determine whether this property is shared by flavonoids. Experimental approach: The hydrolysis of anandamide in homogenates and intact cells was measured using the substrate labelled in the ethanolamine part of the molecule. Key results: Twenty compounds were tested. Among the commonly occurring flavonoids, kaempferol was the most potent, inhibiting FAAH in a competitive manner with a Ki value of 5 μM. Among flavonoids with a more restricted distribution in nature, the two most active toward FAAH were 7-hydroxyflavone (IC50 value of 0.5–1 μM depending on the solvent used) and 3,7-dihydroxyflavone (IC50 value 2.2 μM). All three compounds reduced the FAAH-dependent uptake of anandamide and its metabolism by intact RBL2H3 basophilic leukaemia cells. Conclusions and implications: Inhibition of FAAH is an additional in vitro biochemical property of flavonoids. Kaempferol, 7-hydroxyflavone and 3,7-dihydroxyflavone may be useful as templates for the synthesis of novel compounds, which target several systems that are involved in the control of inflammation and cancer. PMID:18552875

An isotopic investigation of the temperature response of young and old soil organic matter respiration

Science.gov (United States)

Burns, Nancy; Cloy, Joanna; Garnett, Mark; Reay, David; Smith, Keith; Otten, Wilfred

2010-05-01

The effect of temperature on rates of soil respiration is critical to our understanding of the terrestrial carbon cycle and potential feedbacks to climate change. The relative temperature sensitivity of labile and recalcitrant soil organic matter (SOM) is still controversial; different studies have produced contrasting results, indicating limited understanding of the underlying relationships between stabilisation processes and temperature. Current global carbon cycle models still rely on the assumption that SOM pools with different decay rates have the same temperature response, yet small differences in temperature response between pools could lead to very different climate feedbacks. This study examined the temperature response of soil respiration and the age of soil carbon respired from radiocarbon dated fractions of SOM (free, intra-aggregate and mineral-bound) and whole soils (organic and mineral layers). Samples were collected from a peaty gley soil from Harwood Forest, Northumberland, UK. SOM fractions were isolated from organic layer (5 - 17 cm) material using high density flotation and ultrasonic disaggregation - designated as free (aggregate (aggregates > 1.8 g cm-3) and mineral-bound (> 1.8 g cm-3) SOM. Fractions were analysed for chemical composition (FTIR, CHN analysis, ICP-OES), 14C (AMS), δ13C and δ15N (MS) and thermal properties (DSC). SOM fractions and bulk soil from the organic layer and the mineral layer (20 - 30 cm) were incubated in sealed vessels at 30 ° C and 10 ° C for 3 or 9 months to allow accumulation of CO2 sufficient for sampling. Accumulated respired CO2 samples were collected on zeolite molecular sieve cartridges and used for AMS radiocarbon dating. In parallel, material from the same fractions and layers were incubated at 10 ° C, 15 ° C, 25 ° C and 30 ° C for 6 months and sampled weekly for CO2 flux measurements using GC chromatography. Initial data have shown radiocarbon ages ranging from modern to 219 y BP in bulk soil from

Titanocene(III)-Catalyzed Three-Component Reaction of Secondary Amides, Aldehydes, and Electrophilic Alkenes.

Science.gov (United States)

Zheng, Xiao; He, Jiang; Li, Heng-Hui; Wang, Ao; Dai, Xi-Jie; Wang, Ai-E; Huang, Pei-Qiang

2015-11-09

An umpolung Mannich-type reaction of secondary amides, aliphatic aldehydes, and electrophilic alkenes has been disclosed. This reaction features the one-pot formation of C-N and C-C bonds by a titanocene-catalyzed radical coupling of the condensation products, from secondary amides and aldehydes, with electrophilic alkenes. N-substituted γ-amido-acid derivatives and γ-amido ketones can be efficiently prepared by the current method. Extension to the reaction between ketoamides and electrophilic alkenes allows rapid assembly of piperidine skeletons with α-amino quaternary carbon centers. Its synthetic utility has been demonstrated by a facile construction of the tricyclic core of marine alkaloids such as cylindricine C and polycitorol A. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Approaching an experimental electron density model of the biologically active trans -epoxysuccinyl amide group-Substituent effects vs. crystal packing

Energy Technology Data Exchange (ETDEWEB)

Shi, Ming W.; Stewart, Scott G.; Sobolev, Alexandre N.; Dittrich, Birger; Schirmeister, Tanja; Luger, Peter; Hesse, Malte; Chen, Yu-Sheng; Spackman, Peter R.; Spackman, Mark A.; Grabowsky, Simon (Heinrich-Heine); (Freie); (UC); (Bremen); (JG-UM); (UWA)

2017-01-24

The trans-epoxysuccinyl amide group as a biologically active moiety in cysteine protease inhibitors such as loxistatin acid E64c has been used as a benchmark system for theoretical studies of environmental effects on the electron density of small active ingredients in relation to their biological activity. Here, the synthesis and the electronic properties of the smallest possible active site model compound are reported to close the gap between the unknown experimental electron density of trans-epoxysuccinyl amides and the well-known function of related drugs. Intramolecular substituent effects are separated from intermolecular crystal packing effects on the electron density, which allows us to predict the conditions under which an experimental electron density investigation on trans-epoxysuccinyl amides will be possible. In this context, the special importance of the carboxylic acid function in the model compound for both crystal packing and biological activity is revealed through the novel tool of model energy analysis.

The fatty acid amide hydrolase inhibitor URB597 exerts anti-inflammatory effects in hippocampus of aged rats and restores an age-related deficit in long-term potentiation

Directory of Open Access Journals (Sweden)

Murphy Niamh

2012-04-01

Full Text Available Abstract Background Several factors contribute to the deterioration in synaptic plasticity which accompanies age and one of these is neuroinflammation. This is characterized by increased microglial activation associated with increased production of proinflammatory cytokines like interleukin-1β (IL-1β. In aged rats these neuroinflammatory changes are associated with a decreased ability of animals to sustain long-term potentiation (LTP in the dentate gyrus. Importantly, treatment of aged rats with agents which possess anti-inflammatory properties to decrease microglial activation, improves LTP. It is known that endocannabinoids, such as anandamide (AEA, have anti-inflammatory properties and therefore have the potential to decrease the age-related microglial activation. However, endocannabinoids are extremely labile and are hydrolyzed quickly after production. Here we investigated the possibility that inhibiting the degradation of endocannabinoids with the fatty acid amide hydrolase (FAAH inhibitor, URB597, could ameliorate age-related increases in microglial activation and the associated decrease in LTP. Methods Young and aged rats received subcutaneous injections of the FAAH inhibitor URB597 every second day and controls which received subcutaneous injections of 30% DMSO-saline every second day for 28 days. Long-term potentiation was recorded on day 28 and the animals were sacrificed. Brain tissue was analyzed for markers of microglial activation by PCR and for levels of endocannabinoids by liquid chromatography coupled to tandem mass spectrometry. Results The data indicate that expression of markers of microglial activation, MHCII, and CD68 mRNA, were increased in the hippocampus of aged, compared with young, rats and that these changes were associated with increased expression of the proinflammatory cytokines interleukin (IL-1β and tumor necrosis factor-α (TNFα which were attenuated by treatment with URB597. Coupled with these changes, we

Cytotoxic Amides from Fruits of Kawakawa, Macropiper excelsum.

Science.gov (United States)

Lei, Jeremy; Burgess, Elaine J; Richardson, Alistair T B; Hawkins, Bill C; Baird, Sarah K; Smallfield, Bruce M; van Klink, John W; Perry, Nigel B

2015-08-01

Cytotoxic amides have been isolated from the fruits of the endemic New Zealand medicinal plant kawakawa, Macropiper excelsum (Piperaceae). The main amide was piperchabamide A and this is the first report of this rare compound outside the genus Piper. Eleven other amides were purified including two new compounds with the unusual 3,4-dihydro-1(2H)-pyridinyl group. The new compounds were fully characterized by 2D NMR spectroscopy, which showed a slow exchange between two rotamers about the amide bond, and they were chemically synthesized. In view of the antitumor activity of the related piperlongumine, all of these amides plus four synthetic analogs were tested for cytotoxicity. The most active was the piperine homolog piperdardine, with an IC50 of 14 µM against HT 29 colon cancer cells. Georg Thieme Verlag KG Stuttgart · New York.

