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.

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...

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.

Microorganisms hydrolyse amide bonds; knowledge enabling read-across of biodegradability of fatty acid amides

NARCIS (Netherlands)

Geerts, R.; Kuijer, P.; Ginkel, van C.G.; Plugge, C.M.

2014-01-01

To get insight in the biodegradation and potential read-across of fatty acid amides, N-[3-(dimethylamino)propyl] cocoamide and N-(1-ethylpiperazine) tall oil amide were used as model compounds. Two bacteria, Pseudomonas aeruginosa PK1 and Pseudomonas putida PK2 were isolated with

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.

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.

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)

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

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.

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.

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.

Luciferin Amides Enable in Vivo Bioluminescence Detection of Endogenous Fatty Acid Amide Hydrolase Activity.

Science.gov (United States)

Mofford, David M; Adams, Spencer T; Reddy, G S Kiran Kumar; Reddy, Gadarla Randheer; Miller, Stephen C

2015-07-15

Firefly luciferase is homologous to fatty acyl-CoA synthetases. We hypothesized that the firefly luciferase substrate d-luciferin and its analogs are fatty acid mimics that are ideally suited to probe the chemistry of enzymes that release fatty acid products. Here, we synthesized luciferin amides and found that these molecules are hydrolyzed to substrates for firefly luciferase by the enzyme fatty acid amide hydrolase (FAAH). In the presence of luciferase, these molecules enable highly sensitive and selective bioluminescent detection of FAAH activity in vitro, in live cells, and in vivo. The potency and tissue distribution of FAAH inhibitors can be imaged in live mice, and luciferin amides serve as exemplary reagents for greatly improved bioluminescence imaging in FAAH-expressing tissues such as the brain.

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

Science.gov (United States)

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.

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

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...

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.

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 ().

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)

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.

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.

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.

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.

Metal extraction by amides of carboxylic acids

International Nuclear Information System (INIS)

Skorovarov, D.I.; Chumakova, G.M.; Rusin, L.I.; Ul'anov, V.S.; Sviridova, R.A.; Sviridov, A.L.

1988-01-01

Extraction ability of various amides was studied. Data on extraction of rare earths, vanadium, molybdenum, rhenium, uranium, niobium, tantalum by N,N-dibutyl-amides of acetic, nonanic acids and fatly synthetic acids of C 7 -C 9 fractions are presented. Effect of salting-out agents, inorganic acid concentrations on extraction process was studied. Potential ability of using amides of carboxylic acids for extractional concentration of rare earths as well as for recovery and separation of iron, rhenium, vanadium, molybdenum, uranium, niobium, and tantalum was shown

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.

Amide proton temperature coefficients as hydrogen bond indicators in proteins

International Nuclear Information System (INIS)

Cierpicki, Tomasz; Otlewski, Jacek

2001-01-01

Correlations between amide proton temperature coefficients (Δσ HN /ΔT) and hydrogen bonds were investigated for a data set of 793 amides derived from 14 proteins. For amide protons showing temperature gradients more positive than -4.6 ppb/K there is a hydrogen bond predictivity value exceeding 85%. It increases to over 93% for amides within the range between -4 and -1 ppb/K. Detailed analysis shows an inverse proportionality between amide proton temperature coefficients and hydrogen bond lengths. Furthermore, for hydrogen bonds of similar bond lengths, values of temperature gradients in α-helices are on average 1 ppb/K more negative than in β-sheets. In consequence, a number of amide protons in α-helices involved in hydrogen bonds shorter than 2 A show Δσ HN /ΔT 10 helices and 98% in β-turns have temperature coefficients more positive than -4.6ppb/K. Ring current effect also significantly influences temperature coefficients of amide protons. In seven out of eight cases non-hydrogen bonded amides strongly deshielded by neighboring aromatic rings show temperature coefficients more positive than -2 ppb/K. In general, amide proton temperature gradients do not change with pH unless they correspond to conformational changes. Three examples of pH dependent equilibrium showing hydrogen bond formation at higher pH were found. In conclusion, amide proton temperature coefficients offer an attractive and simple way to confirm existence of hydrogen bonds in NMR determined structures

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

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.

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.

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.

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.

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

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.

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...

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

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.

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.

40 CFR 721.720 - Alkoxylated fatty acid amide, alkylsulfate salt.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkoxylated fatty acid amide... Specific Chemical Substances § 721.720 Alkoxylated fatty acid amide, alkylsulfate salt. (a) Chemical... as an alkoxylated fatty acid amide, alkylsulfate salt (PMN P-97-136) is subject to reporting under...

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...

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

Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol

Directory of Open Access Journals (Sweden)

Hailiang Zhao

2016-12-01

Full Text Available Amides are important atmospheric organic–nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH with amides (formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide and N,N-dimethylacetamide have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH–amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O–H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol.

Science.gov (United States)

Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

2016-12-30

Amides are important atmospheric organic-nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N -methylformamide, N , N -dimethylformamide, acetamide, N -methylacetamide and N , N -dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH-amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O-H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

Synthesis of Secondary Aromatic Amides via Pd-Catalyzed Aminocarbonylation of Aryl Halides Using Carbamoylsilane as an Amide Source.

Science.gov (United States)

Tong, Wenting; Cao, Pei; Liu, Yanhong; Chen, Jianxin

2017-11-03

Using N-methoxymethyl-N-organylcarbamoyl(trimethyl)silanes as secondary amides source, the direct transformation of aryl halides into the corresponding secondary aromatic amides via palladium-catalyzed aminocarbonylation is described. The reactions tolerated a broad range of functional groups on the aryl ring except big steric hindrance of substituent. The types and the relative position of substituents on the aryl ring impact the coupling efficiency.

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

Synthesis of amide isosteres of schweinfurthin-based stilbenes.

Science.gov (United States)

Stockdale, David P; Beutler, John A; Wiemer, David F

2017-10-15

The schweinfurthins are plant-derived stilbenes with an intriguing profile of anti-cancer activity. To obtain analogues of the schweinfurthins that might preserve the biological activity but have greater water solubility, a formal replacement of the central olefin with an amide has been explored. Two pairs of amides have been prepared, each containing the same hexahydroxanthene "left half" joined through an amide linkage to two different "right halves." In each series, the amide has been inserted in both possible orientations, placing the carbonyl group on the tricyclic ABC ring system and the amine on the D-ring, or placing the amine on the hexahydroxanthene and the carbonyl group on the D-ring. The four new schweinfurthin analogues have been tested in the NCI 60 cell line screen, and in both cases the more active isomer carried the carbonyl group on the C-ring. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metabolism of amino acid amides in Pseudomonas putida ATCC 12633

NARCIS (Netherlands)

Hermes, H.F.M.; Croes, L.M.; Peeters, W.P.H.; Peters, P.J.H.; Dijkhuizen, L.

1993-01-01

The metabolism of the natural amino acid L-valine, the unnatural amino acids D-valine, and D-, L-phenylglycine (D-, L-PG), and the unnatural amino acid amides D-, L-phenylglycine amide (D, L-PG-NH2) and L-valine amide (L-Val-NH2) was studied in Pseudomonas putida ATCC 12633. The organism possessed

Amide temperature coefficients in the protein G B1 domain

International Nuclear Information System (INIS)

Tomlinson, Jennifer H.; Williamson, Mike P.

2012-01-01

Temperature coefficients have been measured for backbone amide 1 H and 15 N nuclei in the B1 domain of protein G (GB1), using temperatures in the range 283–313 K, and pH values from 2.0 to 9.0. Many nuclei display pH-dependent coefficients, which were fitted to one or two pK a values. 1 H coefficients showed the expected behaviour, in that hydrogen-bonded amides have less negative values, but for those amides involved in strong hydrogen bonds in regular secondary structure there is a negative correlation between strength of hydrogen bond and size of temperature coefficient. The best correlation to temperature coefficient is with secondary shift, indicative of a very approximately uniform thermal expansion. The largest pH-dependent changes in coefficient are for amides in loops adjacent to sidechain hydrogen bonds rather than the amides involved directly in hydrogen bonds, indicating that the biggest determinant of the temperature coefficient is temperature-dependent loss of structure, not hydrogen bonding. Amide 15 N coefficients have no clear relationship with structure.

A Convenient Approach to Synthesizing Peptide C-Terminal N-Alkyl Amides

Science.gov (United States)

Fang, Wei-Jie; Yakovleva, Tatyana; Aldrich, Jane V.

2014-01-01

Peptide C-terminal N-alkyl amides have gained more attention over the past decade due to their biological properties, including improved pharmacokinetic and pharmacodynamic profiles. However, the synthesis of this type of peptide on solid phase by current available methods can be challenging. Here we report a convenient method to synthesize peptide C-terminal N-alkyl amides using the well-known Fukuyama N-alkylation reaction on a standard resin commonly used for the synthesis of peptide C-terminal primary amides, the PAL-PEG-PS (Peptide Amide Linker-polyethylene glycol-polystyrene) resin. The alkylation and oNBS deprotection were conducted under basic conditions and were therefore compatible with this acid labile resin. The alkylation reaction was very efficient on this resin with a number of different alkyl iodides or bromides, and the synthesis of model enkephalin N-alkyl amide analogs using this method gave consistently high yields and purities, demonstrating the applicability of this methodology. The synthesis of N-alkyl amides was more difficult on a Rink amide resin, especially the coupling of the first amino acid to the N-alkyl amine, resulting in lower yields for loading the first amino acid onto the resin. This method can be widely applied in the synthesis of peptide N-alkyl amides. PMID:22252422

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

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.

40 CFR 721.9075 - Quaternary ammonium salt of fluorinated alkylaryl amide.

Science.gov (United States)

2010-07-01

... fluorinated alkylaryl amide. 721.9075 Section 721.9075 Protection of Environment ENVIRONMENTAL PROTECTION... amide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as quaternary ammonium salt of fluorinated alkylaryl amide (PMN No. P-92-688) is...

Non-amidated and amidated members of the C-type allatostatin (AST-C) family are differentially distributed in the stomatogastric nervous system of the American lobster, Homarus americanus.

Science.gov (United States)

Christie, Andrew E; Miller, Alexandra; Fernandez, Rebecca; Dickinson, Evyn S; Jordan, Audrey; Kohn, Jessica; Youn, Mina C; Dickinson, Patsy S

2018-01-13

The crustacean stomatogastric nervous system (STNS) is a well-known model for investigating neuropeptidergic control of rhythmic behavior. Among the peptides known to modulate the STNS are the C-type allatostatins (AST-Cs). In the lobster, Homarus americanus, three AST-Cs are known. Two of these, pQIRYHQCYFNPISCF (AST-C I) and GNGDGRLYWRCYFNAVSCF (AST-C III), have non-amidated C-termini, while the third, SYWKQCAFNAVSCFamide (AST-C II), is C-terminally amidated. Here, antibodies were generated against one of the non-amidated peptides (AST-C I) and against the amidated isoform (AST-C II). Specificity tests show that the AST-C I antibody cross-reacts with both AST-C I and AST-C III, but not AST-C II; the AST-C II antibody does not cross-react with either non-amidated peptide. Wholemount immunohistochemistry shows that both subclasses (non-amidated and amidated) of AST-C are distributed throughout the lobster STNS. Specifically, the antibody that cross-reacts with the two non-amidated peptides labels neuropil in the CoGs and the stomatogastric ganglion (STG), axons in the superior esophageal (son) and stomatogastric (stn) nerves, and ~ 14 somata in each commissural ganglion (CoG). The AST-C II-specific antibody labels neuropil in the CoGs, STG and at the junction of the sons and stn, axons in the sons and stn, ~ 42 somata in each CoG, and two somata in the STG. Double immunolabeling shows that, except for one soma in each CoG, the non-amidated and amidated peptides are present in distinct sets of neuronal profiles. The differential distributions of the two AST-C subclasses suggest that the two peptide groups are likely to serve different modulatory roles in the lobster STNS.

Characteristic conformation of Mosher's amide elucidated using the cambridge structural database.

Science.gov (United States)

Ichikawa, Akio; Ono, Hiroshi; Mikata, Yuji

2015-07-16

Conformations of the crystalline 3,3,3-trifluoro-2-methoxy-2-phenylpropanamide derivatives (MTPA amides) deposited in the Cambridge Structural Database (CSD) were examined statistically as Racid-enantiomers. The majority of dihedral angles (48/58, ca. 83%) of the amide carbonyl groups and the trifluoromethyl groups ranged from -30° to 0° with an average angle θ1 of -13°. The other conformational properties were also clarified: (1) one of the fluorine atoms was antiperiplanar (ap) to the amide carbonyl group, forming a staggered conformation; (2) the MTPA amides prepared from primary amines showed a Z form in amide moieties; (3) in the case of the MTPA amide prepared from a primary amine possessing secondary alkyl groups (i.e., Mosher-type MTPA amide), the dihedral angles between the methine groups and the carbonyl groups were syn and indicative of a moderate conformational flexibility; (4) the phenyl plane was inclined from the O-Cchiral bond of the methoxy moiety with an average dihedral angle θ2 of +21°; (5) the methyl group of the methoxy moiety was ap to the ipso-carbon atom of the phenyl group.

Structural study of salt forms of amides; paracetamol, benzamide and piperine

Science.gov (United States)

Kennedy, Alan R.; King, Nathan L. C.; Oswald, Iain D. H.; Rollo, David G.; Spiteri, Rebecca; Walls, Aiden

2018-02-01

Single crystal x-ray diffraction has been used to investigate the structures of six complexes containing O-atom protonated cations derived from the pharmaceutically relevant amides benzamide (BEN), paracetamol (PAR) and piperine (PIP). The structures of the salt forms [PAR(H)][SO3C6H4Cl], [BEN(H)][O3SC6H4Cl] and [BEN(H)][Br]·H2O are reported along with those of the hemi-halide salt forms [PAR(H)][I3]. PAR, [PIP(H)][I3]·PIP and [PIP(H)][I3]0·5[I]0.5. PIP. The structure of the cocrystal BEN. HOOCCH2Cl is also presented for comparison. The geometry of the amide group is found to systematically change upon protonation, with the Cdbnd O distance increasing and the Csbnd N distance decreasing. The hemi-halide species all feature strongly hydrogen bonded amide(H)/amide pairs. The amide group Cdbnd O and Csbnd N distances for both elements of each such pair are intermediate between those found for simple neutral amide and protonated amide forms. It was found that crystallising paracetamol from aqueous solutions containing Ba2+ ions gave orthorhombic paracetamol.

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.

Tripodal diglycol-amides as highly efficient extractants for f-elements

Energy Technology Data Exchange (ETDEWEB)

Janczewski, D.; Reinhoudt, D. N.; Verboom, W. [Univ Twente, Mesa Res Inst Nanotechnol, Lab Supramol Chem and Technol, NL-7500 AE Enschede, (Netherlands); Janczewski, D. [Inst Mat Res and Engn, Singapore 117602, (Singapore); Verboom, W. [Univ Twente, Mesa Res Inst Nanotechnol, Lab Mol Nanofabricat, NL-7500 AE Enschede, (Netherlands); Hill, C.; Allignol, C.; Duchesne, M. T. [CEA Valrho, DRCP/SCPS/LCSE, F-30207 Bagnols Sur Ceze, (France)

2008-07-01

A series of new ligands bearing three diglycol-amide functions pre-organized at the C-pivot and tri-alkyl-phenyl platforms was synthesized. They are very efficient extractants for Am{sup 3+} and Eu{sup 3+} with an up to five times relative extraction ability for Eu{sup 3+}. The distribution coefficients are up to 1000 times increased upon alkylation or arylation of the N-position of the diglycol-amide moieties. The tripodal diglycol-amides show a 1: 1 metal to ligand stoichiometry as proven with three independent methods for the complexation of the 3-pentyl N-substituted diglycol-amide ligand with Eu{sup 3+} (K = 2.5 x 10{sup 5} M{sup -1} in acetonitrile-water). A cage-like cryptand, containing three diglycol-amide units, was prepared using a Eu{sup 3+} templated synthesis. However, it does not exhibit improved extraction properties. (authors)

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.

40 CFR 721.10176 - Amides, peanut-oil, N-[3-(dimethylamino)propyl].

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amides, peanut-oil, N-[3... Specific Chemical Substances § 721.10176 Amides, peanut-oil, N-[3-(dimethylamino)propyl]. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amides...

40 CFR 721.10192 - Amides, coco, N-[3-(dibutylamino)propyl], acrylates.

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 § 721.10192 Amides, coco, N-[3-(dibutylamino)propyl], acrylates. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amides...

Decarbonylative Phosphorylation of Amides by Palladium and Nickel Catalysis: The Hirao Cross-Coupling of Amide Derivatives.

Science.gov (United States)

Liu, Chengwei; Szostak, Michal

2017-10-02

Considering the ubiquity of organophosphorus compounds in organic synthesis, pharmaceutical discovery agrochemical crop protection and materials chemistry, new methods for their construction hold particular significance. A conventional method for the synthesis of C-P bonds involves cross-coupling of aryl halides and dialkyl phosphites (the Hirao reaction). We report a catalytic deamidative phosphorylation of a wide range of amides using a palladium or nickel catalyst giving aryl phosphonates in good to excellent yields. The present method tolerates a wide range of functional groups. The reaction constitutes the first example of a transition-metal-catalyzed generation of C-P bonds from amides. This redox-neutral protocol can be combined with site-selective conventional cross-coupling for the regioselective synthesis of potential pharmacophores. Mechanistic studies suggest an oxidative addition/transmetallation pathway. In light of the importance of amides and phosphonates as synthetic intermediates, we envision that this Pd and Ni-catalyzed C-P bond forming method will find broad application. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonplanar tertiary amides in rigid chiral tricyclic dilactams. Peptide group distortions and vibrational optical activity.

Science.gov (United States)

Pazderková, Markéta; Profant, Václav; Hodačová, Jana; Sebestík, Jaroslav; Pazderka, Tomáš; Novotná, Pavlína; Urbanová, Marie; Safařík, Martin; Buděšínský, Miloš; Tichý, Miloš; Bednárová, Lucie; Baumruk, Vladimír; Maloň, Petr

2013-08-22

We investigate amide nonplanarity in vibrational optical activity (VOA) spectra of tricyclic spirodilactams 5,8-diazatricyclo[6,3,0,0(1,5)]undecan-4,9-dione (I) and its 6,6',7,7'-tetradeuterio derivative (II). These rigid molecules constrain amide groups to nonplanar geometries with twisted pyramidal arrangements of bonds to amide nitrogen atoms. We have collected a full range vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectra including signals of C-H and C-D stretching vibrations. We report normal-mode analysis and a comparison of calculated to experimental VCD and ROA. The data provide band-to-band assignment and offer a possibility to evaluate roles of constrained nonplanar tertiary amide groups and rigid chiral skeletons. Nonplanarity shows as single-signed VCD and ROA amide I signals, prevailing the couplets expected to arise from the amide-amide interaction. Amide-amide coupling dominates amide II (mainly C'-N stretching, modified in tertiary amides by the absence of a N-H bond) transitions (strong couplet in VCD, no significant ROA) probably due to the close proximity of amide nitrogen atoms. At lower wavenumbers, ROA spectra exhibit another likely manifestation of amide nonplanarity, showing signals of amide V (δ(oop)(N-C) at ~570 cm(-1)) and amide VI (δ(oop)(C'═O) at ~700 cm(-1) and ~650 cm(-1)) vibrations.