High temperature dissolution of chromium substituted nickel ferrite in nitrilotriacetic acid medium

Energy Technology Data Exchange (ETDEWEB)

Sathyaseelan, V.S.; Chandramohan, P.; Velmurugan, S., E-mail: svelu@igcar.gov.in

2016-12-01

High temperature (HT) dissolution of chromium substituted nickel ferrite was carried out with relevance to the decontamination of nuclear reactors by way of chemical dissolution of contaminated corrosion product oxides present on stainless steel coolant circuit surfaces. Chromium substituted nickel ferrites of composition, NiFe{sub (2−x)}Cr{sub x}O{sub 4} (x ≤ 1), was synthetically prepared and characterized. HT dissolution of these oxides was carried out in nitrilotriacetic acid medium at 160 °C. Dissolution was remarkably increased at 160 °C when compared to at 85 °C in a reducing decontamination formulation. Complete dissolution could be achieved for the oxides with chromium content 0 and 0.2. Increasing the chromium content brought about a marked reduction in the dissolution rate. About 40 fold decrease in rate of dissolution was observed when chromium was increased from 0 to 1. The rate of dissolution was not very significantly reduced in the presence of N{sub 2}H{sub 4}. Dissolution of oxide was found to be stoichiometric. - Highlights: • Dissolution of NiFe{sub (2−x)}Cr{sub x}O{sub 4} was remarkably increased at 160 °C in NTA medium. • The dissolution was significantly decreasing with the increase in Cr content in the oxide. • Dissolution rate is dependent on the lability of metal-oxo bonds. • The rate of dissolution was not significantly reduced in the presence of N{sub 2}H{sub 4.} • NTA at high temperature is effective for decontamination of stainless steel surfaces.

Knowledge Lability: Within-Person Changes in Parental Knowledge and Their Associations with Adolescent Problem Behavior.

Science.gov (United States)

Lippold, Melissa A; Fosco, Gregory M; Ram, Nilam; Feinberg, Mark E

2016-02-01

Higher levels of parental knowledge about youth activities have been associated with lower levels of youth risky behavior. Yet little is known about how parental knowledge fluctuates during early adolescence and how those fluctuations are associated with the development of problem behavior. We use the term lability to describe within-person fluctuations in knowledge over time with higher lability indicating greater fluctuations in knowledge from year-to-year. This longitudinal study of rural adolescents (N = 840) investigated if change in parental knowledge across four waves of data from grades 6 to 8 is characterized by lability, and if greater lability is associated with higher youth substance use, delinquency, and internalizing problems in grade 9. Our models indicated that only some of the variance in parental knowledge was accounted for by developmental trends. The remaining residual variance reflects within-person fluctuations around these trends, lability, and measurement and occasion-specific error. Even controlling for level and developmental trends in knowledge, higher knowledge lability (i.e., more fluctuation) was associated with increased risk for later alcohol and tobacco use, and for girls, higher delinquency and internalizing problems. Our findings suggest that lability in parental knowledge has unique implications for adolescent outcomes. The discussion focuses on mechanisms that may link knowledge lability to substance use. Interventions may be most effective if they teach parents to consistently and predictably decrease knowledge across early adolescence.

Molecular insights into the microbial formation of marine dissolved organic matter: recalcitrant or labile?

Science.gov (United States)

Koch, B. P.; Kattner, G.; Witt, M.; Passow, U.

2014-08-01

The degradation of marine dissolved organic matter (DOM) is an important control variable in the global carbon cycle. For our understanding of the kinetics of organic matter cycling in the ocean, it is crucial to achieve a mechanistic and molecular understanding of its transformation processes. A long-term microbial experiment was performed to follow the production of non-labile DOM by marine bacteria. Two different glucose concentrations and dissolved algal exudates were used as substrates. We monitored the bacterial abundance, concentrations of dissolved and particulate organic carbon (DOC, POC), nutrients, amino acids and transparent exopolymer particles (TEP) for 2 years. The molecular characterization of extracted DOM was performed by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) after 70 days and after ∼2 years of incubation. Although glucose quickly degraded, a non-labile DOC background (5-9% of the initial DOC) was generated in the glucose incubations. Only 20% of the organic carbon from the algal exudate degraded within the 2 years of incubation. The degradation rates for the non-labile DOC background in the different treatments varied between 1 and 11 μmol DOC L-1 year-1. Transparent exopolymer particles, which are released by microorganisms, were produced during glucose degradation but decreased back to half of the maximum concentration within less than 3 weeks (degradation rate: 25 μg xanthan gum equivalents L-1 d-1) and were below detection in all treatments after 2 years. Additional glucose was added after 2 years to test whether labile substrate can promote the degradation of background DOC (co-metabolism; priming effect). A priming effect was not observed but the glucose addition led to a slight increase of background DOC. The molecular analysis demonstrated that DOM generated during glucose degradation differed appreciably from DOM transformed during the degradation of the algal exudates. Our

Poly(ether ester amide)s for tissue engineering

NARCIS (Netherlands)

Deschamps, A.A.; van Apeldoorn, Aart A.; de Bruijn, Joost Dick; Grijpma, Dirk W.; Feijen, Jan

2003-01-01

Poly(ether ester amide) (PEEA) copolymers based on poly(ethylene glycol) (PEG), 1,4-butanediol and dimethyl-7,12-diaza-6,13-dione-1,18-octadecanedioate were evaluated as scaffold materials for tissue engineering. A PEEA copolymer based on PEG with a molecular weight of 300 g/mol and 25 wt% of soft

Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides.

Science.gov (United States)

Srimontree, Watchara; Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Rueping, Magnus

2017-06-16

A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides

KAUST Repository

Srimontree, Watchara; Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Rueping, Magnus

2017-01-01

A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides

KAUST Repository

Srimontree, Watchara

2017-06-05

A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

Yakushinamides, Polyoxygenated Fatty Acid Amides That Inhibit HDACs and SIRTs, from the Marine Sponge Theonella swinhoei.

Science.gov (United States)

Takada, Kentaro; Imae, Yasufumi; Ise, Yuji; Ohtsuka, Susumu; Ito, Akihiro; Okada, Shigeru; Yoshida, Minoru; Matsunaga, Shigeki

2016-09-23

Yakushinamides A (1) and B (2), prolyl amides of polyoxygenated fatty acids, have been isolated from the marine sponge Theonella swinhoei as inhibitors of HDACs and SIRTs. Their planar structures were determined by interpretation of the NMR data of the intact molecules and tandem FABMS data of the methanolysis products. For the assignment of the relative configurations of the three contiguous oxymethine carbons in 1 and 2, Kishi's universal NMR database was applied to the methanolysis products. During the assignments of relative configurations of the isolated 1-hydroxy-3-methyl moiety in 1 and the isolated 1-hydroxy-2-methyl moiety in 2, we found diagnostic NMR features to distinguish each pair of diastereomers. The absolute configurations of 1 and 2 were determined by a combination of the modified Mosher's method and Marfey's method. Although the modified Mosher's method was successfully applied to the methanolysis product of 1, this method gave an ambiguous result at C-20 when applied to the methanolysis product of 2, even after oxidative cleavage of the C-14 and C-15 bond.

Characterization of labile organic carbon in coastal wetland soils of the Mississippi River deltaic plain: Relationships to carbon functionalities

Energy Technology Data Exchange (ETDEWEB)

Dodla, Syam K. [School of Plant, Environmental and Soil Sciences, Louisiana State Univ. Agricultural Center, Baton Rouge, LA 70803 (United States); Wang, Jim J., E-mail: jjwang@agcenter.lsu.edu [School of Plant, Environmental and Soil Sciences, Louisiana State Univ. Agricultural Center, Baton Rouge, LA 70803 (United States); DeLaune, Ronald D. [Department of Oceanography and Coastal Sciences, School of the Coast and Environment, Louisiana State University, Baton Rouge, LA 70803 (United States)

2012-10-01

Adequate characterization of labile organic carbon (LOC) is essential to the understanding of C cycling in soil. There has been very little evaluation about the nature of LOC characterizations in coastal wetlands, where soils are constantly influenced by different redox fluctuations and salt water intrusions. In this study, we characterized and compared LOC fractions in coastal wetland soils of the Mississippi River deltaic plain using four different methods including 1) aerobically mineralizable C (AMC), 2) cold water extractable C (CWEC), 3) hot water extractable C (HWEC), and 4) salt extractable C (SEC), as well as acid hydrolysable C (AHC) which includes both labile and slowly degradable organic C. Molecular organic C functional groups of these wetland soils were characterized by {sup 13}C solid-state nuclear magnetic resonance (NMR). The LOC and AHC increased with soil organic C (SOC) regardless of wetland soil type. The LOC estimates by four different methods were positively and significantly linearly related to each other (R{sup 2} = 0.62-0.84) and with AHC (R{sup 2} = 0.47-0.71). The various LOC fractions accounted for {<=} 4.3% of SOC whereas AHC fraction represented 16-49% of SOC. AMC was influenced positively by O/N-alkyl and carboxyl C but negatively by alkyl C, whereas CWEC and SEC fractions were influenced only positively by carboxyl C but negatively by alkyl C in SOC. On the other hand, HWEC fraction was found to be only influenced positively by carbonyl C, and AHC positively by O/N-alkyl and alkyl C but negatively by aromatic C groups in SOC. Overall these relations suggested different contributions of various molecular organic C moieties to LOC in these wetlands from those often found for upland soils. The presence of more than 50% non-acid hydrolysable C suggested the dominance of relatively stable SOC pool that would be sequestered in these Mississippi River deltaic plain coastal wetland soils. The results have important implications to the

Recent progress of partitioning process in JAERI: development of amide-based artist process

International Nuclear Information System (INIS)

Shoichi, Tachimori; Yuji, Sasaki; Yasuji, Morita; Shin-ichi, Suzuki

2003-01-01

A branched-alkyl monoamide which extracts An(VI) exclusively by the steric effect and tridentate diglycol-amide; TODGA, which recovers all actinides and Sr(II) from highly acidic waste solutions, were developed. Then, a new chemical process, ARTIST process, is proposed for the treatment of nuclear spent fuel consolidating plutonium management and the partitioning concept. (author)

Probing the role of backbone hydrogen bonds in protein-peptide interactions by amide-to-ester mutations

DEFF Research Database (Denmark)

Eildal, Jonas N N; Hultqvist, Greta; Balle, Thomas

2013-01-01

-protein interactions, those of the PDZ domain family involve formation of intermolecular hydrogen bonds: C-termini or internal linear motifs of proteins bind as β-strands to form an extended antiparallel β-sheet with the PDZ domain. Whereas extensive work has focused on the importance of the amino acid side chains...... of the protein ligand, the role of the backbone hydrogen bonds in the binding reaction is not known. Using amide-to-ester substitutions to perturb the backbone hydrogen-bonding pattern, we have systematically probed putative backbone hydrogen bonds between four different PDZ domains and peptides corresponding...... to natural protein ligands. Amide-to-ester mutations of the three C-terminal amides of the peptide ligand severely affected the affinity with the PDZ domain, demonstrating that hydrogen bonds contribute significantly to ligand binding (apparent changes in binding energy, ΔΔG = 1.3 to >3.8 kcal mol(-1...

Phase space investigation of the lithium amide halides

Energy Technology Data Exchange (ETDEWEB)

Davies, Rosalind A. [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Hydrogen and Fuel Cell Group, School of Chemical Engineering, University of Birmingham, Edgbaston B15 2TT (United Kingdom); Hewett, David R.; Korkiakoski, Emma [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Thompson, Stephen P. [Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0QX (United Kingdom); Anderson, Paul A., E-mail: p.a.anderson@bham.ac.uk [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

2015-10-05

Highlights: • The lower limits of halide incorporation in lithium amide have been investigated. • The only amide iodide stoichiometry observed was Li{sub 3}(NH{sub 2}){sub 2}I. • Solid solutions were observed in both the amide chloride and amide bromide systems. • A 46% reduction in chloride content resulted in a new phase: Li{sub 7}(NH{sub 2}){sub 6}Cl. • New low-chloride phase maintained improved H{sub 2} desorption properties of Li{sub 4}(NH{sub 2}){sub 3}Cl. - Abstract: An investigation has been carried out into the lower limits of halide incorporation in lithium amide (LiNH{sub 2}). It was found that the lithium amide iodide Li{sub 3}(NH{sub 2}){sub 2}I was unable to accommodate any variation in stoichiometry. In contrast, some variation in stoichiometry was accommodated in Li{sub 7}(NH{sub 2}){sub 6}Br, as shown by a decrease in unit cell volume when the bromide content was reduced. The amide chloride Li{sub 4}(NH{sub 2}){sub 3}Cl was found to adopt either a rhombohedral or a cubic structure depending on the reaction conditions. Reduction in chloride content generally resulted in a mixture of phases, but a new rhombohedral phase with the stoichiometry Li{sub 7}(NH{sub 2}){sub 6}Cl was observed. In comparison to LiNH{sub 2}, this new low-chloride phase exhibited similar improved hydrogen desorption properties as Li{sub 4}(NH{sub 2}){sub 3}Cl but with a much reduced weight penalty through addition of chloride. Attempts to dope lithium amide with fluoride ions have so far proved unsuccessful.

Amino acid metabolism of Lemna minor L

International Nuclear Information System (INIS)

Rhodes, D.; Rich, P.J.; Brunk, D.G.

1989-01-01

A serious limitation to the use of N(O,S)-heptafluorobutyryl isobutyl amino acid derivatives in the analysis of 15 N-labeling kinetics of amino acids in plant tissues, is that the amides glutamine and asparagine undergo acid hydrolysis to glutamate and aspartate, respectively, during derivatization. This led us to consider an alternative procedure for derivatization of glutamine and asparagine with N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide in pyridine. Gas chromatography-mass spectrometry yielded fragment ions (M-57) of mass 417 and 431 for the [ 14 N]asparagine and [ 14 N]glutamine derivatives, respectively, suitable for monitoring unlabeled, single- 15 N- and double- 15 N-labeled amide species from the ion clusters at mass to charge ratio (m/z) 415 to 423 for asparagine, and m/z 429 to 437 for glutamine. From separate analyses of the specific isotope abundance of the amino-N groups of asparagine and glutamine as their N-heptafluorobutyryl isobutyl derivatives, the specific amide-[ 15 N] abundance of these amino acids was determined

Frictional response of fatty acids on steel.

Science.gov (United States)

Sahoo, Rashmi R; Biswas, S K

2009-05-15

Self-assembled monolayers of fatty acids were formed on stainless steel by room-temperature solution deposition. The acids are covalently bound to the surface as carboxylate in a bidentate manner. To explore the effect of saturation in the carbon backbone on friction in sliding tribology, we study the response of saturated stearic acid (SA) and unsaturated linoleic acid (LA) as self-assembled monolayers using lateral force microscopy and nanotribometry and when the molecules are dispersed in hexadecane, using pin-on-disc tribometry. Over a very wide range (10 MPa-2.5 GPa) of contact pressures it is consistently demonstrated that the unsaturated linoleic acid molecules yield friction which is significantly lower than that of the saturated stearic acid. It is argued, using density functional theory predictions and XPS of slid track, that when the molecular backbone of unsaturated fatty acids are tilted and pressed strongly by a probe, in tribological contact, the high charge density of the double bond region of the backbone allows coupling with the steel substrate. The interaction yields a low friction carboxylate soap film on the substrate. The saturated fatty acid does not show this effect.

Assessing SOC labile fractions through respiration test, density-size fractionation and thermal analysis - A comparison of methods

Science.gov (United States)

Soucemarianadin, Laure; Cécillon, Lauric; Chenu, Claire; Baudin, François; Nicolas, Manuel; Savignac, Florence; Barré, Pierre

2017-04-01

) were only weakly positively correlated (Spearman's ρ = 0.26, n = 93). Similarly, soil respiration had only a weak negative correlation (Spearman's ρ = -0.24, n = 93; ρ = -0.33, n = 222) with the RE6 parameter T50 CH pyrolysis. This parameter, previously used as an indicator of labile SOC (Gregorich et al., 2015), represents the temperature at which 50% of the OM was pyrolyzed to effluents (mainly hydrocarbons) during the pyrolysis phase of RE6. Conversely, POC content (% of total SOC) showed a higher negative correlation with T50 CH pyrolysis (ρ = -0.66, n = 93; ρ = -0.65, n = 103) and was positively and negatively correlated to the hydrogen index, HI (mg HC/g TOC; ρ = 0.56/0.53) and the oxygen index, OI (mg CO2/g TOC; ρ = -0.63/-0.62) respectively. Our results showed that RE6 results are consistent with respiration and fractionation results: SOC with higher respiration rate and higher POC content burns at a lower temperature. RE6 thermal analysis could therefore be viewed as a useful fast and cost effective alternative to more time-consuming methods used in SOM fractions determination. Barré, P. et al. Biogeochemistry 2016, 1-12, 130. Gregorich, E.G. et al. Soil Biol. Biochem. 2015, 182-191, 91.

Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques

Science.gov (United States)

Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine

2016-04-01

Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg-1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike -Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L-1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not yet

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

Directory of Open Access Journals (Sweden)

Kevin A Thorn

Full Text Available 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.

NMR studies of the influence of dodecyl sulfate on the amide hydrogen exchange kinetics of a micelle-solubilized hydrophobic tripeptide

International Nuclear Information System (INIS)

O'Neil, J.D.J.; Sykes, B.D.

1989-01-01

Backbone amide hydrogen exchange measurements are an important source of information about the internal dynamics of proteins. Before such measurements can be interpreted unambiguously, contributions to hydrogen exchange rates from the chemical and physical environment of the amides must be taken into account. Membrane proteins are often solubilized in detergents, yet there have not been any systematic investigations of the possible effects detergents may have on the amide hydrogen exchange rates of proteins. To address this question, the authors have measured individual backbone and carboxyl-terminal amide exchange rates for the amphipathic tripeptide Leu-Val-Ile-amide dissolved in water and dodecyl sulfate micelles. Proton NMR spectroscopy was used to measure exchange using the direct exchange-out into D 2 O technique at 5 degree C and using an indirect steady-state saturation-transfer technique at 25 degree C. The broadening effect of micelle-incorporated spin-labeled fatty acid (12-doxylsterate) on the 1 H NMR spectra of both the detergent and the peptide resonances was used to demonstrate that the tripeptide is intimately associated with the micelle. These experiments help to explain the elevated pH min observed for backbone amides in the sodium dodecyl sulfate solubilized M13 coat protein

Partitioning of Minor Actinides from High Active Raffinates using Bis-Diglycol-amides (BisDGA) as new efficient Extractants

Energy Technology Data Exchange (ETDEWEB)