New organic semiconductors with imide/amide-containing molecular systems.

Science.gov (United States)

Liu, Zitong; Zhang, Guanxin; Cai, Zhengxu; Chen, Xin; Luo, Hewei; Li, Yonghai; Wang, Jianguo; Zhang, Deqing

2014-10-29

Due to their high electron affinities, chemical and thermal stabilities, π-conjugated molecules with imide/amide frameworks have received considerable attentions as promising candidates for high-performance optoelectronic materials, particularly for organic semiconductors with high carrier mobilities. The purpose of this Research News is to give an overview of recent advances in development of high performance imide/amide based organic semiconductors for field-effect transistors. It covers naphthalene diimide-, perylene diimide- and amide-based conjugated molecules and polymers for organic semiconductors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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....

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...

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.

The radiation chemistry of organic amides: Pt. 1

International Nuclear Information System (INIS)

Langan, J.R.; Liu, K.J.; Salmon, G.A.; Edwards, P.P.; Ellaboudy, A.; Holton, D.M.

1989-01-01

Pulse radiolysis of four cyclic amides including N-methylpyrrolidinone (NMP), and the non-cyclic amide tetramethylurea (TMU) yielded absorption spectra in the near infrared that are attributed to solvated electrons. Addition of a variety of alkali-metal salts caused no detectable change in the absorption spectrum of e s - and no new absorptions attributable to alkali-metal anions were detected. The effect of dose on the decay of e s - in NMP was studied in detail. The yields of e s - in these amides were estimated by using trans-stilbene as an electron scavenger. Absorption spectra, which are not removed by saturation with N 2 O and CO 2 , are observed in the wavelength range 300-500 nm. (author)

Crystal structure of beryllium amide, Be(NH2)2

International Nuclear Information System (INIS)

Jacobs, H.

1976-01-01

The x-ray investigation of single crystals of beryllium amide led to the following results. The compound crystallizes tetragonally a = 10.170 +- 0.005 A, c = 16.137 +- 0.008 A, and c/a = 1.587. The space group is I4 1 /acd. The lattice contains 32 formula units. The positions of all atoms including hydrogen were determined. The structure of Be(NH 2 ) 2 can be described by a strongly deformed cubic closepacking of anions. The cations occupy tetrahedral interstices so that 4 Be 2+ ions form a regular tetrahedron with the shortest Be-Be distances. This causes units, which can be described by Be 4 (NH 2 ) 6 (NH 2 ) 4 / 2 whereas the outer 4 amide ions serve as bridging anions to give a threedimensional arrangement. The orientation of the amide ions is given and compared with earlier results on similar metal amides. (author)

Poly(ester amide)s based on (L)-lactic acid oligomers and α-amino acids: influence of the α-amino acid side chain in the poly(ester amide)s properties.

Science.gov (United States)

Fonseca, Ana C; Coelho, Jorge F J; Valente, Joana F A; Correia, Tiago R; Correia, Ilídio J; Gil, Maria H; Simões, Pedro N

2013-01-01

Novel biodegradable and low cytotoxic poly(ester amide)s (PEAs) based on α-amino acids and (L)-lactic acid (L-LA) oligomers were successfully synthesized by interfacial polymerization. The chemical structure of the new polymers was confirmed by spectroscopic analyses. Further characterization suggests that the α-amino acid plays a critical role on the final properties of the PEA. L-phenylalanine provides PEAs with higher glass transition temperature, whereas glycine enhances the crystallinity. The hydrolytic degradation in PBS (pH = 7.4) at 37 °C also depends on the α-amino acid, being faster for glycine-based PEAs. The cytotoxic profiles using fibroblast human cells indicate that the PEAs did not elicit an acute cytotoxic effect. The strategy presented in this work opens the possibility of synthesizing biodegradable PEAs with low citotoxicity by an easy and fast method. It is worth to mention also that the properties of these materials can be fine-tuned only by changing the α-amino acid.

Adsorption equilibrium of uranium from seawater on chelating resin containing amide oxime group

International Nuclear Information System (INIS)

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

1987-01-01

Chelating resins containing amide oxime group were synthesized by radiation-induced graft polymerization. The amount of the amide oxime groups was controlled below about 0.1 mol per kg of base polymer. The adsorption equilibrium of uranium from seawater on this resin was investigated. It was suggested that two neighboring amide oxime groups on the grafted chain captured one uranyl ion, and that single amide oxime ligand had little capacity for the adsorption of uranium. The adsorption equilibrium was correlated by a Langmuir-type equation. The content of neighboring amide oxime groups was 0.406 x 10 -3 mol per kg of base polymer, which corresponded to 0.39 % of the total amount of amide oxime groups. The apparent stoichiometric stability constant for the complex of uranyl ion with the neighboring amide oxime groups in seawater was calculated to be 10 -21.7 . (author)

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

AMIDE: A Free Software Tool for Multimodality Medical Image Analysis

Directory of Open Access Journals (Sweden)

Andreas Markus Loening

2003-07-01

Full Text Available Amide's a Medical Image Data Examiner (AMIDE has been developed as a user-friendly, open-source software tool for displaying and analyzing multimodality volumetric medical images. Central to the package's abilities to simultaneously display multiple data sets (e.g., PET, CT, MRI and regions of interest is the on-demand data reslicing implemented within the program. Data sets can be freely shifted, rotated, viewed, and analyzed with the program automatically handling interpolation as needed from the original data. Validation has been performed by comparing the output of AMIDE with that of several existing software packages. AMIDE runs on UNIX, Macintosh OS X, and Microsoft Windows platforms, and it is freely available with source code under the terms of the GNU General Public License.

Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides

Science.gov (United States)

Strieter, Eric R.; Bhayana, Brijesh; Buchwald, Stephen L.

2009-01-01

The copper-catalyzed N-arylation of amides, i.e., the Goldberg reaction, is an efficient method for the construction of products relevant to both industry and academic settings. Herein, we present mechanistic details concerning the catalytic and stoichiometric N-arylation of amides. In the context of the catalytic reaction, our findings reveal the importance of chelating diamine ligands in controlling the concentration of the active catalytic species. The consistency between the catalytic and stoichiometric results suggest that the activation of aryl halides occurs through a 1,2-diamine-ligated copper(I) amidate complex. Kinetic studies on the stoichiometric N-arylation of aryl iodides using 1,2-diamine ligated Cu(I) amidates also provide insights into the mechanism of aryl halide activation. PMID:19072233

Analytical applications of resins containing amide and polyamine functional groups

International Nuclear Information System (INIS)

Orf, G.M.

1977-12-01

A dibutyl amide resin is used for the separation of uranium(VI), thorium(IV), and zirconium(IV) from each other and several other metal ions. Uranium(VI) and thorium(IV) are determined in the presence of large excesses of foreign metal ions and anions. A practical application of the amide resin is studied by determining uranium in low grade uranium ores. The amide resin is also used for the selective concentration of gold(III) from sea water

Analytical applications of resins containing amide and polyamine functional groups

Energy Technology Data Exchange (ETDEWEB)

Orf, Gene Michael [Iowa State Univ., Ames, IA (United States)

1977-12-01

A dibutyl amide resin is used for the separation of uranium(VI), thorium(IV), and zirconium(IV) from each other and several other metal ions. Uranium(VI) and thorium(IV) are determined in the presence of large excesses of foreign metal ions and anions. A practical application of the amide resin is studied by determining uranium in low grade uranium ores. The amide resin is also used for the selective concentration of gold(III) from sea water.

Facile access to amides and hydroxamic acids directly from nitroarenes.

Science.gov (United States)

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

2014-09-07

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

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.

Synthesis and biological activity of pyridazine amides, hydrazones and hydrazides.

Science.gov (United States)

Buysse, Ann M; Yap, Maurice Ch; Hunter, Ricky; Babcock, Jonathan; Huang, Xinpei

2017-04-01

Optimization studies on compounds initially designed to be herbicides led to the discovery of a series of [6-(3-pyridyl)pyridazin-3-yl]amides exhibiting aphicidal properties. Systematic modifications of the amide moiety as well as the pyridine and pyridazine rings were carried out to determine if these changes could improve insecticidal potency. Structure-activity relationship (SAR) studies showed that changes to the pyridine and pyridazine rings generally resulted in a significant loss of insecticidal potency against green peach aphids [Myzus persicae (Sulzer)] and cotton aphids [(Aphis gossypii (Glover)]. However, replacement of the amide moiety with hydrazines, hydrazones, or hydrazides appeared to be tolerated, with small aliphatic substituents being especially potent. A series of aphicidal [6-(3-pyridyl)pyridazin-3-yl]amides were discovered as a result of random screening of compounds that were intially investigated as herbicides. Follow-up studies of the structure-activity relationship of these [6-(3-pyridyl)pyridazin-3-yl]amides showed that biosteric replacement of the amide moiety was widely tolerated suggesting that further opportunities for exploitation may exist for this new area of insecticidal chemistry. Insecticidal efficacy from the original hit, compound 1, to the efficacy of compound 14 produced greater than 10-fold potency improvement against Aphis gossypii and greater than 14-fold potency improvement against Myzus persicae. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Fatty acid amides from freshwater green alga Rhizoclonium hieroglyphicum.

Science.gov (United States)

Dembitsky, V M; Shkrob, I; Rozentsvet, O A

2000-08-01

Freshwater green algae Rhizoclonium hieroglyphicum growing in the Ural Mountains were examined for their fatty acid amides using capillary gas chromatography-mass spectrometry (GC-MS). Eight fatty acid amides were identified by GC-MS. (Z)-9-octadecenamide was found to be the major component (2.26%).

Phenolic Amides Are Potent Inhibitors of De Novo Nucleotide Biosynthesis.

Science.gov (United States)

Pisithkul, Tippapha; Jacobson, Tyler B; O'Brien, Thomas J; Stevenson, David M; Amador-Noguez, Daniel

2015-09-01

An outstanding challenge toward efficient production of biofuels and value-added chemicals from plant biomass is the impact that lignocellulose-derived inhibitors have on microbial fermentations. Elucidating the mechanisms that underlie their toxicity is critical for developing strategies to overcome them. Here, using Escherichia coli as a model system, we investigated the metabolic effects and toxicity mechanisms of feruloyl amide and coumaroyl amide, the predominant phenolic compounds in ammonia-pretreated biomass hydrolysates. Using metabolomics, isotope tracers, and biochemical assays, we showed that these two phenolic amides act as potent and fast-acting inhibitors of purine and pyrimidine biosynthetic pathways. Feruloyl or coumaroyl amide exposure leads to (i) a rapid buildup of 5-phosphoribosyl-1-pyrophosphate (PRPP), a key precursor in nucleotide biosynthesis, (ii) a rapid decrease in the levels of pyrimidine biosynthetic intermediates, and (iii) a long-term generalized decrease in nucleotide and deoxynucleotide levels. Tracer experiments using (13)C-labeled sugars and [(15)N]ammonia demonstrated that carbon and nitrogen fluxes into nucleotides and deoxynucleotides are inhibited by these phenolic amides. We found that these effects are mediated via direct inhibition of glutamine amidotransferases that participate in nucleotide biosynthetic pathways. In particular, feruloyl amide is a competitive inhibitor of glutamine PRPP amidotransferase (PurF), which catalyzes the first committed step in de novo purine biosynthesis. Finally, external nucleoside supplementation prevents phenolic amide-mediated growth inhibition by allowing nucleotide biosynthesis via salvage pathways. The results presented here will help in the development of strategies to overcome toxicity of phenolic compounds and facilitate engineering of more efficient microbial producers of biofuels and chemicals. Copyright © 2015, Pisithkul et al.

Phenolic Amides Are Potent Inhibitors of De Novo Nucleotide Biosynthesis

Science.gov (United States)

Pisithkul, Tippapha; Jacobson, Tyler B.; O'Brien, Thomas J.; Stevenson, David M.

2015-01-01

An outstanding challenge toward efficient production of biofuels and value-added chemicals from plant biomass is the impact that lignocellulose-derived inhibitors have on microbial fermentations. Elucidating the mechanisms that underlie their toxicity is critical for developing strategies to overcome them. Here, using Escherichia coli as a model system, we investigated the metabolic effects and toxicity mechanisms of feruloyl amide and coumaroyl amide, the predominant phenolic compounds in ammonia-pretreated biomass hydrolysates. Using metabolomics, isotope tracers, and biochemical assays, we showed that these two phenolic amides act as potent and fast-acting inhibitors of purine and pyrimidine biosynthetic pathways. Feruloyl or coumaroyl amide exposure leads to (i) a rapid buildup of 5-phosphoribosyl-1-pyrophosphate (PRPP), a key precursor in nucleotide biosynthesis, (ii) a rapid decrease in the levels of pyrimidine biosynthetic intermediates, and (iii) a long-term generalized decrease in nucleotide and deoxynucleotide levels. Tracer experiments using 13C-labeled sugars and [15N]ammonia demonstrated that carbon and nitrogen fluxes into nucleotides and deoxynucleotides are inhibited by these phenolic amides. We found that these effects are mediated via direct inhibition of glutamine amidotransferases that participate in nucleotide biosynthetic pathways. In particular, feruloyl amide is a competitive inhibitor of glutamine PRPP amidotransferase (PurF), which catalyzes the first committed step in de novo purine biosynthesis. Finally, external nucleoside supplementation prevents phenolic amide-mediated growth inhibition by allowing nucleotide biosynthesis via salvage pathways. The results presented here will help in the development of strategies to overcome toxicity of phenolic compounds and facilitate engineering of more efficient microbial producers of biofuels and chemicals. PMID:26070680

‘Umpolung’ Reactivity in Semiaqueous Amide and Peptide Synthesis

Science.gov (United States)

Shen, Bo; Makley, Dawn M.; Johnston, Jeffrey N.

2010-01-01

The amide functional group is one of Nature’s key functional and structural elements, most notably within peptides. Amides are also key intermediates in the preparation of a diverse range of therapeutic small molecules. Its construction using available methods focuses principally upon dehydrative approaches, although oxidative and radical-based methods are representative alternatives. During the carbon-nitrogen bond forming step in most every example, the carbon and nitrogen bear electrophilic and nucleophilic character, respectively. Here we show that activation of amines and nitroalkanes with an electrophilic iodine source in wet THF can lead directly to amide products. Preliminary observations support a mechanistic construct in which reactant polarity is reversed (umpolung) during C-N bond formation relative to traditional approaches. The use of nitroalkanes as acyl anion equivalents provides a conceptually innovative approach to amide and peptide synthesis, and one that might ultimately provide for efficient peptide synthesis that is fully reliant on enantioselective methods. PMID:20577205

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

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

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...

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.

Determination of Structures and Energetics of Small- and Medium-Sized One-Carbon-Bridged Twisted Amides using ab Initio Molecular Orbital Methods: Implications for Amidic Resonance along the C-N Rotational Pathway.

Science.gov (United States)

Szostak, Roman; Aubé, Jeffrey; Szostak, Michal

2015-08-21

Twisted amides containing nitrogen at the bridgehead position are attractive practical prototypes for the investigation of the electronic and structural properties of nonplanar amide linkages. Changes that occur during rotation around the N-C(O) axis in one-carbon-bridged twisted amides have been studied using ab initio molecular orbital methods. Calculations at the MP2/6-311++G(d,p) level performed on a set of one-carbon-bridged lactams, including 20 distinct scaffolds ranging from [2.2.1] to [6.3.1] ring systems, with the C═O bond on the shortest bridge indicate significant variations in structures, resonance energies, proton affinities, core ionization energies, frontier molecular orbitals, atomic charges, and infrared frequencies that reflect structural changes corresponding to the extent of resonance stabilization during rotation along the N-C(O) axis. The results are discussed in the context of resonance theory and activation of amides toward N-protonation (N-activation) by distortion. This study demonstrates that one-carbon-bridged lactams-a class of readily available, hydrolytically robust twisted amides-are ideally suited to span the whole spectrum of the amide bond distortion energy surface. Notably, this study provides a blueprint for the rational design and application of nonplanar amides in organic synthesis. The presented findings strongly support the classical amide bond resonance model in predicting the properties of nonplanar amides.

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

Copper(II)-catalyzed amidations of alkynyl bromides as a general synthesis of ynamides and Z-enamides. An intramolecular amidation for the synthesis of macrocyclic ynamides.

Science.gov (United States)

Zhang, Xuejun; Zhang, Yanshi; Huang, Jian; Hsung, Richard P; Kurtz, Kimberly C M; Oppenheimer, Jossian; Petersen, Matthew E; Sagamanova, Irina K; Shen, Lichun; Tracey, Michael R

2006-05-26

A general and efficient method for the coupling of a wide range of amides with alkynyl bromides is described here. This novel amidation reaction involves a catalytic protocol using copper(II) sulfate-pentahydrate and 1,10-phenanthroline to direct the sp-C-N bond formation, leading to a structurally diverse array of ynamides including macrocyclic ynamides via an intramolecular amidation. Given the surging interest in ynamide chemistry, this atom economical synthesis of ynamides should invoke further attention from the synthetic organic community.

1H NMR spectra. Part 30(+): 1H chemical shifts in amides and the magnetic anisotropy, electric field and steric effects of the amide group.

Science.gov (United States)

Abraham, Raymond J; Griffiths, Lee; Perez, Manuel

2013-03-01

The (1)H spectra of 37 amides in CDCl(3) solvent were analysed and the chemical shifts obtained. The molecular geometries and conformational analysis of these amides were considered in detail. The NMR spectral assignments are of interest, e.g. the assignments of the formamide NH(2) protons reverse in going from CDCl(3) to more polar solvents. The substituent chemical shifts of the amide group in both aliphatic and aromatic amides were analysed using an approach based on neural network data for near (≤3 bonds removed) protons and the electric field, magnetic anisotropy, steric and for aromatic systems π effects of the amide group for more distant protons. The electric field is calculated from the partial atomic charges on the N.C═O atoms of the amide group. The magnetic anisotropy of the carbonyl group was reproduced with the asymmetric magnetic anisotropy acting at the midpoint of the carbonyl bond. The values of the anisotropies Δχ(parl) and Δχ(perp) were for the aliphatic amides 10.53 and -23.67 (×10(-6) Å(3)/molecule) and for the aromatic amides 2.12 and -10.43 (×10(-6) Å(3)/molecule). The nitrogen anisotropy was 7.62 (×10(-6) Å(3)/molecule). These values are compared with previous literature values. The (1)H chemical shifts were calculated from the semi-empirical approach and also by gauge-independent atomic orbital calculations with the density functional theory method and B3LYP/6-31G(++) (d,p) basis set. The semi-empirical approach gave good agreement with root mean square error of 0.081 ppm for the data set of 280 entries. The gauge-independent atomic orbital approach was generally acceptable, but significant errors (ca. 1 ppm) were found for the NH and CHO protons and also for some other protons. Copyright © 2013 John Wiley & Sons, Ltd.