Modolo, G.; Vijgen, H. [Forschungszentrum Juelich GmbH, Institute for Energy Research, Safety Research and Reactor Technology, 52425 Juelich (Germany); Espartero, A.G. [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Avda. Complutense 22, 28040-Madrid (Spain); Prados, P. [Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid - UAM, carretera de Colmenar Viejo km 15.3, 28049-Madrid (Spain); Mendoza, J. de [Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid - UAM, carretera de Colmenar Viejo km 15.3, 28049-Madrid (Spain); Institut Catala d' Investigacio Quimica (ICIQ) Av. Paisos Catalans 16, 43007-Tarragona (Spain)

2008-07-01

Two new polyamide extractants has been selected, namely UAM-069 and UAM-081, both synthesized at the University of Madrid (UAM), to develop a new separation process. These two ligands are bis-diglycol-amides, consisting of two diglycol-amides moieties grafted on an aromatic platform (UAM-069) or on an aliphatic linker (UAM-081), respectively. The extraction of actinides and fission products was studied from synthetic PUREX raffinate. Actinides(III) and lanthanides(III) are highly extracted from acidities > 1 mol/L HNO{sub 3}. The extraction of Zr, Mo and Pd could be suppressed with complexing agents such as oxalic acid and HEDTA. In the present paper the results of the batch extraction results are presented which serve for the development of a new continuous counter current process to be tested in centrifugal contactors. (authors)

A General and Simple Diastereoselective Reduction by L-Selectride: Efficient Synthesis of Protected (4S,5S)-Dihydroxy Amides

OpenAIRE

Yin; Ye; Yu; Liu

2010-01-01

A general approach to (4S,5S)-4-benzyloxy-5-hydroxy-N-(4-methoxybenzyl) amides 10 based on a diastereoselective reduction of (5S,6RS)-6-alkyl-5-benzyloxy-6-hydroxy-2-piperidinones 6 and their tautomeric ring-opened keto amides 7 is described. The reduction with L-Selectride at -20 °C to room temperature afforded the products 10 in excellent yields and moderate to high syn-diastereoselectivities.

A general and simple diastereoselective reduction by L-Selectride: efficient synthesis of protected (4S,5S)-dihydroxy amides.

Science.gov (United States)

Yin, Bo; Ye, Dong-Nai; Yu, Kai-Hui; Liu, Liang-Xian

2010-04-16

A general approach to (4S,5S)-4-benzyloxy-5-hydroxy-N-(4-methoxybenzyl) amides 10 based on a diastereoselective reduction of (5S,6RS)-6-alkyl-5-benzyloxy-6-hydroxy-2-piperidinones 6 and their tautomeric ring-opened keto amides 7 is described. The reduction with L-Selectride at -20 degrees C to room temperature afforded the products 10 in excellent yields and moderate to high syn-diastereoselectivities.

Differential effects of temperature on acid-activated currents mediated by TRPV1 and ASIC channels in rat dorsal root ganglion neurons.

Science.gov (United States)

Neelands, Torben R; Zhang, Xu-Feng; McDonald, Heath; Puttfarcken, Pamela

2010-05-06

Elevated temperature and decreased extracellular pH are hallmarks of inflammatory pain states. Dorsal root ganglia (DRG) neurons are integral in transferring painful stimuli from the periphery to central sites. This study investigated the effect of elevated temperatures on the response of DRG neurons to acute application of acidic solutions. At room temperature (22 degrees C), in response to pH 5.5, there were a variety of kinetic responses consistent with differential expression of TRPV1 and ASIC channels. Increasing the temperature resulted in a significant increase in the peak and total current mediated by TRPV1 in response to an acidic solution. In contrast, the amplitude of a fast activating, rapidly inactivating ASIC1-like current was not affected by increasing the temperature but did result in an increased rate of desensitization that reduced the total current level. This effect on the rate of desensitization was temperature-dependent and could be reversed by returning to 22 degrees C. Likewise, cells exhibiting slowly inactivating ASIC2-like responses also had temperature-dependent increase in the rate of desensitization. The ASIC2-like responses and the TRPV1 responses tended to decrease in amplitude with repetitive application of pH 5.5 even at 22 degrees C. The rate of desensitization of ASIC-like currents activated by less acidic solutions (pH 6.8) was also increased in a temperature-dependent manner. Finally, acidic pH reduced threshold to trigger action potentials, however, the pattern of action potential firing was shaped by the distribution of ASIC and TRPV1 channels. These results indicate that the ambient temperature at which acidosis occurs has a profound effect on the contribution of ASIC and TRPV1 channels, therefore, altering the neuronal excitability. Copyright 2010 Elsevier B.V. All rights reserved.

Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins

Science.gov (United States)

Hu, Jiefeng; Wang, Minyan; Pu, Xinghui; Shi, Zhuangzhi

2017-05-01

Amide and olefins are important synthetic intermediates with complementary reactivity which play a key role in the construction of natural products, pharmaceuticals and manmade materials. Converting the normally highly stable aliphatic amides into olefins directly is a challenging task. Here we show that a Ni/NHC-catalytic system has been established for decarbonylative elimination of aliphatic amides to generate various olefins via C-N and C-C bond cleavage. This study not only overcomes the acyl C-N bond activation in aliphatic amides, but also encompasses distinct chemical advances on a new type of elimination reaction called retro-hydroamidocarbonylation. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for late-stage olefination of amide groups in complex compounds.

Novel endogenous N-acyl amides activate TRPV1-4 receptors, BV-2 microglia, and are regulated in brain in an acute model of inflammation

Science.gov (United States)

Raboune, Siham; Stuart, Jordyn M.; Leishman, Emma; Takacs, Sara M.; Rhodes, Brandon; Basnet, Arjun; Jameyfield, Evan; McHugh, Douglas; Widlanski, Theodore; Bradshaw, Heather B.

2014-01-01

A family of endogenous lipids, structurally analogous to the endogenous cannabinoid, N-arachidonoyl ethanolamine (Anandamide), and called N-acyl amides have emerged as a family of biologically active compounds at TRP receptors. N-acyl amides are constructed from an acyl group and an amine via an amide bond. This same structure can be modified by changing either the fatty acid or the amide to form potentially hundreds of lipids. More than 70 N-acyl amides have been identified in nature. We have ongoing studies aimed at isolating and characterizing additional members of the family of N-acyl amides in both central and peripheral tissues in mammalian systems. Here, using a unique in-house library of over 70 N-acyl amides we tested the following three hypotheses: (1) Additional N-acyl amides will have activity at TRPV1-4, (2) Acute peripheral injury will drive changes in CNS levels of N-acyl amides, and (3) N-acyl amides will regulate calcium in CNS-derived microglia. Through these studies, we have identified 20 novel N-acyl amides that collectively activate (stimulating or inhibiting) TRPV1-4. Using lipid extraction and HPLC coupled to tandem mass spectrometry we showed that levels of at least 10 of these N-acyl amides that activate TRPVs are regulated in brain after intraplantar carrageenan injection. We then screened the BV2 microglial cell line for activity with this N-acyl amide library and found overlap with TRPV receptor activity as well as additional activators of calcium mobilization from these lipids. Together these data provide new insight into the family of N-acyl amides and their roles as signaling molecules at ion channels, in microglia, and in the brain in the context of inflammation. PMID:25136293

Synthesis of Nitriles via Palladium-Catalyzed Water Shuffling from Amides to Acetonitrile

OpenAIRE

Zhang, Wandi; Haskins, Christopher W.; Yang, Yang; Dai, Mingji

2014-01-01

Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

Synthesis of nitriles via palladium-catalyzed water shuffling from amides to acetonitrile.

Science.gov (United States)

Zhang, Wandi; Haskins, Christopher W; Yang, Yang; Dai, Mingji

2014-12-07

Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

Biological effects and metabolic rates of glucagonlike peptide-1 7-36 amide and glucagonlike peptide-1 7-37 in healthy subjects are indistinguishable

DEFF Research Database (Denmark)

Orskov, C; Wettergren, A; Holst, J J

1993-01-01

.0 +/- 34.6 pmol/h x L-1). Both GLP-1 7-36 amide and GLP-1 7-37 lowered the plasma concentration of free fatty acids significantly. The plasma half-lives of GLP-1 7-36 amide and GLP-1 7-37 were 5.3 +/- 0.4 vs. 6.1 +/- 0.8 min, and the metabolic clearance rates of the two peptides also were similar (14...

Ethyl malonate amides: a diketo acid offspring fragment for HIV integrase inhibition.

Science.gov (United States)

Serafin, Katarzyna; Mazur, Pawel; Bak, Andrzej; Laine, Elodie; Tchertanov, Luba; Mouscadet, Jean-François; Polanski, Jaroslaw

2011-08-15

While searching for new HIV integrase inhibitors we discovered that some ethyl malonate amides (EMA) are active against this enzyme. Surprisingly, the main function can only very rarely be found among the reported drug candidates. We synthesised a series of compounds in order to establish and analyse the structure-activity relationship. The similarity to the important classes of HIV integrase inhibitors as well as the synthetic availability of the different targets including this pharmacophore makes EMA compounds an interesting object of investigations. Copyright © 2011 Elsevier Ltd. All rights reserved.

Structure elucidation and in vitro cytotoxicity of ochratoxin α amide, a new degradation product of ochratoxin A.

Science.gov (United States)

Bittner, Andrea; Cramer, Benedikt; Harrer, Henning; Humpf, Hans-Ulrich

2015-05-01

The mycotoxin ochratoxin A is a secondary metabolite occurring in a wide range of commodities. During the exposure of ochratoxin A to white and blue light, a cleavage between the carbon atom C-14 and the nitrogen atom was described. As a reaction product, the new compound ochratoxin α amide has been proposed based on mass spectrometry (MS) experiments. In the following study, we observed that this compound is also formed at high temperatures such as used for example during coffee roasting and therefore represents a further thermal ochratoxin A degradation product. To confirm the structure of ochratoxin α amide, the compound was prepared in large scale and complete structure elucidation via nuclear magnetic resonance (NMR) and MS was performed. Additionally, first studies on the toxicity of ochratoxin α amide were performed using immortalized human kidney epithelial (IHKE) cells, a cell line known to be sensitive against ochratoxin A with an IC50 value of 0.5 μM. Using this system, ochratoxin α amide revealed no cytotoxicity up to concentrations of 50 μM. Thus, these results propose that the thermal degradation of ochratoxin A to ochratoxin α amide might be a detoxification process. Finally, we present a sample preparation and a HPLC-tandem mass spectrometry (HPLC-MS/MS) method for the analysis of ochratoxin α amide in extrudates and checked its formation during the extrusion of artificially contaminated wheat grits at 150 and 180 °C, whereas no ochratoxin α amide was detectable under these conditions.

Targeting fatty acid amide hydrolase and transient receptor potential vanilloid-1 simultaneously to modulate colonic motility and visceral sensation in the mouse: A pharmacological intervention with N-arachidonoyl-serotonin (AA-5-HT).

Science.gov (United States)

Bashashati, M; Fichna, J; Piscitelli, F; Capasso, R; Izzo, A A; Sibaev, A; Timmermans, J-P; Cenac, N; Vergnolle, N; Di Marzo, V; Storr, M

2017-12-01

Endocannabinoid anandamide (AEA) inhibits intestinal motility and visceral pain, but it may also be proalgesic through transient receptor potential vanilloid-1 (TRPV1). AEA is degraded by fatty acid amide hydrolase (FAAH). This study explored whether dual inhibition of FAAH and TRPV1 reduces diarrhea and abdominal pain. Immunostaining was performed on myenteric plexus of the mouse colon. The effects of the dual FAAH/TRPV1 inhibitor AA-5-HT on electrically induced contractility, excitatory junction potential (EJP) and fast (f) and slow (s) inhibitory junction potentials (IJP) in the mouse colon, colonic propulsion and visceromotor response (VMR) to rectal distension were studied. The colonic levels of endocannabinoids and fatty acid amides were measured. CB1-positive neurons exhibited TRPV1; only some TRPV1 positive neurons did not express CB1. CB1 and FAAH did not colocalize. AA-5-HT (100 nM-10 μM) decreased colonic contractility by ~60%; this effect was abolished by TRPV1 antagonist 5'-IRTX, but not by CB1 antagonist, SR141716. AA-5-HT (1 μM-10 μM) inhibited EJP by ~30% and IJPs by ~50%. The effects of AA-5-HT on junction potentials were reversed by SR141716 and 5`-IRTX. AA-5-HT (20 mg/kg; i.p.) inhibited colonic propulsion by ~30%; SR141716 but not 5`-IRTX reversed this effect. AA-5-HT decreased VMR by ~50%-60%; these effects were not blocked by SR141716 or 5`-IRTX. AA-5-HT increased AEA in the colon. The effects of AA-5-HT on visceral sensation and colonic motility are differentially mediated by CB1, TRPV1 and non-CB1/TRPV1 mechanisms, possibly reflecting the distinct neuromodulatory roles of endocannabinoid and endovanilloid FAAH substrates in the mouse intestine. © 2017 John Wiley & Sons Ltd.

Labile pools of Pb in vegetable-growing soils investigated by an isotope dilution method and its influence on soil pH.

Science.gov (United States)

Xie, Hong; Huang, Zhi-Yong; Cao, Ying-Lan; Cai, Chao; Zeng, Xiang-Cheng; Li, Jian

2012-08-01

Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted with EDTA and the Σ(BCR) values extracted with the modified BCR approach are helpful to detect the labile pools of Pb in soils. In addition, the negative correlation between soil pH and the labile pools of Pb in soils

CHROMIUM(II) AMIDES - SYNTHESIS AND STRUCTURES

NARCIS (Netherlands)

EDEMA, JJH; GAMBAROTTA, S; MEETSMA, A; SPEK, AL; SMEETS, WJJ; CHIANG, MY

1993-01-01

A novel class of mono- and di-meric chromium(II) amides has been prepared and characterized. Reaction of [CrCl2(thf)2] (thf = tetrahydrofuran) with 2 equivalents of M(NR2) (R = C6H11, Pr(i), Ph, or phenothiazinyl; M = Li or Na) allowed the formation of the homoleptic amides [{Cr(mu-NR2)(NR2)}2] (R =

Ground-State Distortion in N-Acyl-tert-butyl-carbamates (Boc) and N-Acyl-tosylamides (Ts): Twisted Amides of Relevance to Amide N-C Cross-Coupling.

Science.gov (United States)

Szostak, Roman; Shi, Shicheng; Meng, Guangrong; Lalancette, Roger; Szostak, Michal

2016-09-02

Amide N-C(O) bonds are generally unreactive in cross-coupling reactions employing low-valent transition metals due to nN → π*C═O resonance. Herein we demonstrate that N-acyl-tert-butyl-carbamates (Boc) and N-acyl-tosylamides (Ts), two classes of acyclic amides that have recently enabled the development of elusive amide bond N-C cross-coupling reactions with organometallic reagents, are intrinsically twisted around the N-C(O) axis. The data have important implications for the design of new amide cross-coupling reactions with the N-C(O) amide bond cleavage as a key step.

Fatty Amides from Crude Rice Bran Oil as Green Corrosion Inhibitors

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E. Reyes-Dorantes

2017-01-01

Full Text Available Due to its high oil content, this research proposes the use of an agroindustrial byproduct (rice bran as a sustainable option for the synthesis of corrosion inhibitors. From the crude rice bran oil, the synthesis of fatty amide-type corrosion inhibitors was carried out. The corrosion inhibitory capacity of the fatty amides was evaluated on an API X-70 steel using electrochemical techniques such as real-time corrosion monitoring and potentiodynamic polarization curves. As a corrosive medium, a CO2-saturated solution (3.5% NaCl was used at three temperatures (30, 50, and 70°C and different concentrations of inhibitor (0, 5, 10, 25, 50, and 100 ppm. The results demonstrate that the sustainable use of agroindustrial byproducts is a good alternative to the synthesis of environmentally friendly inhibitors with high corrosion inhibition efficiencies.

A General and Simple Diastereoselective Reduction by L-Selectride: Efficient Synthesis of Protected (4S,5S-Dihydroxy Amides

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Bo Yin

2010-04-01

Full Text Available A general approach to (4S,5S-4-benzyloxy-5-hydroxy-N-(4-methoxybenzyl amides 10 based on a diastereoselective reduction of (5S,6RS-6-alkyl-5-benzyloxy-6-hydroxy-2-piperidinones 6 and their tautomeric ring-opened keto amides 7 is described. The reduction with L-Selectride at -20 °C to room temperature afforded the products 10 in excellent yields and moderate to high syn-diastereoselectivities.

Concentration and distribution of dissolved amino acids in a shallow hydrothermal system, Vulcano Island (Italy)

Energy Technology Data Exchange (ETDEWEB)

Svensson, E.; Skoog, A. [University of Connecticut, Groton, CT (United States). Dept. of Marine Sciences; Amend, J.P. [Washington University, St. Louis, MO (United States). Dept. of Earth and Planetary Sciences

2004-09-01

Hydrothermal systems are known to harbour a large number of microorganisms, but the organic chemical composition of the solution that comprises their potential substrate is largely unknown. Concentrations and distributions of dissolved free amino acids (DFAA) and dissolved combined amino acids (DCAA) were determined in fluids from the moderate-temperature (42-89{sup o}C), shallow hydrothermal system on the volcanically active island of Vulcano, Italy. The seven samples represent three different geological settings on the island; shallow ({approx} 1 m) submarine vents, geothermal wells, and seeps in heated beach sediments, in addition to ambient local seawater from the bay, Baia di Levante. All hydrothermal sites, with one exception, had TDAA concentrations that were 3-114 times higher than local seawater in Baia di Levante. There were large similarities in amino acid concentration and composition among samples from the same geological setting. The highest amino acid concentrations were found at sites with acidic and reducing conditions, which also had the largest freshwater component. An unusually high fraction of the TDAA pool was represented by DFAA (33-87%), possibly due to in situ acid hydrolysis of DCAA to DFAA. Both DFAA and DCAA concentrations were correlated to DOC, indicating similar source and sink functions for these pools. The yield of TDAA (TDAA-carbon as fraction of organic carbon) ranged from 2% to 25%, which is high compared with non-hydrothermal settings, and indicates high biological lability. The mole fraction of {beta}-alanine plus {gamma}-aminobutyric acid (% BALA + GABA) was 2-2.7% of TDAA, also indicating high biological lability. Owing to the high over-all amino acid concentrations, the high fraction of DFAAs, and the high biological lability of the organic matter, organic matter in general and amino acids specifically could represent significant carbon and energy sources for archaea and bacteria in this hydrothermal system. The clear

Acclimation responses to temperature vary with vertical stratification: implications for vulnerability of soil-dwelling species to extreme temperature events.