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

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

Graphical abstract: Molecular architectures of next generation of high-performance advanced heat stable thermoplastic polymer compositions of fluoro-poly(ether amide) (6F-PA) and fluoro-poly(ether amide-imide) (6F-PEAI) having di-ether diamines moieties were designed based on fluoro-polyimide (6F-PI) chemistry, and polymers were synthesized using two novel state-of-the-art 2-(3,4'-carboxy anhydrophenyl-2(4-carboxyphenyl) hexafluoropropane (6FTMA) and 2,2'-bis(4-carboxyphenyl) hexafluropropane (6F-DAc) monomers. Their copolymers: fluoro-copoly(ether amide-(ether imide))s (6F-co(PEA-PEI)), fluoro-copoly(ether amide-(ether amide-imide))s (6F-co(PEA-PEAI)) and fluoro-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) for the advanced aerospace, defense and industrial engineering applications. -- Abstract: A new generation of high-performance polymers for the advanced industrial, aerospace and defense engineering applications are being investigated in the academic and industrial research institutions throughout the world. Fluoro-polyimides (6F-PI) are one such sub-class of high-performance polyimide polymers. In the last 25 years a number of fluoro-polyimides have been reported but only a handful of them have been commercialized. This paper describes the 6F-polyimide chemistry-based designed molecular architectures and synthesis of two series of next generation of heat stable thermoplastic polymer compositions having di-ether diamines moieties, such as fluoro-poly(ether amide) (6F-PA) and fluoro-poly(ether amide-imide) (6F-PEAI) using the novel state-of-the-art 2-(3,4'-carboxy anhydrophenyl-2(4-carboxyphenyl) hexafluoropropane (6F-TMA) and 2,2'-bis(4-carboxyphenyl) hexafluoropropane (6F-DAc) monomers. Their co-polymers: fluoro-copoly(ether amide-(ether imide))s (6F-co(PEA-PEI)), fluoro-copoly(ether amide-(ether amide-imide))s (6F-co(PEA-PEAI)) and fluoro

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

Biosynthesis of amidated joining peptide from pro-adrenocorticotropin-endorphin

Energy Technology Data Exchange (ETDEWEB)

Cullen, E.I.; Mains, R.E. (Johns Hopkins Univ. School of Medicine, Baltimore, MD (USA))

1987-09-01

Joining peptide is the major alpha-amidated product of pro-ACTH/endorphin (PAE) in AtT-20 corticotropic tumor cells. To study intracellular joining peptide synthesis, affinity purified antibodies directed against gamma-MSH, joining peptide, and ACTH were used to immunoprecipitate extracts from biosynthetically labeled AtT-20 cells. Immunoprecipitates were analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and by tryptic peptide mapping on HPLC. In steady labeling experiments, radioactivity in amidated joining peptide (JP) increased roughly linearly with time, in the manner of a final product, whereas radioactivity associated with PAE (1-94)NH2 reached a constant value after 2-4 h, indicating that PAE(1-94)NH2 is an intermediate in the biosynthesis of JP. Radioactivity appeared in ACTH(1-39) well before JP, consistent with a cleavage order in which ACTH is cleaved from PAE(1-95) before JP sequences are cleaved from PAE(1-74). This conclusion was supported by tryptic peptide analyses of immunoprecipitates, which indicated that less than 5% of JP-related material is cleaved from PAE(1-74) before being cleaved from ACTH-related sequences. After a pulse label, radioactivity in PAE(1-94)NH2 reached a peak value after 1 h of chase and declined with a half-life of less than 1 h. Amidated JP increased to a constant level after 2 h of chase. Enough radiolabeled PAE(1-94)NH2 was detected to account for about half of the radioactivity found in amidated JP, indicating that about half of JP-related material is first cleaved from PAE(1-95) before being amidated. This result was corroborated using HPLC purification to determine both amidated and glycine-extended forms of JP.

Biosynthesis of amidated joining peptide from pro-adrenocorticotropin-endorphin

International Nuclear Information System (INIS)

Cullen, E.I.; Mains, R.E.

1987-01-01

Joining peptide is the major alpha-amidated product of pro-ACTH/endorphin (PAE) in AtT-20 corticotropic tumor cells. To study intracellular joining peptide synthesis, affinity purified antibodies directed against gamma-MSH, joining peptide, and ACTH were used to immunoprecipitate extracts from biosynthetically labeled AtT-20 cells. Immunoprecipitates were analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and by tryptic peptide mapping on HPLC. In steady labeling experiments, radioactivity in amidated joining peptide (JP) increased roughly linearly with time, in the manner of a final product, whereas radioactivity associated with PAE (1-94)NH2 reached a constant value after 2-4 h, indicating that PAE(1-94)NH2 is an intermediate in the biosynthesis of JP. Radioactivity appeared in ACTH(1-39) well before JP, consistent with a cleavage order in which ACTH is cleaved from PAE(1-95) before JP sequences are cleaved from PAE(1-74). This conclusion was supported by tryptic peptide analyses of immunoprecipitates, which indicated that less than 5% of JP-related material is cleaved from PAE(1-74) before being cleaved from ACTH-related sequences. After a pulse label, radioactivity in PAE(1-94)NH2 reached a peak value after 1 h of chase and declined with a half-life of less than 1 h. Amidated JP increased to a constant level after 2 h of chase. Enough radiolabeled PAE(1-94)NH2 was detected to account for about half of the radioactivity found in amidated JP, indicating that about half of JP-related material is first cleaved from PAE(1-95) before being amidated. This result was corroborated using HPLC purification to determine both amidated and glycine-extended forms of JP

Effect of amides on lithium tetraborate solubility

Energy Technology Data Exchange (ETDEWEB)

Tsekhanskij, R S; Skvortsov, V C; Molodkin, A K; Sadetdi-pov, Sh V [Chuvashskij Gosudarstvennyj Pedagogicheskij Inst., Cheboksary (USSR); Universitet Druzhby Narodov, Moscow (USSR))

1983-03-01

Using the methods of solubility, densi- and refractometry at 25 deg C, it has been established that the systems lithium tetraborate-formamide (acetamide, dimethyl-formamide)-water are of a simple eutonic type. Amides decrease the salt solubility. Lyotropic effect, as calculated for molar concentrations (-Lsub(M)) relative to the absolute value, increases from formamide to dimethyl-formamide. The sequence is determined by the fact that, when there is one or two hydrophilic methyl groups in amide molecules which are in contact with tetraborate, they decrease the hydration energy of lithium cations.

Effect of amides on sodium tetraborate solubility

International Nuclear Information System (INIS)

Tsekhanskij, R.S.; Skvortsov, V.G.; Molodkin, A.K.; Sadetdinov, Sh.V.

1986-01-01

Methods of solubility and refractometry at 25 deg C were applied to investigate sodium tetraborate - formamide (dimethylformamide) - water systems. It is stated that they are of simple eutonic type as well as the earlier described sodium tetraborate-acetamide-water system. Amides reduce solubility of the salt. The effect of contact interaction between dissolved substances on salt cation hydration and thus on the value of liotropic amide effect is confirmed. This value is found to be also depend on the number of molecules of coordination water in the initial crystalline hydrate

Effect of amides on lithium tetraborate solubility

International Nuclear Information System (INIS)

Tsekhanskij, R.S.; Skvortsov, V.C.; Molodkin, A.K.; Sadetdi- pov, Sh.V.

1983-01-01

Using the methods of solubility, densi- and refractometry at 25 deg C, it has been established that the systemS lithium tetraborate-formamide (acetamide, dimethyl-formamide)-water are of a simple eutonic type. Amides decrease the salt solubility. Lyotropic effect, as calculated for molar concentrations (-Lsub(M)) relative to the absolute value, increases from formamide to dimethylformamide. The sequence is determined by the fact that, when there is one or two hydrophilic methyl groups in amide molecules which are in contact with tetraborate, they decrease the hydration energy of lithium cations

Effect of amides on sodium tetraborate solubility

Energy Technology Data Exchange (ETDEWEB)

Tsekhanskij, R S; Skvortsov, V G; Molodkin, A K; Sadetdinov, Sh V

1986-11-01

Methods of solubility and refractometry at 25 deg C were applied to investigate sodium tetraborate - formamide (dimethylformamide) - water systems. It is stated that they are of simple eutonic type as well as the earlier described sodium tetraborate-acetamide-water system. Amides reduce solubility of the salt. The effect of contact interaction between dissolved substances on salt cation hydration and thus on the value of liotropic amide effect is confirmed. This value is found to be also depend on the number of molecules of coordination water in the initial crystalline hydrate.

TROSY of side-chain amides in large proteins

Science.gov (United States)

Liu, Aizhuo; Yao, Lishan; Li, Yue; Yan, Honggao

2012-01-01

By using the mixed solvent of 50% H2O/50% D2O and employing deuterium decoupling, TROSY experiments exclusively detect NMR signals from semideuterated isotopomers of carboxamide groups with high sensitivities for proteins with molecular weights up to 80 kDa. This isotopomer-selective strategy extends TROSY experiments from exclusively detecting backbone to both backbone and side-chain amides, particularly in large proteins. Because of differences in both TROSY effect and dynamics between 15N–HE{DZ} and 15N–HZ{DE} isotopomers of the same carboxamide, the 15N transverse magnetization of the latter relaxes significantly faster than that of the former, which provides a direct and reliable stereospecific distinction between the two configurations. The TROSY effects on the 15N–HE{DZ} isotopomers of side-chain amides are as significant as on backbone amides. PMID:17347000

Insecticidal, repellent and fungicidal properties of novel trifluoromethylphenyl amides.

Science.gov (United States)

Tsikolia, Maia; Bernier, Ulrich R; Coy, Monique R; Chalaire, Katelyn C; Becnel, James J; Agramonte, Natasha M; Tabanca, Nurhayat; Wedge, David E; Clark, Gary G; Linthicum, Kenneth J; Swale, Daniel R; Bloomquist, Jeffrey R

2013-09-01

Twenty trifluoromethylphenyl amides were synthesized and evaluated as fungicides and as mosquito toxicants and repellents. Against Aedes aegypti larvae, N-(2,6-dichloro-4-(trifluoromethyl)phenyl)-3,5-dinitrobenzamide (1e) was the most toxic compound (24 h LC50 1940 nM), while against adults N-(2,6-dichloro-4-(trifluoromethyl)phenyl)-2,2,2-trifluoroacetamide (1c) was most active (24 h LD50 19.182 nM, 0.5 μL/insect). However, the 24 h LC50 and LD50 values of fipronil against Ae. aegypti larvae and adults were significantly lower: 13.55 nM and 0.787 × 10(-4) nM, respectively. Compound 1c was also active against Drosophila melanogaster adults with 24 h LC50 values of 5.6 and 4.9 μg/cm(2) for the Oregon-R and 1675 strains, respectively. Fipronil had LC50 values of 0.004 and 0.017 μg/cm(2) against the two strains of D. melanogaster, respectively. In repellency bioassays against female Ae. aegypti, 2,2,2-trifluoro-N-(2-(trifluoromethyl)phenyl)acetamide (4c) had the highest repellent potency with a minimum effective dosage (MED) of 0.039 μmol/cm(2) compared to DEET (MED of 0.091 μmol/cm(2)). Compound N-(2-(trifluoromethyl)phenyl)hexanamide (4a) had an MED of 0.091 μmol/cm(2) which was comparable to DEET. Compound 4c was the most potent fungicide against Phomopsis obscurans. Several trends were discerned between the structural configuration of these molecules and the effect of structural changes on toxicity and repellency. Para- or meta- trifluoromethylphenyl amides with an aromatic ring attached to the carbonyl carbon showed higher toxicity against Ae. aegypti larvae, than ortho- trifluoromethylphenyl amides. Ortho- trifluoromethylphenyl amides with trifluoromethyl or alkyl group attached to the carbonyl carbon produced higher repellent activity against female Ae. aegypti and Anopheles albimanus than meta- or para- trifluoromethylphenyl amides. The presence of 2,6-dichloro- substitution on the phenyl ring of the amide had an influence on larvicidal and repellent

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.

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 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

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)

Amide Synthesis from Alcohols and Amines by the Extrusion of Dihydrogen

DEFF Research Database (Denmark)

Nordstrøm, Lars Ulrik Rubæk; Vogt, Henning; Madsen, R.

2008-01-01

An environmentally friendly method for synthesis of amides is presented where a simple ruthenium catalyst mediates the direct coupling between an alcohol and an amine with the liberation of two molecules of dihydrogen. The active catalyst is generated in situ from an easily available ruthenium...... complex, an N-heterocyclic carbene and a phosphine. The reaction allows primary alcohols to be coupled with primary alkyamines to afford the corresponding secondary amides in good yields. The amide formation presumably proceeds through a catalytic cycle where the intermediate aldehyde and hemiaminal...

Cytotoxic cassaine diterpenoid-diterpenoid amide dimers and diterpenoid amides from the leaves of Erythrophleum fordii.

Science.gov (United States)

Du, Dan; Qu, Jing; Wang, Jia-Ming; Yu, Shi-Shan; Chen, Xiao-Guang; Xu, Song; Ma, Shuang-Gang; Li, Yong; Ding, Guang-Zhi; Fang, Lei

2010-10-01

Detailed phytochemical investigation from the leaves of Erythrophleum fordii resulted in the isolation of 13 compounds, including three cassaine diterpenoid-diterpenoid amide dimers (1, 3 and 5), and seven cassaine diterpenoid amides (6 and 8-13), together with three previously reported ones, erythrophlesins D (2), C (4) and 3beta-hydroxynorerythrosuamide (7). Compounds 1, 3 and 5 are further additions to the small group of cassaine diterpenoid dimers represented by erythrophlesins A-D. Their structures were determined by analysis of extensive one- and two-dimensional NMR experiments and ESIMS methods. Cytotoxic activities of the isolated compounds were tested against HCT-8, Bel-7402, BGC-823, A549 and A2780 human cancer cell lines in the MTT test. Results showed that compounds 1 and 3-5 exhibited significantly selective cytotoxic activities (IC(50)<10 microM) against these cells, respectively. Copyright © 2010 Elsevier Ltd. All rights reserved.

Pain and beyond: fatty acid amides and fatty acid amide hydrolase inhibitors in cardiovascular and metabolic diseases.

Science.gov (United States)

Pillarisetti, Sivaram; Alexander, Christopher W; Khanna, Ish

2009-12-01

Fatty acid amide hydrolase (FAAH) is responsible for the hydrolysis of several important endogenous fatty acid amides (FAAs), including anandamide, oleoylethanolamide and palmitoylethanolamide. Because specific FAAs interact with cannabinoid and vanilloid receptors, they are often referred to as 'endocannabinoids' or 'endovanilloids'. Initial interest in this area, therefore, has focused on developing FAAH inhibitors to augment the actions of FAAs and reduce pain. However, recent literature has shown that these FAAs - through interactions with unique receptors (extracellular and intracellular) - can induce a diverse array of effects that include appetite suppression, modulation of lipid and glucose metabolism, vasodilation, cardiac function and inflammation. This review gives an overview of FAAs and diverse FAAH inhibitors and their potential therapeutic utility in pain and non-pain indications.

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.

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.

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...

Carryover potassium amide in cracker at HWP, Hazira - a case study (Paper No. 1.5)

International Nuclear Information System (INIS)

Anon.

1992-01-01

The liquid ammonia fed to cracker is made available from potassium amide catalyst recovery unit, where catalyst potassium amide is separated by distillation. Extreme care is taken to ensure that ammonia is totally free from potassium. Also the gas used for catalyst heating during start up, should be free of any possible amide contamination and should be pure and dry as moisture is a poison for the catalyst. In order to prevent the recurrence of amide carryover to cracker tubes from start up gas line, certain modifications were carried out besides removal of amide from pipings. Details are discussed. (author)

Uranyl Photocleavage of Phosphopeptides Yields Truncated C-Terminally Amidated Peptide Products

DEFF Research Database (Denmark)

Elnegaard, Rasmus L B; Møllegaard, Niels Erik; Zhang, Qiang

2017-01-01

photocleavage reaction of a tetraphosphorylated β-casein model peptide. We show that the primary photocleavage products of the uranyl-catalysed reaction are C-terminally amidated. This could be of great interest to the pharmaceutical industry, as efficient peptide amidation reactions are one of the top...

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.

Use of triphenyl phosphate as risk mitigant for metal amide hydrogen storage materials

Science.gov (United States)

Cortes-Concepcion, Jose A.; Anton, Donald L.

2016-04-26

A process in a resulting product of the process in which a hydrogen storage metal amide is modified by a ball milling process using an additive of TPP. The resulting product provides for a hydrogen storage metal amide having a coating that renders the hydrogen storage metal amide resistant to air, ambient moisture, and liquid water while improving useful hydrogen storage and release kinetics.

Amide-based inhibitors of p38alpha MAP kinase. Part 2: design, synthesis and SAR of potent N-pyrimidyl amides.

Science.gov (United States)

Tester, Richland; Tan, Xuefei; Luedtke, Gregory R; Nashashibi, Imad; Schinzel, Kurt; Liang, Weiling; Jung, Joon; Dugar, Sundeep; Liclican, Albert; Tabora, Jocelyn; Levy, Daniel E; Do, Steven

2010-04-15

Optimization of a tri-substituted N-pyridyl amide led to the discovery of a new class of potent N-pyrimidyl amide based p38alpha MAP kinase inhibitors. Initial SAR studies led to the identification of 5-dihydrofuran as an optimal hydrophobic group. Additional side chain modifications resulted in the introduction of hydrogen bond interactions. Through extensive SAR studies, analogs bearing free amino groups and alternatives to the parent (S)-alpha-methyl benzyl moiety were identified. These compounds exhibited improved cellular activities and maintained balance between p38alpha and CYP3A4 inhibition. Copyright 2010 Elsevier Ltd. All rights reserved.

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.