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van Dooremalen, Coby; Berg, Matty P; Ellers, Jacintha

2013-03-01

The occurrence of summer heat waves is predicted to increase in amplitude and frequency in the near future, but the consequences of such extreme events are largely unknown, especially for belowground organisms. Soil organisms usually exhibit strong vertical stratification, resulting in more frequent exposure to extreme temperatures for surface-dwelling species than for soil-dwelling species. Therefore soil-dwelling species are expected to have poor acclimation responses to cope with temperature changes. We used five species of surface-dwelling and four species of soil-dwelling Collembola that habituate different depths in the soil. We tested for differences in tolerance to extreme temperatures after acclimation to warm and cold conditions. We also tested for differences in acclimation of the underlying physiology by looking at changes in membrane lipid composition. Chill coma recovery time, heat knockdown time and fatty acid profiles were determined after 1 week of acclimation to either 5 or 20 °C. Our results showed that surface-dwelling Collembola better maintained increased heat tolerance across acclimation temperatures, but no such response was found for cold tolerance. Concordantly, four of the five surface-dwelling Collembola showed up to fourfold changes in relative abundance of fatty acids after 1 week of acclimation, whereas none of the soil-dwelling species showed a significant adjustment in fatty acid composition. Strong physiological responses to temperature fluctuations may have become redundant in soil-dwelling species due to the relative thermal stability of their subterranean habitat. Based on the results of the four species studied, we expect that unless soil-dwelling species can temporarily retreat to avoid extreme temperatures, the predicted increase in heat waves under climatic change renders these soil-dwelling species more vulnerable to extinction than species with better physiological capabilities. Being able to act under a larger thermal

Amide Link Scission in the Polyamide Active Layers of Thin-Film Composite Membranes upon Exposure to Free Chlorine: Kinetics and Mechanisms.

Science.gov (United States)

Powell, Joshua; Luh, Jeanne; Coronell, Orlando

2015-10-20

The volume-averaged amide link scission in the aromatic polyamide active layer of a reverse osmosis membrane upon exposure to free chlorine was quantified at a variety of free chlorine exposure times, concentrations, and pH and rinsing conditions. The results showed that (i) hydroxyl ions are needed for scission to occur, (ii) hydroxide-induced amide link scission is a strong function of exposure to hypochlorous acid, (iii) the ratio between amide links broken and chlorine atoms taken up increased with the chlorination pH and reached a maximum of ∼25%, (iv) polyamide disintegration occurs when high free chlorine concentrations, alkaline conditions, and high exposure times are combined, (v) amide link scission promotes further chlorine uptake, and (vi) scission at the membrane surface is unrepresentative of volume-averaged scission in the active layer. Our observations are consistent with previously proposed mechanisms describing amide link scission as a result of the hydrolysis of the N-chlorinated amidic N-C bond due to nucleophilic attack by hydroxyl ions. This study increases the understanding of the physicochemical changes that could occur for membranes in treatment plants using chlorine as an upstream disinfectant and the extent and rate at which those changes would occur.

Semi-catalytic reduction of secondary amides to imines and aldehydes.

Science.gov (United States)

Lee, Sun-Hwa; Nikonov, Georgii I

2014-06-21

Secondary amides can be reduced by silane HSiMe2Ph into imines and aldehydes by a two-stage process involving prior conversion of amides into iminoyl chlorides followed by catalytic reduction mediated by the ruthenium complex [Cp(i-Pr3P)Ru(NCCH3)2]PF6 (1). Alkyl and aryl amides bearing halogen, ketone, and ester groups were converted with moderate to good yields under mild reaction conditions to the corresponding imines and aldehydes. This procedure does not work for substrates bearing the nitro-group and fails for heteroaromatic amides. In the case of cyano substituted amides, the cyano group is reduced to imine.

Rhizosphere Environment and Labile Phosphorus Release from Organic Waste-Amended Soils.

Science.gov (United States)

Dao, Thanh H.

2015-04-01

Crop residues and biofertilizers are primary sources of nutrients for organic crop production. However, soils treated with large amounts of nutrient-enriched manure have elevated phosphorus (P) levels in regions of intensive animal agriculture. Surpluses occurred in these amended soils, resulting in large pools of exchangeable inorganic P (Pi) and enzyme-labile organic P (Po) that averaging 30.9 and 68.2 mg kg-1, respectively. Organic acids produced during crop residue decomposition can promote the complexation of counter-ions and decouple and release unbound Pi from metal and alkali metal phosphates. Animal manure and cover crop residues also contain large amounts of soluble organic matter, and likely generate similar ligands. However, a high degree of heterogeneity in P spatial distribution in such amended fields, arising from variances in substrate physical forms ranging from slurries to dried solids, composition, and diverse application methods and equipment. Distinct clusters of Pi and Po were observed, where accumulation of the latter forms was associated with high soil microbial biomass C and reduced phosphomonoesterases' activity. Accurate estimates of plant requirements and lability of soil P pools, and real-time plant and soil P sensing systems are critical considerations to optimally manage manure-derived nutrients in crop production systems. An in situ X-ray fluorescence-based approach to sensing canopy and soil XRFS-P was developed to improve the yield-soil P relationship for optimal nutrient recommendations in addition to allowing in-the-field verification of foliar P status.

Characterization of a novel alpha-amidated decapeptide derived from proopiomelanocortin-A in the trout pituitary.

Science.gov (United States)

Tollemer, H; Leprince, J; Bailhache, T; Chauveau, I; Vandesande, F; Tonon, M C; Jego, P; Vaudry, H

1997-01-01

Two complementary DNAs encoding distinct forms of POMC have been characterized in the trout pituitary. One of the POMC variants (POMC-A) possesses a C-terminal extension of 25 amino acids, which has no equivalent in other POMCs described to date. This C-terminal peptide contains three pairs of basic amino acids, suggesting that it may be the precursor of multiple processed peptides. In addition, the presence of a C-terminal glycine residue suggests that some of the processing products may be alpha-amidated. To characterize the molecular forms of the peptides generated from the C-terminal domain of trout POMC-A, we have developed specific antibodies against the C-terminal pentapeptide YHFQG and its alpha-amidated derivative YHFQ-NH2. Immunocytochemical labeling of pituitary sections with antibodies against YHFQ-NH2 revealed the presence of numerous immunoreactive cells in the pars intermedia and the rostral pars distalis. In contrast, the antibodies against YHFQG produced only weak immunostaining. HPLC analysis combined with RIA detection revealed that extracts of the pars intermedia and pars distalis contain several peptides derived from the C-terminal extension of trout POMC-A, with the predominant molecular form exhibiting the same retention time as ALGERKYHFQ-NH2. Tryptic digestion of this major form produced a peptide that coeluted with YHFQ-NH2. These data indicate that the processing of the C-terminal extension of trout POMC-A generates several novel peptides including the decapeptide amide ALGERKYHFQ-NH2.

The synthesis of taurine-conjugated bile acids and bile acid sulfates labeled with 14C or 3H in the taurine moiety

International Nuclear Information System (INIS)

Jie Zhang; Griffiths, W.J.; Sjoevall, Jan

1997-01-01

Studies of bile acid transport systems require radio-labeled taurine-conjugated bile acids with high specific activity. An established procedure was optimized to provide mild, fast, and effective conjugation of radio-labeled taurine with different types of bile acids, including those with labile 7α-hydroxy-3-oxo-Δ 4 or 3β, 7α-dihydroxy-Δ 5 structures. Taurine labeled with 14 C or 3 H was reacted with excess bile acid anhydride formed from the tributylamine salt and ethylchloroformate (2/1 M/M) in aqueous dioxane for 15 min at room temperature. The yields were higher than 95% and less than 2% side products were formed. Bile acid sulfates were conjugated with 14 C- or 3 H-labeled taurine by using N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline as the coupling reagent. The products were effectively purified by chromatography of the sodium salts on Sephadex LH-20. The yields of taurine-conjugated bile acid sulfates were 65-70%. (author)

40 CFR 721.10063 - Halo substituted hydroxy nitrophenyl amide (generic).

Science.gov (United States)

2010-07-01

... amide (generic). 721.10063 Section 721.10063 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10063 Halo substituted hydroxy nitrophenyl amide (generic). (a) Chemical... as halo substituted hydroxy nitrophenyl amide (PMN P-04-792) is subject to reporting under this...