FMRF-amide-like immunoreactivity in brain and pituitary of the hagfish Eptatretus burgeri (Cyclostomata)

DEFF Research Database (Denmark)

Jirikowski, G; Erhart, G; Grimmelikhuijzen, C J

1984-01-01

Paraffin sections of brain and pituitary of the hagfish Eptatretus burgeri were immunostained with an antiserum to FMRF-amide. Immunoreactivity was visible in a large number of neurons in the posterior part of the ventromedial hypothalamus and in long neuronal processes extending cranially from...... the hypothalamus to the olfactory system and caudally to the medulla oblongata. FMRF-amide-like immunoreactivity was also found in cells of the adenohypophysis. These observations suggest that the hagfish possesses a brain FMRF-amide-like transmitter system and pituitary cells containing FMRF-amide-like material...

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

Catalytic asymmetric epoxidation of alpha,beta-unsaturated amides: efficient synthesis of beta-aryl alpha-hydroxy amides using a one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process.

Science.gov (United States)

Nemoto, Tetsuhiro; Kakei, Hiroyuki; Gnanadesikan, Vijay; Tosaki, Shin-Ya; Ohshima, Takashi; Shibasaki, Masakatsu

2002-12-11

The catalytic asymmetric epoxidation of alpha,beta-unsaturated amides using Sm-BINOL-Ph3As=O complex was succeeded. Using 5-10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding alpha,beta-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of beta-aryl alpha-hydroxy amides, including beta-aryllactyl-leucine methyl esters. Interestingly, it was found that beneficial modifications on the Pd catalyst were achieved by the constituents of the first epoxidation, producing a more suitable catalyst for the Pd-catalyzed epoxide opening reaction in terms of chemoselectivity.

Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

Science.gov (United States)

Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.

2016-01-01

An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. PMID:26110812

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

Science.gov (United States)

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 of new fatty acids amides from aminolysis of fatty acid methyl esters (FAMEs)

International Nuclear Information System (INIS)

Lopes, Carolina R.; Montes D'Oca, Caroline da Ros; Duarte, Rodrigo da C.; Kurz, Marcia H.S.; Primel, Ednei G.; Clementin, Rosilene M.; Villarreyes, Joaquin Ariel M.; Montes D'Oca, Marcelo G.

2010-01-01

Recent biochemical and pharmacological studies have led to the characterization of different fatty acid amides as a new family of biologically active lipids. Here, we describe the synthesis of new amides from C16:0, 18:0, 18:1 and 18:1, OH fatty acids (FFA) families with cyclic and acyclic amines and demonstrate for the first time that these compounds produce cytotoxic effects. Application of this method to the synthesis of fatty acid amides was performed using the esters aminolysis as a key step and various carboxylic amides were prepared in good yield from fatty acid methyl esters (FAMEs). (author)

Detection of amide I signals of interfacial proteins in situ using SFG.

Science.gov (United States)

Wang, Jie; Even, Mark A; Chen, Xiaoyun; Schmaier, Alvin H; Waite, J Herbert; Chen, Zhan

2003-08-20

In this Communication, we demonstrate the novel observation that it is feasible to collect amide signals from polymer/protein solution interfaces in situ using sum frequency generation (SFG) vibrational spectroscopy. Such SFG amide signals allow for acquisition of more detailed molecular level information of entire interfacial protein structures. Proteins investigated include bovine serum albumin, mussel protein mefp-2, factor XIIa, and ubiquitin. Our studies indicate that different proteins generate different SFG amide signals at the polystyrene/protein solution interface, showing that they have different interfacial coverage, secondary structure, or orientation.

Accurate determination of interfacial protein secondary structure by combining interfacial-sensitive amide I and amide III spectral signals.

Science.gov (United States)

Ye, Shuji; Li, Hongchun; Yang, Weilai; Luo, Yi

2014-01-29

Accurate determination of protein structures at the interface is essential to understand the nature of interfacial protein interactions, but it can only be done with a few, very limited experimental methods. Here, we demonstrate for the first time that sum frequency generation vibrational spectroscopy can unambiguously differentiate the interfacial protein secondary structures by combining surface-sensitive amide I and amide III spectral signals. This combination offers a powerful tool to directly distinguish random-coil (disordered) and α-helical structures in proteins. From a systematic study on the interactions between several antimicrobial peptides (including LKα14, mastoparan X, cecropin P1, melittin, and pardaxin) and lipid bilayers, it is found that the spectral profiles of the random-coil and α-helical structures are well separated in the amide III spectra, appearing below and above 1260 cm(-1), respectively. For the peptides with a straight backbone chain, the strength ratio for the peaks of the random-coil and α-helical structures shows a distinct linear relationship with the fraction of the disordered structure deduced from independent NMR experiments reported in the literature. It is revealed that increasing the fraction of negatively charged lipids can induce a conformational change of pardaxin from random-coil to α-helical structures. This experimental protocol can be employed for determining the interfacial protein secondary structures and dynamics in situ and in real time without extraneous labels.

Synthesis, anticancer and antibacterial activity of salinomycin N-benzyl amides.

Science.gov (United States)

Antoszczak, Michał; Maj, Ewa; Napiórkowska, Agnieszka; Stefańska, Joanna; Augustynowicz-Kopeć, Ewa; Wietrzyk, Joanna; Janczak, Jan; Brzezinski, Bogumil; Huczyński, Adam

2014-11-25

A series of 12 novel monosubstituted N-benzyl amides of salinomycin (SAL) was synthesized for the first time and characterized by NMR and FT-IR spectroscopic methods. Molecular structures of three salinomycin derivatives in the solid state were determined using single crystal X-ray method. All compounds obtained were screened for their antiproliferative activity against various human cancer cell lines as well as against the most problematic bacteria strains such as methicillin-resistant Staphylococcus aureus (MRSA) and Staphylococcus epidermidis (MRSE), and Mycobacterium tuberculosis. Novel salinomycin derivatives exhibited potent anticancer activity against drug-resistant cell lines. Additionally, two N-benzyl amides of salinomycin revealed interesting antibacterial activity. The most active were N-benzyl amides of SAL substituted at -ortho position and the least anticancer active derivatives were those substituted at the -para position.

Amidation of single-walled carbon nanotubes by a hydrothermal process for the electrooxidation of nitric oxide

International Nuclear Information System (INIS)

Kan Kan; Xia Tingliang; Li Li; Bi Hongmei; Fu Honggang; Shi Keying

2009-01-01

Single-walled carbon nanotubes (SWCNTs) have been amidated by hydrothermal treatment with different aliphatic amines. The amido groups modified on the surface of the SWCNTs were characterized by Fourier transform infrared spectroscopy. The electrooxidation of nitric oxide (NO) at the modified electrodes of amidated SWCNTs was investigated. The modified electrodes of amidated SWCNTs exhibited different electrocatalytic activity for NO when different aliphatic amines were being used. The electrode amidated by ammonia has the highest activity, which is 1.8 times value of the SWCNT modified electrode. The electrocatalytic activity of the amidated SWCNT modified electrodes depends on the length of the alkyl groups. The results demonstrate that hydrothermal treatment is an efficient way to modify SWCNTs with amines, and the reaction rate of NO electrooxidation can be changed by the amidation of SWCNTs.

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

A catalyst-free addition reaction of zinc amide enolates to N-sulfonyle imines

Energy Technology Data Exchange (ETDEWEB)

Joo, Seong Ryu; Im, Pyeong Won; Kim, Jong Sung; Kim, Seung Hoi [Dept. of Chemistry, Dankook University, Cheonan (Korea, Republic of); Park Soo Youl [Interface Chemistry and Engineering Research Team, Korea Research Institute of Chemical Technology, Daejon (Korea, Republic of)

2016-12-15

Despite the remarkable expansion of the imino-Reformatsky reaction, one interesting aspect is that, to the best of our knowledge, zinc enolates derived solely from α-halo esters have been mainly used in the recent progress. In contrast, a few limited examples have been reported concerning the application of zinc enolates derived from α-halo amide to the imino-Reformatsky reaction. In recent years, Rodriguez-Solla and co-workers reported the addition reaction of samarium enolates derived from both α-halo esters and amides to imines, resulting in the synthe- sis of β-amino esters or amides. In conclusion, we established a potential synthetic proto- col for the preparation of β-amino amides. This work was accomplished by the direct addition of zinc amide enolates to N-sulfonyl imines in the absence of any metal-catalyst under mild conditions. Due to the operational simplicity of the proposed method, it can be further utilized in synthetic organic chemistry. Further studies to elucidate the scope of this approach are currently underway in our laboratory.

A catalyst-free addition reaction of zinc amide enolates to N-sulfonyle imines

International Nuclear Information System (INIS)

Joo, Seong Ryu; Im, Pyeong Won; Kim, Jong Sung; Kim, Seung Hoi; Park Soo Youl

2016-01-01

Despite the remarkable expansion of the imino-Reformatsky reaction, one interesting aspect is that, to the best of our knowledge, zinc enolates derived solely from α-halo esters have been mainly used in the recent progress. In contrast, a few limited examples have been reported concerning the application of zinc enolates derived from α-halo amide to the imino-Reformatsky reaction. In recent years, Rodriguez-Solla and co-workers reported the addition reaction of samarium enolates derived from both α-halo esters and amides to imines, resulting in the synthe- sis of β-amino esters or amides. In conclusion, we established a potential synthetic proto- col for the preparation of β-amino amides. This work was accomplished by the direct addition of zinc amide enolates to N-sulfonyl imines in the absence of any metal-catalyst under mild conditions. Due to the operational simplicity of the proposed method, it can be further utilized in synthetic organic chemistry. Further studies to elucidate the scope of this approach are currently underway in our laboratory

Actinides complexes in solvent extraction. The amide type of extractants

International Nuclear Information System (INIS)

Musikas, C.; Condamines, N.; Charbonnel, M.C.; Hubert, H.

1989-01-01

The N,N-dialkylamides and the N,N'-tetraalkyl. 2-alkyl 1,3-diamide propane are two promising classes of extractants which could replace advantageously the organophosphorus molecules for the separations of the actinide. The main advantages of the amides lie in their complete incinerability and the small interference of their radiolytic and hydrolytic degradation products for the processes. The actinide extraction chemistry with various amides is reviewed in this paper

Pressure effect on the amide I frequency of the solvated α-helical structure in water

International Nuclear Information System (INIS)

Takekiyo, T; Yoshimura, Y; Shimizu, A; Koizumi, T; Kato, M; Taniguchi, Y

2007-01-01

As a model system of the pressure dependence of the amide I mode of the solvated α-helical structure in a helical peptide, we have calculated the frequency shifts of the amide I modes as a function of the distance between trans-N-methylacetamide (t-NMA) dimer and a water molecule (d C=O···H-O ) by the density-functional theory (DFT) method at the B3LYP/6-31G++(d,p) level. Two amide I frequencies at 1652 and 1700 cm -1 were observed under this calculation. The former is ascribed to the amide I mode forming the intermolecular hydrogen bond (H-bond) between t-NMA and H 2 O in addition to the intermolecular H-bond in the t-NMA dimer. The latter is due to the amide I mode forming only the intermolecular H-bond in the t-NMA dimer. We have found that the amide I frequency at 1652 cm -1 shifts to a lower frequency with decreasing d C=O···H-O ) (i.e., increasing pressure), whereas that at 1700 cm -1 shifts to a higher frequency. The amide I frequency shift of 1652 cm -1 is larger than that of 1700 cm -1 by the intermolecular H-bond. Thus, our results clearly indicate that the pressure-induced amide I frequency shift of the solvated α-helical structure correlates with the change in d C=O···H-O )

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.

40 CFR 721.6183 - Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow alkyl amines...

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amides, from ammonium hydroxide... Substances § 721.6183 Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow... subject to reporting. (1) The chemical substance identified as amides, from ammonium hydroxide - maleic...

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.

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.

Communication: Quantitative multi-site frequency maps for amide I vibrational spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Reppert, Mike [Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States); Tokmakoff, Andrei, E-mail: tokmakoff@uchicago.edu [Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States)

2015-08-14

An accurate method for predicting the amide I vibrational spectrum of a given protein structure has been sought for many years. Significant progress has been made recently by sampling structures from molecular dynamics simulations and mapping local electrostatic variables onto the frequencies of individual amide bonds. Agreement with experiment, however, has remained largely qualitative. Previously, we used dipeptide fragments and isotope-labeled constructs of the protein G mimic NuG2b as experimental standards for developing and testing amide I frequency maps. Here, we combine these datasets to test different frequency-map models and develop a novel method to produce an optimized four-site potential (4P) map based on the CHARMM27 force field. Together with a charge correction for glycine residues, the optimized map accurately describes both experimental datasets, with average frequency errors of 2–3 cm{sup −1}. This 4P map is shown to be convertible to a three-site field map which provides equivalent performance, highlighting the viability of both field- and potential-based maps for amide I spectral modeling. The use of multiple sampling points for local electrostatics is found to be essential for accurate map performance.

76 FR 69636 - Amides, C5

Science.gov (United States)

2011-11-09

... in guinea pigs showed that amides, C 5 - C 9 , N-[3-(dimethylamino) propyl] was not a skin sensitizer.... Potentially affected entities may include, but are not limited to: Crop production (NAICS code 111). Animal production (NAICS code 112). Food manufacturing (NAICS code 311). Pesticide manufacturing (NAICS code 32532...

Optimization of Aryl Amides that Extend Survival in Prion-Infected Mice.

Science.gov (United States)

Giles, Kurt; Berry, David B; Condello, Carlo; Dugger, Brittany N; Li, Zhe; Oehler, Abby; Bhardwaj, Sumita; Elepano, Manuel; Guan, Shenheng; Silber, B Michael; Olson, Steven H; Prusiner, Stanley B

2016-09-01

Developing therapeutics for neurodegenerative diseases (NDs) prevalent in the aging population remains a daunting challenge. With the growing understanding that many NDs progress by conformational self-templating of specific proteins, the prototypical prion diseases offer a platform for ND drug discovery. We evaluated high-throughput screening hits with the aryl amide scaffold and explored the structure-activity relationships around three series differing in their N-aryl core: benzoxazole, benzothiazole, and cyano. Potent anti-prion compounds were advanced to pharmacokinetic studies, and the resulting brain-penetrant leads from each series, together with a related N-aryl piperazine lead, were escalated to long-term dosing and efficacy studies. Compounds from each of the four series doubled the survival of mice infected with a mouse-passaged prion strain. Treatment with aryl amides altered prion strain properties, as evidenced by the distinct patterns of neuropathological deposition of prion protein and associated astrocytic gliosis in the brain; however, none of the aryl amide compounds resulted in drug-resistant prion strains, in contrast to previous studies on compounds with the 2-aminothiazole (2-AMT) scaffold. As seen with 2-AMTs and other effective anti-prion compounds reported to date, the novel aryl amides reported here were ineffective in prolonging the survival of transgenic mice infected with human prions. Most encouraging is our discovery that aryl amides show that the development of drug resistance is not an inevitable consequence of efficacious anti-prion therapeutics. Copyright © 2016 by The American Society for Pharmacology and Experimental Therapeutics.

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

Binary and ternary cocrystals of sulfa drug acetazolamide with pyridine carboxamides and cyclic amides

OpenAIRE

Bolla, Geetha; Nangia, Ashwini

2016-01-01

A novel design strategy for cocrystals of a sulfonamide drug with pyridine carboxamides and cyclic amides is developed based on synthon identification as well as size and shape match of coformers. Binary adducts of acetazolamide (ACZ) with lactams (valerolactam and caprolactam, VLM, CPR), cyclic amides (2-pyridone, labeled as 2HP and its derivatives MeHP, OMeHP) and pyridine amides (nicotinamide and picolinamide, NAM, PAM) were obtained by manual grinding, and their single crystals by solutio...

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.

Equilibrium amide hydrogen exchange and protein folding kinetics

International Nuclear Information System (INIS)

Bai Yawen

1999-01-01

The classical Linderstrom-Lang hydrogen exchange (HX) model is extended to describe the relationship between the HX behaviors (EX1 and EX2) and protein folding kinetics for the amide protons that can only exchange by global unfolding in a three-state system including native (N), intermediate (I), and unfolded (U) states. For these slowly exchanging amide protons, it is shown that the existence of an intermediate (I) has no effect on the HX behavior in an off-pathway three-state system (I↔U↔N). On the other hand, in an on-pathway three-state system (U↔I↔N), the existence of a stable folding intermediate has profound effect on the HX behavior. It is shown that fast refolding from the unfolded state to the stable intermediate state alone does not guarantee EX2 behavior. The rate of refolding from the intermediate state to the native state also plays a crucial role in determining whether EX1 or EX2 behavior should occur. This is mainly due to the fact that only amide protons in the native state are observed in the hydrogen exchange experiment. These new concepts suggest that caution needs to be taken if one tries to derive the kinetic events of protein folding from equilibrium hydrogen exchange experiments

Intramolecular migration of amide hydrogens in protonated peptides upon collisional activation

DEFF Research Database (Denmark)

Jørgensen, Thomas J. D.; Gårdsvoll, H.; Ploug, M.

2005-01-01

Presently different opinions exist as to the degree of scrambling of amide hydrogens in gaseous protonated peptides and proteins upon collisional activation in tandem mass spectrometry experiments. This unsettled controversy is not trivial, since only a very low degree of scrambling is tolerable...... if collision-induced dissociation (CID) should provide reliable site-specific information from (1)H/(2)H exchange experiments. We have explored a series of unique, regioselectively deuterium-labeled peptides as model systems to probe for intramolecular amide hydrogen migration under low-energy collisional...... are protected against exchange with the solvent, while the amide hydrogens of the nonbinding sequences exchange rapidly with the solvent. We have utilized such long-lived complexes to generate peptides labeled with deuterium in either the binding or nonbinding region, and the expected regioselectivity...

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.

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.

Direct Amination of alpha-Hydroxy Amides

NARCIS (Netherlands)

Chandgude, Ajay L.; Dömling, Alexander

A TiCl4-mediated reaction for the direct amination of alpha-hydroxy amides has been developed. This simple, general, additive/base/ligand-free reaction is mediated by economical TiCl4. The reaction runs under mild conditions. This highly efficient C-N bond formation protocol is valid for diverse

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...

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.

Segmented poly(ether ester)s and poly(ether ester amide)s for use in tissue engineering

OpenAIRE

Deschamps, A.A.

2002-01-01

The objective of the studies described in this thesis is to investigate the applicability of these slowly degradable thermoplastic elastomers as scaffolds for tissue engineering, with emphasis on their phase separation and degradation properties. A second thermoplastic elastomer in which the terephthalic moieties have been replaced by ester-amide segments, is also investigated for use in scaffolding.

A molecular mechanics (MM3(96)) force field for metal-amide complexes

International Nuclear Information System (INIS)

Hay, B.P.; Clement, O.; Sandrone, G.; Dixon, D.A.

1998-01-01

A molecular mechanics (MM3(96)) force field is reported for modeling metal complexes of amides in which the amide is coordinated through oxygen. This model uses a points-on-a-sphere approach which involves the parameterization of the Msingle bondO stretch, the Msingle bondO double-bond C bend, and the Msingle bondO double-bond Csingle bondX (X = C, H, N) torsion interactions. Relationships between force field parameters and metal ion properties (charge, ionic radius, and electronegativity) are presented that allow the application of this model to a wide range of metal ions. The model satisfactorily reproduces the structures of over fifty amide complexes with the alkaline earths, transition metals, lanthanides, and actinides

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…

Pd-Catalyzed N-Arylation of Secondary Acyclic Amides: Catalyst Development, Scope, and Computational Study

Science.gov (United States)

Hicks, Jacqueline D.; Hyde, Alan M.; Cuezva, Alberto Martinez; Buchwald, Stephen L.

2009-01-01

We report the efficient N-arylation of acyclic secondary amides and related nucleophiles with aryl nonaflates, triflates, and chlorides. This method allows for easy variation of the aromatic component in tertiary aryl amides. A new biaryl phosphine with P-bound 3,5-(bis)trifluoromethylphenyl groups was found to be uniquely effective for this amidation. The critical aspects of the ligand were explored through synthetic, mechanistic, and computational studies. Systematic variation of the ligand revealed the importance of (1) a methoxy group on the aromatic carbon of the “top ring” ortho to the phosphorus and (2) two highly electron-withdrawing P-bound 3,5-(bis)trifluoromethylphenyl groups. Computational studies suggest the electron-deficient nature of the ligand is important in facilitating amide binding to the LPd(II)(Ph)(X) intermediate. PMID:19886610

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.

Study on selective separation of uranium(VI) by new N,N-dialkyl carboxy-amides

International Nuclear Information System (INIS)

Suzuki, Shinichi; Sugo, Yumi; Kimura, Takaumi; Yaita, Tsuyoshi

2007-01-01

The Feasibility study (FS) on commercialized FR cycle systems has been carried out in Japan. In this Feasibility study, 'Advanced Aqueous' reprocessing was designed as a new reprocessing concept to enhance nuclear non-proliferation by recycling U, Pu and minor actinides (MA) with some fission products (FP). The crystallization and U(VI)/TRU(transuranics) co-extraction technique have been selected as candidate technique in the 'Advanced Aqueous' reprocessing. In JAEA, the result of Feasibility study was received and Fast Reactor Cycle Technology Development Project (FaCT) was started. In the nuclear spent fuel reprocessing, FBR spent fuels will coexist with LWR spent fuels for several decades until FBR cycle begins to operate. For the treatment of LWR spent fuels, high decontamination factor for FP was required for U(VI) storage, and solvent extraction technique was selected in the nuclear fuel treatment. In our laboratory, N,N-di-alkyl carboxy-amides have been developed as extractant based on solvent extraction technique for one of a back-up technology of 'Advanced Aqueous' reprocessing in FBR spent fuel treatments. N,N-di-alkyl carboxy-amides were noted as one of the alternative extractant of tri-butylphosphate (TBP) in the field of nuclear fuel reprocessing. Extraction behavior of U(VI) and Pu(IV) with N,N-di-alkyl carboxy-amides was almost similar to those with TBP. N,N-di-alkyl carboxy-amides have some advantages, namely, their complete incinerability (CHON principle) and high stability for hydrolysis and radiolysis. Their main degradation products are carboxylic acids and secondary amines which hardly affect the separation of U(VI) and Pu(IV) from fission products. Further, the synthesis of N,N-di-alkyl carboxy-amides was relatively easy with reaction of carboxylic chloride and secondary amine. The main purpose of this solvent extraction technique using N,N-di-alkyl carboxy-amides is selective separation of Uranium(VI) with branched N,N-di-alkyl carboxy-amides

An Efficient Computational Model to Predict Protonation at the Amide Nitrogen and Reactivity along the C–N Rotational Pathway

Science.gov (United States)

Szostak, Roman; Aubé, Jeffrey

2015-01-01

N-protonation of amides is critical in numerous biological processes, including amide bonds proteolysis and protein folding, as well as in organic synthesis as a method to activate amide bonds towards unconventional reactivity. A computational model enabling prediction of protonation at the amide bond nitrogen atom along the C–N rotational pathway is reported. Notably, this study provides a blueprint for the rational design and application of amides with a controlled degree of rotation in synthetic chemistry and biology. PMID:25766378

Indoline Amide Glucosides from Portulaca oleracea: Isolation, Structure, and DPPH Radical Scavenging Activity.

Science.gov (United States)

Jiao, Ze-Zhao; Yue, Su; Sun, Hong-Xiang; Jin, Tian-Yun; Wang, Hai-Na; Zhu, Rong-Xiu; Xiang, Lan

2015-11-25

A polyamide column chromatography method using an aqueous ammonia mobile phase was developed for large-scale accumulation of water-soluble indoline amide glucosides from a medicinal plant, Portulaca oleracea. Ten new [oleraceins H, I, K, L, N, O, P, Q, R, S (1-10)] and four known [oleraceins A-D (11-14)] indoline amide glucosides were further purified and structurally characterized by various chromatographic and spectroscopic methods. The DPPH radical scavenging activities of oleraceins K (5) and L (6), with EC50 values of 15.30 and 16.13 μM, respectively, were twice that of a natural antioxidant, vitamin C; the EC50 values of the 12 other indoline amides, which ranged from 29.05 to 43.52 μM, were similar to that of vitamin C. Structure-activity relationships indicated that the DPPH radical scavenging activities of these indoline amides correlate with the numbers and positions of the phenolic hydroxy groups.

Application of N,N-dialkyl aliphatic amides in the separation of some actinides

International Nuclear Information System (INIS)

Gasparini, G.M.; Grossi, G.

1980-01-01

N,N-dialkyl substituted alkyl amides are known to be good extractants of some actinides such as U, Pu, and Th. Their stability is comparable to that of TBP, and their degradation products do not interfere as do the degradation products of TBP. On the other hand, the principal disadvantage of the amides is their tendency to form poorly soluble U adducts in organic diluents. A systematic investigation has been carried out on the extractive behavior of two typical alkyl amides of different structures with respect to the actinide ions UO/sub 2/ /sup 2+/, Th /sup 4+/, Np /sup +4/, Pu /sup +4/, NpO /sub 2/ /sup 2+/, PuO /sub 2/ / sup 2+/, Pu /sup 3+/, and Am /sup 3+/, as well as with respect to the most significant fission products. The results obtained have been compared with those obtained using TBP in the same experimental conditions, verifying the applicability of amides in the separation of U from Th

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

DEFF Research Database (Denmark)

Fenger, M; Johnsen, A H

1988-01-01

Human pituitary tumours, obtained at surgery for Cushing's disease and Nelson's syndrome, were extracted and the content and molecular forms of pro-opiomelanocortin (POMC)-derived peptides determined by radioimmunoassay, gel chromatography, reversed-phase high-performance liquid chromatography....... In conclusion, all the molecular forms of the amidated peptides detected in tumours from patients with Cushing's disease and Nelson's syndrome were similar to the molecular forms found in the normal human pituitary. The main difference between the tumours and the normal pituitary was the greater amount...... (HPLC) and sequence analysis. In the tumours from patients with Cushing's disease the mean concentrations of amidated peptides relative to the total amount of POMC were as follows: alpha-MSH, 1.7%; amidated gamma-MSH (gamma 1-MSH), 8.5% and the peptide linking gamma-MSH and ACTH in the precursor (hinge...

RF-amide neuropeptides and their receptors in Mammals: Pharmacological properties, drug development and main physiological functions.

Science.gov (United States)

Quillet, Raphaëlle; Ayachi, Safia; Bihel, Frédéric; Elhabazi, Khadija; Ilien, Brigitte; Simonin, Frédéric

2016-04-01

RF-amide neuropeptides, with their typical Arg-Phe-NH2 signature at their carboxyl C-termini, belong to a lineage of peptides that spans almost the entire life tree. Throughout evolution, RF-amide peptides and their receptors preserved fundamental roles in reproduction and feeding, both in Vertebrates and Invertebrates. The scope of this review is to summarize the current knowledge on the RF-amide systems in Mammals from historical aspects to therapeutic opportunities. Taking advantage of the most recent findings in the field, special focus will be given on molecular and pharmacological properties of RF-amide peptides and their receptors as well as on their implication in the control of different physiological functions including feeding, reproduction and pain. Recent progress on the development of drugs that target RF-amide receptors will also be addressed. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Orientation and Order of the Amide Group of Sphingomyelin in Bilayers Determined by Solid-State NMR

Science.gov (United States)

Matsumori, Nobuaki; Yamaguchi, Toshiyuki; Maeta, Yoshiko; Murata, Michio

2015-01-01

Sphingomyelin (SM) and cholesterol (Chol) are considered essential for the formation of lipid rafts; however, the types of molecular interactions involved in this process, such as intermolecular hydrogen bonding, are not well understood. Since, unlike other phospholipids, SM is characterized by the presence of an amide group, it is essential to determine the orientation of the amide and its order in the lipid bilayers to understand the nature of the hydrogen bonds in lipid rafts. For this study, 1′-13C-2-15N-labeled and 2′-13C-2-15N-labeled SMs were prepared, and the rotational-axis direction and order parameters of the SM amide in bilayers were determined based on 13C and 15N chemical-shift anisotropies and intramolecular 13C-15N dipole coupling constants. Results revealed that the amide orientation was minimally affected by Chol, whereas the order was enhanced significantly in its presence. Thus, Chol likely promotes the formation of an intermolecular hydrogen-bond network involving the SM amide without significantly changing its orientation, providing a higher order to the SM amide. To our knowledge, this study offers new insight into the significance of the SM amide orientation with regard to molecular recognition in lipid rafts, and therefore provides a deeper understanding of the mechanism of their formation. PMID:26083921

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

2014-01-01

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. PMID:24813446

Hydrophilic segmented block copolymers based on poly(ethylene oxide) and monodisperse amide segments

NARCIS (Netherlands)

Husken, D.; Feijen, Jan; Gaymans, R.J.

2007-01-01

Segmented block copolymers based on poly(ethylene oxide) (PEO) flexible segments and monodisperse crystallizable bisester tetra-amide segments were made via a polycondensation reaction. The molecular weight of the PEO segments varied from 600 to 4600 g/mol and a bisester tetra-amide segment (T6T6T)

Binary and ternary cocrystals of sulfa drug acetazolamide with pyridine carboxamides and cyclic amides.

Science.gov (United States)

Bolla, Geetha; Nangia, Ashwini

2016-03-01

A novel design strategy for cocrystals of a sulfonamide drug with pyridine carboxamides and cyclic amides is developed based on synthon identification as well as size and shape match of coformers. Binary adducts of acetazolamide (ACZ) with lactams (valerolactam and caprolactam, VLM, CPR), cyclic amides (2-pyridone, labeled as 2HP and its derivatives MeHP, OMeHP) and pyridine amides (nicotinamide and picolinamide, NAM, PAM) were obtained by manual grinding, and their single crystals by solution crystallization. The heterosynthons in the binary cocrystals of ACZ with these coformers suggested a ternary combination for ACZ with pyridone and nicotinamide. Novel supramolecular synthons of ACZ with lactams and pyridine carboxamides are reported together with binary and ternary cocrystals for a sulfonamide drug. This crystal engineering study resulted in the first ternary cocrystal of acetazolamide with amide coformers, ACZ-NAM-2HP (1:1:1).

First Novozym 435 lipase-catalyzed Morita-Baylis-Hillman reaction in the presence of amides.

Science.gov (United States)

Tian, Xuemei; Zhang, Suoqin; Zheng, Liangyu

2016-03-01

The first Novozym 435 lipase-catalyzed Morita-Baylis-Hillman (MBH) reaction with amides as co-catalyst was realized. Results showed that neither Novozym 435 nor amide can independently catalyze the reaction. This co-catalytic system that used a catalytic amount of Novozym 435 with a corresponding amount of amide was established and optimized. The MBH reaction strongly depended on the structure of aldehyde substrate, amide co-catalyst, and reaction additives. The optimized reaction yield (43.4%) was achieved in the Novozym 435-catalyzed MBH reaction of 2, 4-dinitrobenzaldehyde and cyclohexenone with isonicotinamide as co-catalyst and β-cyclodextrin as additive only in 2 days. Although enantioselectivity of Novozym 435 was not found, the results were still significant because an MBH reaction using lipase as biocatalyst was realized for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

Quantitative structure-cytotoxicity relationship of phenylpropanoid amides.

Science.gov (United States)

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

2014-07-01

A total of 12 phenylpropanoid amides were subjected to quantitative structure-activity relationship (QSAR) analysis, based on their cytotoxicity, tumor selectivity and anti-HIV activity, in order to investigate on their 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 CC50 (50% cytotoxic concentration) against normal oral cells to that against OSCC cell lines. Anti-HIV activity was evaluated by the ratio of CC50 to EC50 (50% cytoprotective concentration from HIV infection). Physicochemical, structural, and quantum-chemical parameters were calculated based on the conformations optimized by the LowModeMD method followed by density functional theory (DFT) method. Twelve phenylpropanoid amides showed moderate cytotoxicity against both normal and OSCC cell lines. N-Caffeoyl derivatives coupled with vanillylamine and tyramine exhibited relatively higher tumor selectivity. Cytotoxicity against normal cells was correlated with descriptors related to electrostatic interaction such as polar surface area and chemical hardness, whereas cytotoxicity against tumor cells correlated with free energy, surface area and ellipticity. The tumor-selective cytotoxicity correlated with molecular size (surface area) and electrostatic interaction (the maximum electrostatic potential). The molecular size, shape and ability for electrostatic interaction are useful parameters for estimating the tumor selectivity of phenylpropanoid amides. Copyright© 2014 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

Protein folding kinetics by combined use of rapid mixing techniques and NMR observation of individual amide protons

International Nuclear Information System (INIS)

Roder, H.; Wuethrich, K.

1986-01-01

A method to be used for experimental studies of protein folding introduced by Schmid and Baldwin, which is based on the competition between amide hydrogen exchange and protein refolding, was extended by using rapid mixing techniques and 1 H NMR to provide site-resolved kinetic information on the early phases of protein structure acquisition. In this method, a protonated solution of the unfolded protein is rapidly mixed with a deuterated buffer solution at conditions assuring protein refolding in the mixture. This simultaneously initiates the exchange of unprotected amide protons with solvent deuterium and the refolding of protein segments which can protect amide groups from further exchange. After variable reaction times the amide proton exchange is quenched while folding to the native form continues to completion. By using 1 H NMR, the extent of exchange at individual amide sites is then measured in the refolded protein. Competition experiments at variable reaction times or variable pH indicate the time at which each amide group is protected in the refolding process. This technique was applied to the basic pancreatic trypsin inhibitor, for which sequence-specific assignments of the amide proton NMR lines had previously been obtained. For eight individual amide protons located in the beta-sheet and the C-terminal alpha-helix of this protein, apparent refolding rates in the range from 15 s-1 to 60 s-1 were observed. These rates are on the time scale of the fast folding phase observed with optical probes

Multidrug resistance-selective antiproliferative activity of Piper amide alkaloids and synthetic analogues.

Science.gov (United States)

Wang, Yue-Hu; Goto, Masuo; Wang, Li-Ting; Hsieh, Kan-Yen; Morris-Natschke, Susan L; Tang, Gui-Hua; Long, Chun-Lin; Lee, Kuo-Hsiung

2014-10-15

Twenty-five amide alkaloids (1-25) from Piper boehmeriifolium and 10 synthetic amide alkaloid derivatives (39-48) were evaluated for antiproliferative activity against eight human tumor cell lines, including chemosensitive and multidrug-resistant (MDR) cell lines. The results suggested tumor type-selectivity. 1-[7-(3,4,5-Trimethoxyphenyl)heptanoyl]piperidine (46) exhibited the best inhibitory activity (IC50=4.94 μM) against the P-glycoprotein (P-gp)-overexpressing KBvin MDR sub-line, while it and all other tested compounds, except 9, were inactive (IC50 >40 μM) against MDA-MB-231 and SK-BR-3. Structure-activity relationships (SARs) indicated that (i) 3,4,5-trimethoxy phenyl substitution is critical for selectivity against KBvin, (ii) the 4-methoxy group in this pattern is crucial for antiproliferative activity, (iii) double bonds in the side chain are not needed for activity, and (iv), in arylalkenylacyl amide alkaloids, replacement of an isobutylamino group with pyrrolidin-1-yl or piperidin-1-yl significantly improved activity. Further study on Piper amides is warranted, particularly whether side chain length affects the ability to overcome the MDR cancer phenotype. Copyright © 2014 Elsevier Ltd. All rights reserved.

Solvent and conformation dependence of amide I vibrations in peptides and proteins containing proline

NARCIS (Netherlands)

Roy, Santanu; Lessing, Joshua; Meisl, Georg; Ganim, Ziad; Tokmakoff, Andrei; Knoester, Jasper; Jansen, Thomas L. C.

2011-01-01

We present a mixed quantum-classical model for studying the amide I vibrational dynamics (predominantly CO stretching) in peptides and proteins containing proline. There are existing models developed for determining frequencies of and couplings between the secondary amide units. However, these are

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, 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.

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.

Binary and ternary cocrystals of sulfa drug acetazolamide with pyridine carboxamides and cyclic amides

Directory of Open Access Journals (Sweden)

Geetha Bolla

2016-03-01

Full Text Available A novel design strategy for cocrystals of a sulfonamide drug with pyridine carboxamides and cyclic amides is developed based on synthon identification as well as size and shape match of coformers. Binary adducts of acetazolamide (ACZ with lactams (valerolactam and caprolactam, VLM, CPR, cyclic amides (2-pyridone, labeled as 2HP and its derivatives MeHP, OMeHP and pyridine amides (nicotinamide and picolinamide, NAM, PAM were obtained by manual grinding, and their single crystals by solution crystallization. The heterosynthons in the binary cocrystals of ACZ with these coformers suggested a ternary combination for ACZ with pyridone and nicotinamide. Novel supramolecular synthons of ACZ with lactams and pyridine carboxamides are reported together with binary and ternary cocrystals for a sulfonamide drug. This crystal engineering study resulted in the first ternary cocrystal of acetazolamide with amide coformers, ACZ–NAM–2HP (1:1:1.

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

Benzoylureas as removable cis amide inducers: synthesis of cyclic amides via ring closing metathesis (RCM).