Redox-active labile iron in fortified flours from the Brazilian market Ferro lábil redox-ativo em farinhas fortificadas do mercado brasileiro

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Breno Pannia Espósito

2007-08-01

Full Text Available OBJECTIVE: To quantify the fraction of redox-active labile iron in iron-fortified flours acquired on the Brazilian market. METHODS: Samples of wheat flour, maize flour and breadcrumbs were extracted with buffers that mimic gastric juice, saliva and intestinal juice. Redox-active labile iron levels were assessed through the reaction of autoxidation of ascorbic acid catalyzed by iron in the presence of a fluorescence probe. RESULTS: Redox-active labile iron represents 1% to 9% of the total iron in the flour and breadcrumb samples, with the lowest values found under gastric juice conditions and the highest in the more alkaline media. Redox-active labile iron possibly arises from the decomposition of an iron-phytic acid complex. A positive correlation between redox-active labile iron and total iron was found in saline biomimetic fluids. CONCLUSION: Redox-active labile iron may be a risk factor for people with impaired antioxidant defenses, such as those who are atransferrinemic or iron overloaded (e.g. thalassemic. Total iron can be used to predict redox-active labile iron absorption at each stage of the gastrointestinal tract after ingestion of iron-fortified flours.OBJETIVO: Quantificar a porcentagem de ferro lábil redox ativo em farinhas fortificadas adquiridas no comércio popular. MÉTODOS: Amostras de farinha de trigo, fubá e rosca foram extraídas com tampões miméticos de suco gástrico, saliva e suco intestinal. Os níveis de ferro lábil redox ativo foram determinados por meio da reação de auto-oxidação do ácido ascórbico catalisada pelo ferro, em presença de uma sonda fluorimétrica. RESULTADOS: A fração de ferro lábil redox ativo representa entre 1% e 9% do ferro total nas farinhas estudadas, sendo os menores valores encontrados em condições miméticas do suco gástrico e os maiores nos meios mais alcalinos. Há indícios de que o ferro lábil redox ativo origina-se da decomposição de um complexo entre ferro e ácido f

Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

Science.gov (United States)

Benson, Oguarabau; da Silva, Ivan; Argent, Stephen P; Cabot, Rafel; Savage, Mathew; Godfrey, Harry G W; Yan, Yong; Parker, Stewart F; Manuel, Pascal; Lennox, Matthew J; Mitra, Tamoghna; Easun, Timothy L; Lewis, William; Blake, Alexander J; Besley, Elena; Yang, Sihai; Schröder, Martin

2016-11-16

An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO 2 uptake of 12.6 mmol g -1 at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffraction reveals that, surprisingly, there is no direct binding between the adsorbed CO 2 /CH 4 molecules and the pendant amide group in the pore. This observation has been confirmed unambiguously by inelastic neutron spectroscopy. This suggests that introduction of functional groups solely may not necessarily induce specific guest-host binding in porous materials, but it is a combination of pore size, geometry, and functional group that leads to enhanced gas adsorption properties.

Investigation of uranyl phosphite interaction with some amides

International Nuclear Information System (INIS)

Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Mukhajlov, Yu.N.; Kanishcheva, A.S.; Grevtseva, T.G.

1981-01-01

Uranyl (amide) phosphitocomplexes of [UO 2 HPO 3 H 2 OAA]xH 2 O, [UO 2 HPO 3 (AA) 2 ], [UO 2 HPO 3 H 2 O DMC], [UO 2 HPO 3 H 2 ODMFA], [UO 2 HPO 3 DAMA] and UO 2 HPO 3 x2FAxH 2 O compositions, where AA-acetamide; DMC-N, N-dimetyl carbamide, DMFA-dimetyl formamide; DAMA-diamide of malonic acid; FA-formamide, are separated, identified and investigated. Derivatives of mono substituted uranyl phosphite of UO 2 (H 2 PO 3 ) 2 x2FA and [UO 2 (H 2 PO 3 ) 2 H 2 O]x2TMC composition (where TMC-tetramethyl carbamide), are synthesized. Structures of complexes with DAMA, TMC, DMFA and acid dimethyl-ammonium diphosphitouranylate-(CH 3 ] 2 NH 2 x[UO 2 (HPO 3 ) 3 (H 2 PO 3 )] are investigated [ru

Influence of photoperiod and temperature on frost hardiness and free amino acid concentrations in black spruce seedlings

Energy Technology Data Exchange (ETDEWEB)

1993-01-01

Because photoperiod and temperature both influence amino acid metabolism in plants, seasonal reductions in day length and temperature may be responsible for the changes in amino acid concentrations that occur in conifers with the onset of winter. Since such fluctuations in conifers occur in association with the development of frost hardiness, it has been suggested that the accumulation of specific free amino acids may be related to the development of frost hardiness. This study was designed to determine the effects of photoperiod and temperature on proline, arginine, and tryptophan concentrations in the shoots of black spruce seedlings in relation to the development of hardiness to -20C.

Physiological and biochemical responses of Ricinus communis seedlings to different temperatures: a metabolomics approach.

Science.gov (United States)

Ribeiro, Paulo Roberto; Fernandez, Luzimar Gonzaga; de Castro, Renato Delmondez; Ligterink, Wilco; Hilhorst, Henk W M

2014-08-12

Compared with major crops, growth and development of Ricinus communis is still poorly understood. A better understanding of the biochemical and physiological aspects of germination and seedling growth is crucial for the breeding of high yielding varieties adapted to various growing environments. In this context, we analysed the effect of temperature on growth of young R. communis seedlings and we measured primary and secondary metabolites in roots and cotyledons. Three genotypes, recommended to small family farms as cash crop, were used in this study. Seedling biomass was strongly affected by the temperature, with the lowest total biomass observed at 20°C. The response in terms of biomass production for the genotype MPA11 was clearly different from the other two genotypes: genotype MPA11 produced heavier seedlings at all temperatures but the root biomass of this genotype decreased with increasing temperature, reaching the lowest value at 35°C. In contrast, root biomass of genotypes MPB01 and IAC80 was not affected by temperature, suggesting that the roots of these genotypes are less sensitive to changes in temperature. In addition, an increasing temperature decreased the root to shoot ratio, which suggests that biomass allocation between below- and above ground parts of the plants was strongly affected by the temperature. Carbohydrate contents were reduced in response to increasing temperature in both roots and cotyledons, whereas amino acids accumulated to higher contents. Our results show that a specific balance between amino acids, carbohydrates and organic acids in the cotyledons and roots seems to be an important trait for faster and more efficient growth of genotype MPA11. An increase in temperature triggers the mobilization of carbohydrates to support the preferred growth of the aerial parts, at the expense of the roots. A shift in the carbon-nitrogen metabolism towards the accumulation of nitrogen-containing compounds seems to be the main biochemical

Effect of exogenous phosphate on the lability and phytoavailability of arsenic in soils.

Science.gov (United States)

Wang, Jinjin; Zeng, Xibai; Zhang, Hao; Li, Yongtao; Zhao, Shizhen; Su, Shiming; Bai, Lingyu; Wang, Yanan; Zhang, Tuo

2018-04-01

The effect of exogenous phosphate (P, 200 mg⋅kg -1 soil) on the lability and phytoavailability of arsenic (As) was studied using the diffusive gradients in thin films (DGT) technique. Lettuce were grown on the As-amended soils following the stabilization of soil labile As after 90 days incubation. Phosphate (P) application generally facilitated plant growth except one grown on P-sufficient soil. Soil labile As concentration increased in all the soils after P application due to a competition effect. Plant As concentration increased in red soils collected from Hunan Province, while decreases were observed in the other soils. Even though, an overall trend of decrease was obtained in As phytoavailability along with the increase of DGT-measured soil labile P/As molar ratio. The functional equation between P/As and As phytoavailability provided a critical value of 1.7, which could be used as a guidance for rational P fertilization, thus avoiding overfertilization. Copyright © 2018 Elsevier Ltd. All rights reserved.

Spectral response of crystalline acetanilide and N -methylacetamide: Vibrational self-trapping in hydrogen-bonded crystals

Science.gov (United States)

Edler, Julian; Hamm, Peter

2004-06-01

Femtosecond pump-probe and Fourier transform infrared spectroscopy is applied to compare the spectral response of the amide I band and the NH-stretching band of acetanilide (ACN) and N -methylacetamide (NMA), as well as their deuterated derivatives. Both molecules form hydrogen-bonded molecular crystals that are regarded to be model systems for polypeptides and proteins. The amide I bands of both ACN and NMA show a temperature-dependent sideband, while the NH bands are accompanied by a sequence of equidistantly spaced satellite peaks. These spectral anomalies are interpreted as a signature of vibrational self-trapping. Two different types of states can be identified in both crystals in the pump-probe signal: a delocalized free-exciton state and a set of localized self-trapped states. The phonons that mediate self-trapping in ACN and deuterated ACN are identified by their temperature dependence, confirming our previous results. The study shows that the substructure of the NH band in NMA (amide A and amide B bands) originates, at least partly, from vibrational self-trapping and not, as often assumed, from a Fermi resonance.

40 CFR 721.10191 - Amides, coco, N-[3-(dibutylamino)propyl].

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amides, coco, N-[3-(dibutylamino... Specific Chemical Substances § 721.10191 Amides, coco, N-[3-(dibutylamino)propyl]. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amides, coco...

NMR Analysis of Amide Hydrogen Exchange Rates in a Pentapeptide-Repeat Protein from A. thaliana.