Science.gov (United States)

Brady, Ryan M; Khakham, Yelena; Lessene, Guillaume; Baell, Jonathan B

2011-02-07

Rapid and high yielding synthesis of medium ring lactams was made possible through the use of a benzoylurea auxiliary that serves to stabilize a cisoid amide conformation, facilitating cyclization. The auxiliary is released after activation under the mild conditions required to deprotect a primary amine, such as acidolysis of a Boc group in the examples given here. This methodology is a promising tool for the synthesis of medium ring lactams, macrocyclic natural products and peptides.

Protein proton-proton dynamics from amide proton spin flip rates

International Nuclear Information System (INIS)

Weaver, Daniel S.; Zuiderweg, Erik R. P.

2009-01-01

Residue-specific amide proton spin-flip rates K were measured for peptide-free and peptide-bound calmodulin. K approximates the sum of NOE build-up rates between the amide proton and all other protons. This work outlines the theory of multi-proton relaxation, cross relaxation and cross correlation, and how to approximate it with a simple model based on a variable number of equidistant protons. This model is used to extract the sums of K-rates from the experimental data. Error in K is estimated using bootstrap methodology. We define a parameter Q as the ratio of experimental K-rates to theoretical K-rates, where the theoretical K-rates are computed from atomic coordinates. Q is 1 in the case of no local motion, but decreases to values as low as 0.5 with increasing domination of sidechain protons of the same residue to the amide proton flips. This establishes Q as a monotonous measure of local dynamics of the proton network surrounding the amide protons. The method is applied to the study of proton dynamics in Ca 2+ -saturated calmodulin, both free in solution and bound to smMLCK peptide. The mean Q is 0.81 ± 0.02 for free calmodulin and 0.88 ± 0.02 for peptide-bound calmodulin. This novel methodology thus reveals the presence of significant interproton disorder in this protein, while the increase in Q indicates rigidification of the proton network upon peptide binding, confirming the known high entropic cost of this process

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.

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.

Direct Reaction of Amides with Nitric Oxide To Form Diazeniumdiolates

Science.gov (United States)

2015-01-01

We report the apparently unprecedented direct reaction of nitric oxide (NO) with amides to generate ions of structure R(C=O)NH–N(O)=NO–, with examples including R = Me (1a) or 3-pyridyl (1b). The sodium salts of both released NO in pH 7.4 buffer, with 37 °C half-lives of 1–3 min. As NO-releasing drug candidates, diazeniumdiolated amides would have the advantage of generating only 1 equiv of base on hydrolyzing exhaustively to NO, in contrast to their amine counterparts, which generate 2 equiv of base. PMID:25210948

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.

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

Directory of Open Access Journals (Sweden)

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.

An Experimental and Computational Study of the Gas-Phase Acidities of the Common Amino Acid Amides.

Science.gov (United States)

Plummer, Chelsea E; Stover, Michele L; Bokatzian, Samantha S; Davis, John T M; Dixon, David A; Cassady, Carolyn J

2015-07-30

Using proton-transfer reactions in a Fourier transform ion cyclotron resonance mass spectrometer and correlated molecular orbital theory at the G3(MP2) level, gas-phase acidities (GAs) and the associated structures for amides corresponding to the common amino acids have been determined for the first time. These values are important because amino acid amides are models for residues in peptides and proteins. For compounds whose most acidic site is the C-terminal amide nitrogen, two ions populations were observed experimentally with GAs that differ by 4-7 kcal/mol. The lower energy, more acidic structure accounts for the majority of the ions formed by electrospray ionization. G3(MP2) calculations predict that the lowest energy anionic conformer has a cis-like orientation of the [-C(═O)NH](-) group whereas the higher energy, less acidic conformer has a trans-like orientation of this group. These two distinct conformers were predicted for compounds with aliphatic, amide, basic, hydroxyl, and thioether side chains. For the most acidic amino acid amides (tyrosine, cysteine, tryptophan, histidine, aspartic acid, and glutamic acid amides) only one conformer was observed experimentally, and its experimental GA correlates with the theoretical GA related to side chain deprotonation.

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

Application of mid-infrared free-electron laser tuned to amide bands for dissociation of aggregate structure of protein.

Science.gov (United States)

Kawasaki, Takayasu; Yaji, Toyonari; Ohta, Toshiaki; Tsukiyama, Koichi

2016-01-01

A mid-infrared free-electron laser (FEL) is a linearly polarized, high-peak powered pulse laser with tunable wavelength within the mid-infrared absorption region. It was recently found that pathogenic amyloid fibrils could be partially dissociated to the monomer form by the irradiation of the FEL targeting the amide I band (C=O stretching vibration), amide II band (N-H bending vibration) and amide III band (C-N stretching vibration). In this study, the irradiation effect of the FEL on keratin aggregate was tested as another model to demonstrate an applicability of the FEL for dissociation of protein aggregates. Synchrotron radiation infrared microscopy analysis showed that the α-helix content in the aggregate structure decreased to almost the same level as that in the monomer state after FEL irradiation tuned to 6.06 µm (amide I band). Both irradiations at 6.51 µm (amide II band) and 8.06 µm (amide III band) also decreased the content of the aggregate but to a lesser extent than for the irradiation at the amide I band. On the contrary, the irradiation tuned to 5.6 µm (non-absorbance region) changed little the secondary structure of the aggregate. Scanning-electron microscopy observation at the submicrometer order showed that the angular solid of the aggregate was converted to non-ordered fragments by the irradiation at each amide band, while the aggregate was hardly deformed by the irradiation at 5.6 µm. These results demonstrate that the amide-specific irradiation by the FEL was effective for dissociation of the protein aggregate to the monomer form.

Nickel-Catalyzed Phosphine Free Direct N-Alkylation of Amides with Alcohols.

Science.gov (United States)

Das, Jagadish; Banerjee, Debasis

2018-03-16

Herein, we developed an operational simple, practical, and selective Ni-catalyzed synthesis of secondary amides. Application of renewable alcohols, earth-abundant and nonprecious nickel catalyst facilitates the transformations, releasing water as byproduct. The catalytic system is tolerant to a variety of functional groups including nitrile, allylic ether, and alkene and could be extended to the synthesis of bis-amide, antiemetic drug Tigan, and dopamine D2 receptor antagonist Itopride. Preliminary mechanistic studies revealed the participation of a benzylic C-H bond in the rate-determining step.

Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase.

Science.gov (United States)

Kim, In-Hae; Park, Yong-Kyu; Nishiwaki, Hisashi; Hammock, Bruce D; Nishi, Kosuke

2015-11-15

Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase (sEH) were investigated. First, a series of alkyl or aryl groups were substituted on the carbon alpha to the phosphonate function in amide compounds to see whether substituted phosphonates can act as a secondary pharmacophore. A tert-butyl group (16) on the alpha carbon was found to yield most potent inhibition on the target enzyme. A 4-50-fold drop in inhibition was induced by other substituents such as aryls, substituted aryls, cycloalkyls, and alkyls. Then, the modification of the O-substituents on the phosphonate function revealed that diethyl groups (16 and 23) were preferable for inhibition to other longer alkyls or substituted alkyls. In amide compounds with the optimized diethylphosphonate moiety and an alkyl substitution such as adamantane (16), tetrahydronaphthalene (31), or adamantanemethane (36), highly potent inhibitions were gained. In addition, the resulting potent amide-phosphonate compounds had reasonable water solubility, suggesting that substituted phosphonates in amide inhibitors are effective for both inhibition potency on the human sEH and water solubility as a secondary pharmacophore. Copyright © 2015 Elsevier Ltd. All rights reserved.

Inhibition effect of fatty amides with secondary compound on carbon steel corrosion in hydrodynamic condition

Science.gov (United States)

Ibrahim, I. M.; Jai, J.; Daud, M.; Hashim, Md A.

2018-03-01

The inhibition effect demonstrates an increase in the inhibition performance in presence of a secondary compound in the inhibited solution. This study introduces fatty amides as corrosion inhibitor and oxygen scavenger, namely, sodium sulphite as a secondary compound. The main objective is to determine the synergistic inhibition effect of a system by using fatty amides together with sodium sulphite in hydrodynamic condition. The synergistic inhibition of fatty amides and sodium sulphite on corrosion of carbon steel in 3.5 wt% sodium chloride solution had been studied using linear polarization resistance method and scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDX). Electrochemical measurement was carried out using rotating cylinder electrode at different flow regimes (static, laminar, transition and turbulent). Linear polarization resistance experiments showed the changes in polarization resistance when the rotation speed increased. It found that, by addition of fatty amides together with sodium sulphite in test solution, the inhibition efficiency increased when rotation speed increased. The results collected from LPR experiment correlated with results from SEM-EDX. The results showed inhibition efficiency of system was enhanced when fatty amides and oxygen scavengers were present together.

Steroids linked with amide bond - extended cholesterol

Czech Academy of Sciences Publication Activity Database

Černý, Ivan; Buděšínský, Miloš; Pouzar, Vladimír; Drašar, P.

2009-01-01

Roč. 74, č. 1 (2009), s. 88-94 ISSN 0039-128X R&D Projects: GA MŠk(CZ) LC06077; GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z40550506 Keywords : synthesis * oligomers * amides Subject RIV: CC - Organic Chemistry Impact factor: 2.905, year: 2009

Chiral amides via copper-catalysed enantioselective conjugate addition

NARCIS (Netherlands)

Schoonen, Anne K.; Fernández-Ibáñez, M. Ángeles; Fañanás-Mastral, Martín; Teichert, Johannes F.; Feringa, Bernard

2014-01-01

A highly enantioselective one pot procedure for the synthesis of beta-substituted amides was developed starting from the corresponding alpha,beta-unsaturated esters. This new methodology is based on the copper-catalysed enantioselective conjugate addition of Grignard reagents to

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.

Lipase-catalyzed synthesis of fatty acid amide (erucamide) using fatty acid and urea.

Science.gov (United States)

Awasthi, Neeraj Praphulla; Singh, R P

2007-01-01

Ammonolysis of fatty acids to the corresponding fatty acid amides is efficiently catalysed by Candida antartica lipase (Novozym 435). In the present paper lipase-catalysed synthesis of erucamide by ammonolysis of erucic acid and urea in organic solvent medium was studied and optimal conditions for fatty amides synthesis were established. In this process erucic acid gave 88.74 % pure erucamide after 48 hour and 250 rpm at 60 degrees C with 1:4 molar ratio of erucic acid and urea, the organic solvent media is 50 ml tert-butyl alcohol (2-methyl-2-propanol). This process for synthesis is economical as we used urea in place of ammonia or other amidation reactant at atmospheric pressure. The amount of catalyst used is 3 %.

Nitrotriazole- and imidazole-based amides and sulfonamides as antitubercular agents.

Science.gov (United States)

Papadopoulou, Maria V; Bloomer, William D; Rosenzweig, Howard S; Arena, Alexander; Arrieta, Francisco; Rebolledo, Joseph C J; Smith, Diane K

2014-11-01

Twenty-three 3-nitrotriazole-based and 2-nitroimidazole-based amides and sulfonamides were screened for antitubercular (anti-TB) activity in aerobic Mycobacterium tuberculosis H37Rv by using the BacTiter-Glo (BTG) microbial cell viability assay. In general, 3-nitrotriazole-based sulfonamides demonstrated anti-TB activity, whereas 3-nitrotriazole-based amides and 2-nitroimidazole-based amides and sulfonamides were inactive. Three 3-nitrotriazole-based sulfonamides (compounds 4, 2, and 7) demonstrated 50% inhibitory concentration (IC50), IC90, and MIC values of 0.38, 0.43, and 1.56 μM (compound 4), 0.57, 0.98, and 3.13 μM (compound 2), and 0.79, 0.87, and 3.13 μM (compound 7), respectively. For 3-nitrotriazole-based sulfonamides, anti-TB activity increased with lipophilicity, whereas the one-electron reduction potential (E1/2) did not play a role. 2-Nitroimidazole-based analogs, which were inactive in the BTG assay, were significantly more active in the low-oxygen assay and more active than the 3-nitrotriazoles. All active nitrotriazoles in the BTG assay were similarly active or more potent (lower MIC values) against resistant strains, with the exception of compounds 2, 3, 4, and 8, which demonstrated greater MIC values against isoniazid-resistant strains. Five 3-nitrotriazole-based sulfonamides demonstrated activity in infected murine J774 macrophages, causing log reductions similar to those seen with rifampin. However, some compounds caused toxicity in uninfected macrophages. In conclusion, the classes of 3-nitrotriazole-based amides and sulfonamides merit further investigation as potential antitubercular agents. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Pregna-5,17(20)-dien-21-oyl amides affecting sterol and triglyceride biosynthesis in Hep G2 cells.

Science.gov (United States)

Stulov, Sergey V; Mankevich, Olga V; Dugin, Nikita O; Novikov, Roman A; Timofeev, Vladimir P; Misharin, Alexander Yu

2013-04-01

Synthesis of series [17(20)Z]- and [17(20)E]-pregna-5,17(20)-dien-21-oyl amides, containing polar substituents in amide moiety, based on rearrangement of 17α-bromo-21-iodo-3β-acetoxypregn-5-en-20-one caused by amines, is presented. The titled compounds were evaluated for their potency to regulate sterol and triglyceride biosynthesis in human hepatoma Hep G2 cells in comparison with 25-hydroxycholesterol. Three [17(20)E]-pregna-5,17(20)-dien-21-oyl amides at a concentrations of 5 μM inhibited sterol biosynthesis and stimulated triglyceride biosynthesis; their regulatory potency was dependent on the structure of amide moiety; the isomeric [17(20)Z]-pregna-5,17(20)-dien-21-oyl amides were inactive. Copyright © 2013 Elsevier Ltd. All rights reserved.

Apoptosis-inducing Factor (AIF) and Its Family Member Protein, AMID, Are Rotenone-sensitive NADH:Ubiquinone Oxidoreductases (NDH-2)*

Science.gov (United States)

Elguindy, Mahmoud M.; Nakamaru-Ogiso, Eiko

2015-01-01

Apoptosis-inducing factor (AIF) and AMID (AIF-homologous mitochondrion-associated inducer of death) are flavoproteins. Although AIF was originally discovered as a caspase-independent cell death effector, bioenergetic roles of AIF, particularly relating to complex I functions, have since emerged. However, the role of AIF in mitochondrial respiration and redox metabolism has remained unknown. Here, we investigated the redox properties of human AIF and AMID by comparing them with yeast Ndi1, a type 2 NADH:ubiquinone oxidoreductase (NDH-2) regarded as alternative complex I. Isolated AIF and AMID containing naturally incorporated FAD displayed no NADH oxidase activities. However, after reconstituting isolated AIF or AMID into bacterial or mitochondrial membranes, N-terminally tagged AIF and AMID displayed substantial NADH:O2 activities and supported NADH-linked proton pumping activities in the host membranes almost as efficiently as Ndi1. NADH:ubiquinone-1 activities in the reconstituted membranes were highly sensitive to 2-n-heptyl-4-hydroxyquinoline-N-oxide (IC50 = ∼1 μm), a quinone-binding inhibitor. Overexpressing N-terminally tagged AIF and AMID enhanced the growth of a double knock-out Escherichia coli strain lacking complex I and NDH-2. In contrast, C-terminally tagged AIF and NADH-binding site mutants of N-terminally tagged AIF and AMID failed to show both NADH:O2 activity and the growth-enhancing effect. The disease mutant AIFΔR201 showed decreased NADH:O2 activity and growth-enhancing effect. Furthermore, we surprisingly found that the redox activities of N-terminally tagged AIF and AMID were sensitive to rotenone, a well known complex I inhibitor. We propose that AIF and AMID are previously unidentified mammalian NDH-2 enzymes, whose bioenergetic function could be supplemental NADH oxidation in cells. PMID:26063804

Apoptosis-inducing Factor (AIF) and Its Family Member Protein, AMID, Are Rotenone-sensitive NADH:Ubiquinone Oxidoreductases (NDH-2).

Science.gov (United States)

Elguindy, Mahmoud M; Nakamaru-Ogiso, Eiko

2015-08-21

Apoptosis-inducing factor (AIF) and AMID (AIF-homologous mitochondrion-associated inducer of death) are flavoproteins. Although AIF was originally discovered as a caspase-independent cell death effector, bioenergetic roles of AIF, particularly relating to complex I functions, have since emerged. However, the role of AIF in mitochondrial respiration and redox metabolism has remained unknown. Here, we investigated the redox properties of human AIF and AMID by comparing them with yeast Ndi1, a type 2 NADH:ubiquinone oxidoreductase (NDH-2) regarded as alternative complex I. Isolated AIF and AMID containing naturally incorporated FAD displayed no NADH oxidase activities. However, after reconstituting isolated AIF or AMID into bacterial or mitochondrial membranes, N-terminally tagged AIF and AMID displayed substantial NADH:O₂ activities and supported NADH-linked proton pumping activities in the host membranes almost as efficiently as Ndi1. NADH:ubiquinone-1 activities in the reconstituted membranes were highly sensitive to 2-n-heptyl-4-hydroxyquinoline-N-oxide (IC₅₀ = ∼1 μm), a quinone-binding inhibitor. Overexpressing N-terminally tagged AIF and AMID enhanced the growth of a double knock-out Escherichia coli strain lacking complex I and NDH-2. In contrast, C-terminally tagged AIF and NADH-binding site mutants of N-terminally tagged AIF and AMID failed to show both NADH:O₂ activity and the growth-enhancing effect. The disease mutant AIFΔR201 showed decreased NADH:O₂ activity and growth-enhancing effect. Furthermore, we surprisingly found that the redox activities of N-terminally tagged AIF and AMID were sensitive to rotenone, a well known complex I inhibitor. We propose that AIF and AMID are previously unidentified mammalian NDH-2 enzymes, whose bioenergetic function could be supplemental NADH oxidation in cells. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

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.

Novel amide-based inhibitors of inosine 5'-monophosphate dehydrogenase.

Science.gov (United States)

Watterson, Scott H; Liu, Chunjian; Dhar, T G Murali; Gu, Henry H; Pitts, William J; Barrish, Joel C; Fleener, Catherine A; Rouleau, Katherine; Sherbina, N Z; Hollenbaugh, Diane L; Iwanowicz, Edwin J

2002-10-21

A series of novel amide-based small molecule inhibitors of inosine monophosphate dehydrogenase (IMPDH) was explored. The synthesis and the structure-activity relationships (SARs) derived from in vitro studies are described.

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)

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.

The glucagon-like peptide-1 metabolite GLP-1-(9-36) amide reduces postprandial glycemia independently of gastric emptying and insulin secretion in humans

DEFF Research Database (Denmark)

Meier, Juris J; Gethmann, Arnica; Nauck, Michael A

2006-01-01

Glucagon-like peptide 1 (GLP-1) lowers glycemia by modulating gastric emptying and endocrine pancreatic secretion. Rapidly after its secretion, GLP-1-(7-36) amide is degraded to the metabolite GLP-1-(9-36) amide. The effects of GLP-1-(9-36) amide in humans are less well characterized. Fourteen...... healthy volunteers were studied with intravenous infusion of GLP-1-(7-36) amide, GLP-1-(9-36) amide, or placebo over 390 min. After 30 min, a solid test meal was served, and gastric emptying was assessed. Blood was drawn for GLP-1 (total and intact), glucose, insulin, C-peptide, and glucagon measurements....... Administration of GLP-1-(7-36) amide and GLP-1-(9-36) amide significantly raised total GLP-1 plasma levels. Plasma concentrations of intact GLP-1 increased to 21 +/- 5 pmol/l during the infusion of GLP-1-(7-36) amide but remained unchanged during GLP-1-(9-36) amide infusion [5 +/- 3 pmol/l; P

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

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.

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.

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.

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.

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.

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.

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)

Amides and Hydrazides from Amine and Hydrazine Hydrochlorides.

Science.gov (United States)

Shama, Sami A.; Tran, Thuan L.

1978-01-01

This safe and efficient procedure for the synthesis of N-substituted amides and hydrazides is a modification of the Schotten-Bausmann procedure in which the amine or hydrazide is replaced by the corresponding hydrochloride salt, and the use of alkali is eliminated. (Author/BB)

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.

Ternary (liquid + liquid) equilibria of {bis(trifluoromethylsulfonyl)-amide based ionic liquids + butan-1-ol + water}

International Nuclear Information System (INIS)

Marciniak, Andrzej; Wlazło, Michał; Gawkowska, Joanna

2016-01-01

Highlights: • Ternary (liquid + liquid) equilibria for 3 ionic liquid + butanol + water systems. • The influence of ionic liquid structure on phase diagrams is discussed. • Influence of IL structure on S and β for butanol/water separation is discussed. - Abstract: Ternary (liquid + liquid) phase equilibria for 3 systems containing bis(trifluoromethylsulfonyl)-amide ionic liquids (1-buthyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide, 1-(2-methoxyethyl)-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide, {1-(2-methoxyethyl)-1-methylpyrrolidinium bis(trifluorylsulfonyl)-amide) + butan-1-ol + water} have been determined at T = 298.15 K. The selectivity and solute distribution ratio were calculated for investigated systems and compared with literature data for other systems containing ionic liquids. In each system total solubility of butan-1-ol and low solubility of water in the ionic liquid is observed. The experimental results have been correlated using NRTL model. The influence of the structure of ionic liquid on phase equilibria, selectivity and solute distribution ratio is shortly discussed.

Chemometric characterization of the hydrogen bonding complexes of secondary amides and aromatic hydrocarbons

OpenAIRE

Jović, Branislav; Nikolić, Aleksandar; Petrović, Slobodan

2012-01-01

The paper reports the results of the study of hydrogen bonding complexes between secondary amides and various aromatic hydrocarbons. The possibility of using chemometric methods was investigated in order to characterize N-H•••π hydrogen bonded complexes. Hierarchical clustering and Principal Component Analysis (PCA) have been applied on infrared spectroscopic and Taft parameters of 43 N-substituted amide complexes with different aromatic hydrocarbons. Results obtained in this report are...

Studies on supercritical fluid extraction behaviour of uranium and thorium nitrates using amides

International Nuclear Information System (INIS)

Sujatha, K.; Kumar, R.; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2007-01-01

Supercritical fluid extraction studies of uranyl nitrate and thorium nitrate in mixture were carried out using various amides such as N,N-di(2-ethylhexyl) isobutyramide (D2EHIBA),N,N-dihexyl octanamide (DHOA) and Diisooctyl Butanamide (DiOBA). These studies established a preferential extraction of uranium over thorium. Among the various amides studied, D2EHIBA offered the best rate of preferential extraction of uranium over thorium. (author)

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.

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.

Electrostatic frequency maps for amide-I mode of β-peptide: Comparison of molecular mechanics force field and DFT calculations

Science.gov (United States)

Cai, Kaicong; Zheng, Xuan; Du, Fenfen

2017-08-01

The spectroscopy of amide-I vibrations has been widely utilized for the understanding of dynamical structure of polypeptides. For the modeling of amide-I spectra, two frequency maps were built for β-peptide analogue (N-ethylpropionamide, NEPA) in a number of solvents within different schemes (molecular mechanics force field based, GM map; DFT calculation based, GD map), respectively. The electrostatic potentials on the amide unit that originated from solvents and peptide backbone were correlated to the amide-I frequency shift from gas phase to solution phase during map parameterization. GM map is easier to construct with negligible computational cost since the frequency calculations for the samples are purely based on force field, while GD map utilizes sophisticated DFT calculations on the representative solute-solvent clusters and brings insight into the electronic structures of solvated NEPA and its chemical environments. The results show that the maps' predicted amide-I frequencies present solvation environmental sensitivities and exhibit their specific characters with respect to the map protocols, and the obtained vibrational parameters are in satisfactory agreement with experimental amide-I spectra of NEPA in solution phase. Although different theoretical schemes based maps have their advantages and disadvantages, the present maps show their potentials in interpreting the amide-I spectra for β-peptides, respectively.

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

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amides, tall-oil fatty, N-[2-[2... Significant New Uses for Specific Chemical Substances § 721.9672 Amides, tall-oil fatty, N-[2-[2-hydroxyethyl... identified as amides, tall-oil fatty, N-[2-[2-hydroxyethyl)amino]ethyl], reaction products with sulfur...

Dynamics of urokinase receptor interaction with Peptide antagonists studied by amide hydrogen exchange and mass spectrometry

DEFF Research Database (Denmark)

Jørgensen, Thomas J D; Gårdsvoll, Henrik; Danø, Keld

2004-01-01

Using amide hydrogen exchange combined with electrospray ionization mass spectrometry, we have in this study determined the number of amide hydrogens on several peptides that become solvent-inaccessible as a result of their high-affinity interaction with the urokinase-type plasminogen activator...... receptor (uPAR). These experiments reveal that at least six out of eight amide hydrogens in a synthetic nine-mer peptide antagonist (AE105) become sequestered upon engagement in uPAR binding. Various uPAR mutants with decreased affinity for this peptide antagonist gave similar results, thereby indicating...... that deletion of the favorable interactions involving the side chains of these residues in uPAR does not affect the number of hydrogen bonds established by the main chain of the peptide ligand. The isolated growth factor-like domain (GFD) of the cognate serine protease ligand for uPAR showed 11 protected amide...

Investigation of Uranyl Nitrate Ion Pairs Complexed with Amide Ligands using Electrospray Ionization Ion Trap Mass Spectrometry and Density Functional Theory

International Nuclear Information System (INIS)

Groenewold, Gary S.; Dinescu, Adriana; Benson, Michael T.; Gresham, Garold L.; van Stipdonk, Michael J.

2011-01-01

Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula (UO2(NO3)(amide)n=2,3)+, and complexes containing the amide conjugate base, reduced uranyl UO2+, and a 2+ charge were also formed. The formamide experiment produced the greatest diversity of species that stems from weaker amide binding leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant, and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed reduced doubly charged complexes and augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that inter-ligand repulsion distorts the amide ligands out of the uranyl equatorial plane, and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion, and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and methyl-acetamide ligands.

The spectroscopy and structure of some lanthanide chlorides in amide solutions

International Nuclear Information System (INIS)

Legendziewicz, J.; Bukietynska, K; Jezowsky-Trzebiatowska, B.

1974-01-01

The absorption spectra of Pr, Nd, Ho, and Er anhydrous and hydrated chlorides in formamide, methyl-, dimethyl-, and diethylformamide solutions have been investigated in the range of 8000 - 4200 cm -1 . By the Judd-Oefelt method of intensity analysis and by calculating the nepheloauxetic effect, the first coordination sphere of lanthanide ions and the approximate symmetry of amide solvates of anhydrous and hydrated lanthanide chlorides were determined. A difference between symmetry and coordination numbers for light and heavy lanthanide solvates has been found. Some considerations regarding the structure of lanthanide solvates and structure of amide molecules have been made. (B.T.)

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.

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).

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

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

Design, synthesis, and fungicidal activities of imino diacid analogs of valine amide fungicides.

Science.gov (United States)

Sun, Man; Yang, Hui-Hui; Tian, Lei; Li, Jian-Qiang; Zhao, Wei-Guang

2015-12-15

The novel imino diacid analogs of valine amides were synthesized via several steps, including the protection, amidation, deprotection, and amino alkylation of valine, with the resulting structures confirmed by (1)H and (13)C NMR and HRMS. Bioassays showed that some of these compounds exhibited good fungicidal activity. Notably, isopropyl 2-((1-((1-(3-fluorophenyl)ethyl)amino)-3-methyl-1-oxobutan-2-yl)amino)propanoate 5i displayed significant levels of control, at 50%, against Erysiphe graminis at 3.9μM as well as a level of potency very similar to the reference azoxystrobin, which gave 60% activity at this concentration. The present work demonstrates that imino diacid analogs of valine amides could be potentially useful key compounds for the development of novel fungicides against wheat powdery mildew. Copyright © 2015 Elsevier Ltd. All rights reserved.

Amide Synthesis from Alcohols and Amines Catalyzed by Ruthenium N-Heterocyclic Carbene Complexes

DEFF Research Database (Denmark)

Dam, Johan Hygum; Osztrovszky, Gyorgyi; Nordstrøm, Lars Ulrik Rubæk

2010-01-01

The direct synthesis of amides from alcohols and amines is described with the simultaneous liberation of dihydrogen. The reaction does not require any stoichiometric additives or hydrogen acceptors and is catalyzed by ruthenium N-heterocyclic carbene complexes. Three different catalyst systems...... are presented that all employ 1,3-diisopropylimidazol-2-ylidene (IiPr) as the carbene ligand. In addition, potassium tert-butoxide and a tricycloalkylphosphine are required for the amidation to proceed. In the first system, the active catalyst is generated in situ from [RuCl2(cod)] (cod = 1,5-cyclooctadiene), 1...... chloride and base. A range of different primary alcohols and amines have been coupled in the presence of the three catalyst systems to afford the corresponding amides in moderate to excellent yields. The best results are obtained with sterically unhindered alcohols and amines. The three catalyst systems do...

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.

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

Amphiphilic poly(ether ester amide) multiblock copolymers as biodegradable matrices for the controlled release of proteins

NARCIS (Netherlands)

Bezemer, J.M.; Oude Weme, P.; Grijpma, Dirk W.; Dijkstra, Pieter J.; van Blitterswijk, Clemens; Feijen, Jan

2000-01-01

Amphiphilic poly(ether ester amide) (PEEA) multiblock copolymers were synthesized by polycondensation in the melt from hydrophilic poly(ethylene glycol) (PEG), 1,4-dihydroxybutane and short bisester-bisamide blocks. These amide blocks were prepared by reaction of 1,4-diaminobutane with dimethyl

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

Amides are novel protein modifications formed by physiological sugars.

Science.gov (United States)

Glomb, M A; Pfahler, C

2001-11-09

The Maillard reaction, or nonenzymatic browning, proceeds in vivo, and the resulting protein modifications (advanced glycation end products) have been associated with various pathologies. Despite intensive research only very few structures have been established in vivo. We report here for the first time N(6)-[2-[(5-amino-5-carboxypentyl)amino]-2-oxoethyl]lysine (GOLA) and N(6)-glycoloyllysine (GALA) as prototypes for novel amide protein modifications produced by reducing sugars. Their identity was confirmed by independent synthesis and coupled liquid chromatography/mass spectrometry. Model reactions with N(alpha)-t-butoxycarbonyl-lysine showed that glyoxal and glycolaldehyde are immediate precursors, and reaction pathways are directly linked to N(epsilon)-carboxymethyllysine via glyoxal-imine structures. GOLA, the amide cross-link, and 1,3-bis(5-amino-5-carboxypentyl)imidazolium salt (GOLD), the imidazolium cross-link, share a common intermediate. The ratio of GOLA to GOLD is greater when glyoxal levels are low at constant lysine concentrations. GOLA and GALA formation from the Amadori product of glucose and lysine depends directly upon oxidation. With the advanced glycation end product inhibitors aminoguanidine and pyridoxamine we were able to dissect oxidative fragmentation of the Amadori product as a second mechanism of GOLA formation exactly coinciding with N(epsilon)-carboxymethyllysine synthesis. In contrast, the formation of GALA appears to depend solely upon glyoxal-imines. After enzymatic hydrolysis GOLA was found at 66 pmol/mg of brunescent lens protein. This suggests amide protein modifications as important markers of pathophysiological processes.

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.

Coumarin amide derivatives as fluorescence chemosensors for cyanide anions

Energy Technology Data Exchange (ETDEWEB)

Wu, Qianqian [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Liu, Zhiqiang [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, Shandong (China); Cao, Duxia, E-mail: duxiacao@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Guan, Ruifang, E-mail: mse_guanrf@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Wang, Kangnan; Shan, Yanyan; Xu, Yongxiao; Ma, Lin [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China)

2015-07-01

Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group have been synthesized. Their photophysical properties and recognition properties for cyanide anions have been examined. The results indicate that the compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change, at the same time, obvious color and fluorescence change can be observed by naked eye. The in situ hydrogen nuclear magnetic resonance spectra and photophysical properties change confirm that Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin. - Highlights: • Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group were synthesized. • The compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change. • Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin.

Energetically Unfavorable Amide Conformations for N6-Acetyllysine Side Chains in Refined Protein Structures

Science.gov (United States)

Genshaft, Alexander; Moser, Joe-Ann S.; D'Antonio, Edward L.; Bowman, Christine M.; Christianson, David W.

2013-01-01

The reversible acetylation of lysine to form N6-acetyllysine in the regulation of protein function is a hallmark of epigenetics. Acetylation of the positively charged amino group of the lysine side chain generates a neutral N-alkylacetamide moiety that serves as a molecular “switch” for the modulation of protein function and protein-protein interactions. We now report the analysis of 381 N6-acetyllysine side chain amide conformations as found in 79 protein crystal structures and 11 protein NMR structures deposited in the Protein Data Bank (PDB) of the Research Collaboratory for Structural Bioinformatics. We find that only 74.3% of N6-acetyllysine residues in protein crystal structures and 46.5% in protein NMR structures contain amide groups with energetically preferred trans or generously trans conformations. Surprisingly, 17.6% of N6-acetyllysine residues in protein crystal structures and 5.3% in protein NMR structures contain amide groups with energetically unfavorable cis or generously cis conformations. Even more surprisingly, 8.1% of N6-acetyllysine residues in protein crystal structures and 48.2% in NMR structures contain amide groups with energetically prohibitive twisted conformations that approach the transition state structure for cis-trans isomerization. In contrast, 109 unique N-alkylacetamide groups contained in 84 highly-accurate small molecule crystal structures retrieved from the Cambridge Structural Database exclusively adopt energetically preferred trans conformations. Therefore, we conclude that cis and twisted N6-acetyllysine amides in protein structures deposited in the PDB are erroneously modeled due to their energetically unfavorable or prohibitive conformations. PMID:23401043

Synthesis, characterization and photo behavior of new poly(amide ...

African Journals Online (AJOL)

... and the interaction between clay and polymeric chains on the properties of nanocomposites films were investigated by using UV-Vis spectroscopy, thermogravimetric analysis (TGA) and water uptake measurements. KEY WORDS: Nanocomposite, Poly(amide-imide), Silicate particle, Polycondensation, Thermal behavior.

MICROBIAL DEGRADATION OF SEVEN AMIDES BY SUSPENDED BACTERIAL POPULATIONS

Science.gov (United States)

Microbial transformation rate constants were determined for seven amides in natural pond water. A second-order mathematical rate expression served as the model for describing the microbial transformation. Also investigated was the relationship between the infrared spectra and the...

Silver-catalyzed synthesis of amides from amines and aldehydes

Science.gov (United States)

Madix, Robert J; Zhou, Ling; Xu, Bingjun; Friend, Cynthia M; Freyschlag, Cassandra G

2014-11-18

The invention provides a method for producing amides via the reaction of aldehydes and amines with oxygen adsorbed on a metallic silver or silver alloy catalyst. An exemplary reaction is shown in Scheme 1: (I), (II), (III). ##STR00001##

Synthesis and characterization of new optically active poly(amide

African Journals Online (AJOL)

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Six new optically active poly(amide-imide)s (8a-f) were synthesized through the direct ... polyimides are widely used in the semiconductor and electronic packaging ... chiral polymers is of particular interest from the viewpoint of material science ...

Mesoporous Niobium Oxide Spheres as an Effective Catalyst for the Transamidation of Primary Amides with Amines

KAUST Repository

Ghosh, Subhash Chandra; Li, Cheng Chao; Zeng, Hua Chun; Ngiam, Joyce S Y; Seayad, Abdul M.; Chen, Anqi

2014-01-01

Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds. © 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

Stereoelectronic model to explain the resolution of enantiomeric ibuprofen amides on the Pirkle chiral stationary phase.

Science.gov (United States)

Nicoll-Griffith, D A

1987-07-31

A chiral recognition model is proposed which incorporates the electronic and steric interactions between amide derivatives of ibuprofen and the (R)-N-(3,5-dinitrobenzoyl)phenylglycine-derived Pirkle chiral stationary phase during high-performance liquid chromatography. Based on this rationale, amide derivatives of ibuprofen were prepared using 4-chloroaniline, 4-bromoaniline, aniline, 4-methoxyaniline and 1-aminonaphthylene to improve the enantiomer separation over previously reported results with this column. The amides prepared gave separation values of 1.16, 1.16, 1.19, 1.21 and 1.23, respectively. These high separation values are consistent with the proposed model.

Mesoporous Niobium Oxide Spheres as an Effective Catalyst for the Transamidation of Primary Amides with Amines

KAUST Repository

Ghosh, Subhash Chandra

2014-02-06

Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds. © 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

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.

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.

Polyurethanes elastomers with amide chain extenders of uniform length

NARCIS (Netherlands)

van der Schuur, J.M.; Noordover, B.A.J.; Noordover, Bart; Gaymans, R.J.

2006-01-01

Toluene diisocyanate based polyurethanes with amide extenders were synthesized poly(propylene oxide) with a number average molecular weight of 2000 and endcapped with toluene diisocyanate was used as the polyether segment. The chain extenders were based on poly(hexamethylene terephthalamide):

Polyuretehane elastomers with amide chain extenders of uniform length

NARCIS (Netherlands)

Schuur, van der M.; Noordover, B.A.J.; Gaymans, R.J.