Science.gov (United States)

Xu, Shenyuan; Ni, Shuisong; Kennedy, Michael A

2017-05-23

At2g44920 from Arabidopsis thaliana is a pentapeptide-repeat protein (PRP) composed of 25 repeats capped by N- and C-terminal α-helices. PRP structures are dominated by four-sided right-handed β-helices typically consisting of mixtures of type II and type IV β-turns. PRPs adopt repeated five-residue (Rfr) folds with an Rfr consensus sequence (STAV)(D/N)(L/F)(S/T/R)(X). Unlike other PRPs, At2g44920 consists exclusively of type II β-turns. At2g44920 is predicted to be located in the thylakoid lumen although its biochemical function remains unknown. Given its unusual structure, we investigated the biophysical properties of At2g44920 as a representative of the β-helix family to determine if it had exceptional global stability, backbone dynamics, or amide hydrogen exchange rates. Circular dichroism measurements yielded a melting point of 62.8°C, indicating unexceptional global thermal stability. Nuclear spin relaxation measurements indicated that the Rfr-fold core was rigid with order parameters ranging from 0.7 to 0.9. At2g44920 exhibited a striking range of amide hydrogen exchange rates spanning 10 orders of magnitude, with lifetimes ranging from minutes to several months. A weak correlation was found among hydrogen exchange rates, hydrogen bonding energies, and amino acid solvent-accessible areas. Analysis of contributions from fast (approximately picosecond to nanosecond) backbone dynamics to amide hydrogen exchange rates revealed that the average order parameter of amides undergoing fast exchange was significantly smaller compared to those undergoing slow exchange. Importantly, the activation energies for amide hydrogen exchange were found to be generally higher for the slowest exchanging amides in the central Rfr coil and decreased toward the terminal coils. This could be explained by assuming that the concerted motions of two preceding or following coils required for hydrogen bond disruption and amide hydrogen exchange have a higher activation energy

Stability of poly(N-isopropylacrylamide-co-acrylic acid polymer microgels under various conditions of temperature, pH and salt concentration

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Zahoor H. Farooqi

2017-03-01

Full Text Available This research article describes the colloidal stability of poly(N-isopropylacrylamide-co-acrylic acid [P(NIPAM-co-AAc] polymer microgels with different acrylic acid contents in aqueous medium under various conditions of temperature, pH and sodium chloride concentrations. Three samples of multi-responsive P(NIPAM-co-AAc polymer microgels were synthesized using different amounts of acrylic acid by free radical emulsion polymerization. Dynamic laser light scattering was used to investigate the responsive behavior and stability of the prepared microgels under various conditions of pH, temperature and ionic strength. The microgels were found to be stable at all pH values above the pKa value of acrylic acid moiety in the temperature range from 15 to 60 °C in the presence and absence of sodium chloride. Increase in temperature, salt concentration and decrease in pH causes aggregation and decreases the stability of microgels due to the decrease in hydrophilicity.

Trans labilization of am(m)ine ligands from platinum(II) complexes by cancer cell extracts.

Science.gov (United States)

Kasherman, Yonit; Sturup, Stefan; Gibson, Dan

2009-03-01

Cisplatin, cis-[Pt(NH(3))(2)Cl(2)], is an effective anticancer agent in wide clinical use whose efficacy is affected by cellular interactions with sulfur-containing nucleophiles. These interactions can potentially enhance the efficacy of the drug by mediating its delivery to nuclear DNA or inactivate the drug by binding to it irreversibly or by labilizing the NH(3) ligands. Despite the potential importance of trans-labilization reactions in the mechanism of action of the drug, few detailed studies on trans labilization of the ammines have been conducted. We used 2D NMR to show that some trans labilization occurs in proliferating cells and that aqueous extracts of cancer cells labilized 20% of the amine ligands of cis-[PtCl(2)((13)CH(3)NH(2))(2)] after a 12-h incubation. Both low molecular mass nucleophiles (less than 3 kDa) and high molecular mass nucleophiles (more than 3 kDa) labilize the amines with similar efficiency. Studies with model compounds show that thiols and thioethers bind to platinum(II) at similar rates, but thioethers are significantly more efficient at labilizing the am(m)ine at lower pH. N-Acetylcysteine is a more efficient trans-labilizer than glutathione, suggesting that the displacement of the amine proceeds through an associative mechanism. The lag time, the time that elapses from the formation of the Pt-S bond till the release of the amine trans to the sulfur, depends on the pH (for thiols), increasing at lower pH. Quantification of the platinum adducts obtained from incubation of cisplatin with cell extracts indicates that two thirds of the platinum is bound to cellular components with molecular mass greater than 3 kDa.

3-Aminoquinoline/p-coumaric acid as a MALDI matrix for glycopeptides, carbohydrates, and phosphopeptides.

Science.gov (United States)

Fukuyama, Yuko; Funakoshi, Natsumi; Takeyama, Kohei; Hioki, Yusaku; Nishikaze, Takashi; Kaneshiro, Kaoru; Kawabata, Shin-Ichirou; Iwamoto, Shinichi; Tanaka, Koichi

2014-02-18

Glycosylation and phosphorylation are important post-translational modifications in biological processes and biomarker research. The difficulty in analyzing these modifications is mainly their low abundance and dissociation of labile regions such as sialic acids or phosphate groups. One solution in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is to improve matrices for glycopeptides, carbohydrates, and phosphopeptides by increasing the sensitivity and suppressing dissociation of the labile regions. Recently, a liquid matrix 3-aminoquinoline (3-AQ)/α-cyano-4-hydroxycinnamic acid (CHCA) (3-AQ/CHCA), introduced by Kolli et al. in 1996, has been reported to increase sensitivity for carbohydrates or phosphopeptides, but it has not been systematically evaluated for glycopeptides. In addition, 3-AQ/CHCA enhances the dissociation of labile regions. In contrast, a liquid matrix 1,1,3,3-tetramethylguanidium (TMG, G) salt of p-coumaric acid (CA) (G3CA) was reported to suppress dissociation of sulfate groups or sialic acids of carbohydrates. Here we introduce a liquid matrix 3-AQ/CA for glycopeptides, carbohydrates, and phosphopeptides. All of the analytes were detected as [M + H](+) or [M - H](-) with higher or comparable sensitivity using 3-AQ/CA compared with 3-AQ/CHCA or 2,5-dihydroxybenzoic acid (2,5-DHB). The sensitivity was increased 1- to 1000-fold using 3-AQ/CA. The dissociation of labile regions such as sialic acids or phosphate groups and the fragmentation of neutral carbohydrates were suppressed more using 3-AQ/CA than using 3-AQ/CHCA or 2,5-DHB. 3-AQ/CA was thus determined to be an effective MALDI matrix for high sensitivity and the suppression of dissociation of labile regions in glycosylation and phosphorylation analyses.

N-acetyl lysyltyrosylcysteine amide inhibits myeloperoxidase, a novel tripeptide inhibitor1[S

OpenAIRE

Zhang, Hao; Jing, Xigang; Shi, Yang; Xu, Hao; Du, Jianhai; Guan, Tongju; Weihrauch, Dorothee; Jones, Deron W.; Wang, Weiling; Gourlay, David; Oldham, Keith T.; Hillery, Cheryl A.; Pritchard, Kirkwood A.

2013-01-01

Myeloperoxidase (MPO) plays important roles in disease by increasing oxidative and nitrosative stress and oxidizing lipoproteins. Here we report N-acetyl lysyltyrosylcysteine amide (KYC) is an effective inhibitor of MPO activity. We show KYC inhibits MPO-mediated hypochlorous acid (HOCl) formation and nitration/oxidation of LDL. Disulfide is the major product of MPO-mediated KYC oxidation. KYC (⩽4,000 μM) does not induce cytotoxicity in bovine aortic endothelial cells (BAECs). KYC inhibits HO...

Photoinduced gelation by stilbene oxalyl amide compounds.

Science.gov (United States)

Miljanić, Snezana; Frkanec, Leo; Meić, Zlatko; Zinić, Mladen

2005-03-29

Oxalyl amide derivatives bearing 4-dodecyloxy-stilbene as a cis-trans photoisomerizing unit were synthesized. The trans derivative acted as a versatile gelator of various organic solvents, whereas the corresponding cis derivative showed a poor gelation ability or none at all. In diluted solution (c = 2.0 x10(-5) mol dm(-3), ethanol), the cis isomer was photochemically converted into the trans isomer within 4 min. Depending on the radiation wavelength, the trans isomer was stable or liable to photodecomposition. When exposed to irradiation, a concentrated solution of the cis isomer (c = 2.0 x 10(-2) mol dm(-3), ethanol) turned into a gel. The FT-Raman, FT-IR, and 1H NMR spectra demonstrated that the gelation process occurred because of a rapid cis --> trans photoisomerization followed by a self-assembly of the trans molecules. Apart from the formation of hydrogen bonding between the oxalyl amide parts of the molecules, confirmed by FT-IR spectroscopy, it was assumed that the pi-pi stacking between the trans-stilbene units of the molecule and a lipophilic interaction between long alkyl chains were the interactions responsible for gelation.

Anticholesterolemic effect of 3,4-di(OH)-phenylpropionic amides in high-cholesterol fed rats

International Nuclear Information System (INIS)

Kim, Soon-Ja; Bok, Song-Hae; Lee, Sangku; Kim, Hye-Jin; Lee, Mi-Kyung; Park, Yong Bok; Choi, Myung-Sook