2006-01-01

Toluene diisocyanate based polyurethanes with amide extenders were synthesized poly(propylene oxide) with a number average molecular weight of 2000 and endcapped with toluene diisocyanate was used as the polyether segment. The chain extenders were based on poly(hexamethylene terephthalamide):

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

Insight into the SEA amide thioester equilibrium. Application to the synthesis of thioesters at neutral pH.

Science.gov (United States)

Pira, S L; El Mahdi, O; Raibaut, L; Drobecq, H; Dheur, J; Boll, E; Melnyk, O

2016-07-26

The bis(2-sulfanylethyl)amide (SEA) N,S-acyl shift thioester surrogate has found a variety of useful applications in the field of protein total synthesis. Here we present novel insights into the SEA amide/thioester equilibrium in water which is an essential step in any reaction involving the thioester surrogate properties of the SEA group. We also show that the SEA amide thioester equilibrium can be efficiently displaced at neutral pH for accessing peptide alkylthioesters, i.e. the key components of the native chemical ligation (NCL) reaction.

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.

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.

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.

GLP-1 Amidation Efficiency Along the Length of the Intestine in Mice, Rats and Pigs and in GLP-1 Secreting Cell Lines

DEFF Research Database (Denmark)

Kuhre, Rune Ehrenreich; Albrechtsen, Nicolai Jacob Wewer; Windeløv, Johanne Agerlin

2014-01-01

and whether this varied with the six different locations. We also analyzed the amidation in 3 GLP-1 secreting cell lines (GLUTag, NCI-H716 and STC-1). To our surprise there were marked differences between the 3 species with respect to the concentration of GLP-1 in gut. In the mouse, concentrations increased...... sites, whereas rats and pigs on average had around 2.5 and 4 times higher levels of amidated compared to non-amidated GLP-1, although the ratio varied depending upon the location. GLUTag, NCI-H716 and STC-1 cells all exhibited partial amidation with 2-4 times higher levels of amidated compared to non...

Recombinant production of peptide C-terminal α-amides using an engineered intein

DEFF Research Database (Denmark)

Albertsen, Louise; Shaw, Allan C; Norrild, Jens Chr.

2013-01-01

is that they contain a C-terminal that is α-amidated, and this amidation is crucial for biological function. A challenge is to generate such peptides by recombinant means and particularly in a production scale. Here, we have examined an intein-mediated approach to generate a PYY derivative in a larger scale. Initially......, we experienced challenges with hydrolysis of the intein fusion protein, which was reduced by a T3C mutation in the intein. Subsequently, we further engineered the intein to decrease the absolute size and improve the relative yield of the PYY derivative, which was achieved by substituting 54 residues...

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

Novel amide derivatives as inhibitors of histone deacetylase: design, synthesis and SAR

DEFF Research Database (Denmark)

Andrianov, V.; Gailite, V.; Lola, D.

2009-01-01

Enzymatic inhibition of histone deacetylase (HDAC) activity is emerging as an innovative and effective approach for the treatment of cancer. A series of novel amide derivatives have been synthesized and evaluated for their ability to inhibit human HDACs. Multiple compounds were identified as potent...... HDAC inhibitors (HDACi), with IC(50) values in the low nanomolar (nM) range against enzyme activity in HeLa cell extracts and sub-microM for their in vitro anti-proliferative effect on cell lines. The introduction of an unsaturated linking group between the terminal aryl ring and the amide moiety...

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

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

Occurrence, biological activities and 13C NMR data of amides from Piper (Piperaceae)

International Nuclear Information System (INIS)

Nascimento, Jeferson C. do; Paula, Vanderlucia F. de; David, Jorge M.; David, Juceni P.

2012-01-01

This manuscript describes an update review with up to 285 references concerning the occurrence of amides from a variety of species of the genus Piper (Piperaceae). Besides addressing occurrence, this review also describes the biological activities attributed to extracts and pure compounds, a compiled 13 C NMR data set, the main correlations between structural and NMR spectroscopic data of these compounds, and employment of hyphened techniques such as LC-MS, GC-MS and NMR for analysis of amides from biological samples and crude Piper extracts. (author)

Chemometric characterization of the hydrogen bonding complexes of secondary amides and aromatic hydrocarbons

Directory of Open Access Journals (Sweden)

Jović Branislav

2012-01-01

Full Text Available The paper reports the results of the study of hydrogen bonding complexes between secondary amides and various aromatic hydrocarbons. The possibility of using chemometric methods was investigated in order to characterize N-H•••π hydrogen bonded complexes. Hierarchical clustering and Principal Component Analysis (PCA have been applied on infrared spectroscopic and Taft parameters of 43 N-substituted amide complexes with different aromatic hydrocarbons. Results obtained in this report are in good agreement with conclusions of other spectroscopic and thermodynamic analysis.

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.

Polyimides containing amide and perfluoroisopropylidene connecting groups

Science.gov (United States)

Dezern, James F. (Inventor)

1993-01-01

New, thermooxidatively stable polyimides were prepared from the reaction of aromatic dianhydrides containing isopropylidene bridging groups with aromatic diamines containing amide connecting groups between the rings. Several of these polyimides were shown to be semi-crystalline as evidenced by wide angle x ray scattering and differential scanning calorimetry. Most of the polyimides form tough, flexible films with high tensile properties. These polyimide films exhibit enhanced solubility in organic solvents.

Detection of atmospheric gaseous amines and amides by a high-resolution time-of-flight chemical ionization mass spectrometer with protonated ethanol reagent ions

Directory of Open Access Journals (Sweden)

L. Yao

2016-11-01

Full Text Available Amines and amides are important atmospheric organic-nitrogen compounds but high time resolution, highly sensitive, and simultaneous ambient measurements of these species are rather sparse. Here, we present the development of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS method, utilizing protonated ethanol as reagent ions to simultaneously detect atmospheric gaseous amines (C1 to C6 and amides (C1 to C6. This method possesses sensitivities of 5.6–19.4 Hz pptv−1 for amines and 3.8–38.0 Hz pptv−1 for amides under total reagent ion signals of  ∼  0.32 MHz. Meanwhile, the detection limits were 0.10–0.50 pptv for amines and 0.29–1.95 pptv for amides at 3σ of the background signal for a 1 min integration time. Controlled characterization in the laboratory indicates that relative humidity has significant influences on the detection of amines and amides, whereas the presence of organics has no obvious effects. Ambient measurements of amines and amides utilizing this method were conducted from 25 July to 25 August 2015 in urban Shanghai, China. While the concentrations of amines ranged from a few parts per trillion by volume to hundreds of parts per trillion by volume, concentrations of amides varied from tens of parts per trillion by volume to a few parts per billion by volume. Among the C1- to C6-amines, the C2-amines were the dominant species with concentrations up to 130 pptv. For amides, the C3-amides (up to 8.7 ppb were the most abundant species. The diurnal and backward trajectory analysis profiles of amides suggest that in addition to the secondary formation of amides in the atmosphere, industrial emissions could be important sources of amides in urban Shanghai. During the campaign, photo-oxidation of amines and amides might be a main loss pathway for them in daytime, and wet deposition was also an important sink.

Carbamoyl anion-initiated cascade reaction for stereoselective synthesis of substituted α-hydroxy-β-amino amides.

Science.gov (United States)

Lin, Chao-Yang; Ma, Peng-Ju; Sun, Zhao; Lu, Chong-Dao; Xu, Yan-Jun

2016-01-18

A carbamoyl anion-initiated cascade reaction with acylsilanes and imines has been used to rapidly construct substituted α-hydroxy-β-amino amides. The Brook rearrangement-mediated cascade allows the formation of two C-C bonds and one O-Si bond in a single pot. Using this approach, a range of α-aryl α-hydroxy-β-amino amides has been synthesized in high yields with excellent diastereoselectivities.

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.

Occurrence, biological activities and 13C NMR data of amides from Piper (Piperaceae

Directory of Open Access Journals (Sweden)

Jeferson C. do Nascimento

2012-01-01

Full Text Available This manuscript describes an update review with up to 285 references concerning the occurrence of amides from a variety of species of the genus Piper (Piperaceae. Besides addressing occurrence, this review also describes the biological activities attributed to extracts and pure compounds, a compiled 13C NMR data set, the main correlations between structural and NMR spectroscopic data of these compounds, and employment of hyphened techniques such as LC-MS, GC-MS and NMR for analysis of amides from biological samples and crude Piper extracts.

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

Directory of Open Access Journals (Sweden)

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.

Catalytic properties of lanthanide amide, imide and nitride formed by thermal degradation of liquid ammonia solutions of Eu and Yb metal

International Nuclear Information System (INIS)

Imamura, H.; Mizuno, K.; Ohishi, K.; Suda, E.; Kanda, K.; Sakata, Y.; Tsuchiya, S.

1998-01-01

The catalytic properties of lanthanide amide, imide and nitride prepared by the use of liquid ammonia solutions of lanthanide metals (Ln=Eu and Yb) were studied for catalytic hydrogenation. The reaction of Eu or Yb metal solutions in liquid ammonia with silica yielded SiO 2 -grafted lanthanide amide in the divalent state. The divalent amide showed catalytic activity for the selective hydrogenation of dienes and benzene. It was found that partial hydrogenation of benzene occurred with a very high selectivity for cyclohexene. Amides of calcium, strontium and barium were examined similarly in connection with catalytic studies on divalent amides. Imide and nitride, into which the lanthanide (Ln/AC) deposited by impregnation of active carbon (AC) with liquid ammonia solutions of lanthanide metals were converted thermally, were studied catalytically. It was concluded that imide or imide-like species generated during the thermal degradation of lanthanide amide to nitride were very active in the hydrogenation of ethene. Lanthanide nitride was virtually inactive, but the nitride highly dispersed on active carbon was activated when subjected to evacuation treatment above about 1000 K. (orig.)

Studies on peptide amidase-catalysed C-terminal peptide amidation in organic media with respect to its substrate specificity

Czech Academy of Sciences Publication Activity Database

Čeřovský, Václav; Kula, M. R.

2001-01-01

Roč. 33, - (2001), s. 183-187 ISSN 0885-4513 R&D Projects: GA ČR GA203/99/1458 Keywords : enzymic amidation * peptide amides * peptide synthesis Subject RIV: CC - Organic Chemistry Impact factor: 1.408, year: 2001

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

2005-01-01

Two amide synthetic derivatives of 3,4-di(OH)-hydrocinnamate (HC), 3,4-dihydroxyphenylpropionic (L-serine methyl ester) amide (E030) and 3,4-dihydroxyphenylpropionic (L-aspartic acid) amide (E076), were investigated to compare their lipid-lowering efficacy with HC. Male rats were fed a 1 g/100 g high-cholesterol diet for 6 weeks with supplements of either clofibrate (0.02%, w/w), HC (0.025%, w/w), E030 (0.039%, w/w) or E076 (0.041%, w/w). The clofibrate supplement was used as a positive control for the lipid-lowering efficacy. The food intakes and body weight gains were not significantly different among the groups. The plasma and hepatic cholesterol and triglyceride levels were lower in clofibrate, HC, E030, and E076-supplemented groups compared to the control group. The supplementation of HC and its amide derivatives was as effective as clofibrate in increasing the ratio of HDL-cholesterol to total plasma cholesterol and reducing the atherogenic index (AI). The hepatic cholesterol level in the HC and E076 groups was significantly lower than that in the clofibrate group. The hepatic 3-hydroxy-3-methylglutaryl-CoA (HMG-CoA reductase) and acyl-CoA:cholesterol acyltransferase (ACAT) activities were significantly lower in the all test groups than in the control group. The excretion of neutral sterol was significantly higher in the HC, E030, and E076-supplemented groups compared to the control group. The plasma AST and ALT activities, indirect indexes of hepatic toxicity, were significantly lower in the HC, E030, and E076-supplemented groups than in the control group. Accordingly, the current results suggest that E030 and E076, two amide synthetic derivatives of HC, are effective in lowering lipid activity

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...

Stereoselective reactions. XXXII. Enantioselective deprotonation of 4-tert-butylcyclohexanone by fluorine-containing chiral lithium amides derived from 1-phenylethylamine and 1-(1-naphthyl)ethylamine.

Science.gov (United States)

Aoki, K; Koga, K

2000-04-01

Enantioselective deprotonation of 4-tert-butylcyclohexanone was examined using 1-phenylethylamine- and 1-(1-naphthyl)ethylamine-derived chiral lithium amides having an alkyl or a fluoroalkyl substituent at the amide nitrogen. The lithium amides having a 2,2,2-trifluoroethyl group on the amide nitrogen are easily accessible in both enantiomeric forms, and were found to induce good enantioselectivity in the present reaction.

Enantioselective synthesis of almorexant via iridium-catalysed intramolecular allylic amidation

NARCIS (Netherlands)

Fananas Mastral, Martin; Teichert, Johannes F.; Fernandez-Salas, Jose Antonio; Heijnen, Dorus; Feringa, Ben L.

2013-01-01

An enantioselective synthesis of almorexant, a potent antagonist of human orexin receptors, is presented. The chiral tetrahydroisoquinoline core structure was prepared via iridium-catalysed asymmetric intramolecular allylic amidation. Further key catalytic steps of the synthesis include an oxidative

Green and selective synthesis of N-substituted amides using water soluble porphyrazinato copper(II) catalyst

International Nuclear Information System (INIS)

Ghodsinia, Sara S.E.; Akhlaghinia, Batool; Eshghi, Hossein; Safaei, Elham

2013-01-01

N, N',N , N ' -Tetramethyl tetra-2,3-pyridinoporphyrazinato copper(II) methyl sulfate ([Cu(2,3-tmtppa)](MeSO 4 ) 4 ) efficiently catalyzed the direct conversion of nitriles to N-substituted amides. The one pot selective synthesis of the N-substituted amides from nitriles and primary amines was performed in refluxing H 2 O. The catalyst was recovered and reused at least four times, maintaining its efficiency. (author)

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.

Practical Synthesis of Amides via Copper/ABNO-Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines.

Science.gov (United States)

Zultanski, Susan L; Zhao, Jingyi; Stahl, Shannon S

2016-05-25

A modular Cu/ABNO catalyst system has been identified that enables efficient aerobic oxidative coupling of alcohols and amines to amides. All four permutations of benzylic/aliphatic alcohols and primary/secondary amines are viable in this reaction, enabling broad access to secondary and tertiary amides. The reactions exhibit excellent functional group compatibility and are complete within 30 min-3 h at rt. All components of the catalyst system are commercially available.

Catalytic Ester and Amide to Amine Interconversion: Nickel-Catalyzed Decarbonylative Amination of Esters and Amides by C−O and C−C Bond Activation

KAUST Repository

Yue, Huifeng

2017-03-15

An efficient nickel-catalyzed decarbonylative amination reaction of aryl and heteroaryl esters has been achieved for the first time. The new amination protocol allows the direct interconversion of esters and amides into the corresponding amines and represents a good alternative to classical rearrangements as well as cross coupling reactions.

Catalytic Ester and Amide to Amine Interconversion: Nickel-Catalyzed Decarbonylative Amination of Esters and Amides by C−O and C−C Bond Activation

KAUST Repository

Yue, Huifeng; Guo, Lin; Liao, Hsuan-Hung; Cai, Yunfei; Zhu, Chen; Rueping, Magnus

2017-01-01

An efficient nickel-catalyzed decarbonylative amination reaction of aryl and heteroaryl esters has been achieved for the first time. The new amination protocol allows the direct interconversion of esters and amides into the corresponding amines and represents a good alternative to classical rearrangements as well as cross coupling reactions.

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....

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...

Steric effects in release of amides from linkers in solid-phase synthesis. Molecular mechanics modeling of key step in peptide and combinatorial chemistry

DEFF Research Database (Denmark)

Norrby, Per-Ola; Jensen, Knud Jørgen

2006-01-01

Acidolytic release of an amide from a solid support by C-N bond cleavage is all ubiquitous and crucial step in many solid-phase syntheses. We have used molecular modeling of a pseudo-equilibrium to explore substituent and steric effects in the release of peptides. The high acid-lability of the ba......Acidolytic release of an amide from a solid support by C-N bond cleavage is all ubiquitous and crucial step in many solid-phase syntheses. We have used molecular modeling of a pseudo-equilibrium to explore substituent and steric effects in the release of peptides. The high acid......-lability of the backbone amide linkage (BAL), which releases sec. amides, compared to C-terminal amide anchoring, which releases primary amides, was rationalized by steric relief upon cleavage. Thus, the relative stability of the carbenium ion formed from the linker in the acidolytic release is an insufficient measure...

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

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

Preparation and Evaluation at the Delta Opioid Receptor of a Series of Linear Leu-Enkephalin Analogues Obtained by Systematic Replacement of the Amides

Science.gov (United States)

2013-01-01

Leu-enkephalin analogues, in which the amide bonds were sequentially and systematically replaced either by ester or N-methyl amide bonds, were prepared using classical organic chemistry as well as solid phase peptide synthesis (SPPS). The peptidomimetics were characterized using competition binding, ERK1/2 phosphorylation, receptor internalization, and contractility assays to evaluate their pharmacological profile over the delta opioid receptor (DOPr). The lipophilicity (LogD7.4) and plasma stability of the active analogues were also measured. Our results revealed that the last amide bond can be successfully replaced by either an ester or an N-methyl amide bond without significantly decreasing the biological activity of the corresponding analogues when compared to Leu-enkephalin. The peptidomimetics with an N-methyl amide function between residues Phe and Leu were found to be more lipophilic and more stable than Leu-enkephalin. Findings from the present study further revealed that the hydrogen-bond donor properties of the fourth amide of Leu-enkephalin are not important for its biological activity on DOPr. Our results show that the systematic replacement of amide bonds by isosteric functions represents an efficient way to design and synthesize novel peptide analogues with enhanced stability. Our findings further suggest that such a strategy can also be useful to study the biological roles of amide bonds. PMID:23650868

Green and selective synthesis of N-substituted amides using water soluble porphyrazinato copper(II) catalyst

Energy Technology Data Exchange (ETDEWEB)

Ghodsinia, Sara S.E.; Akhlaghinia, Batool; Eshghi, Hossein, E-mail: akhlaghinia@um.ac.ir [Ferdowsi University of Mashhad (Iran, Islamic Republic of). Faculty of Sciences. Department of Chemistry; Safaei, Elham [Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan (Iran, Islamic Republic of). Department of Chemistry

2013-06-15

N, N',N{sup ,} N{sup '}-Tetramethyl tetra-2,3-pyridinoporphyrazinato copper(II) methyl sulfate ([Cu(2,3-tmtppa)](MeSO{sub 4}){sub 4}) efficiently catalyzed the direct conversion of nitriles to N-substituted amides. The one pot selective synthesis of the N-substituted amides from nitriles and primary amines was performed in refluxing H{sub 2}O. The catalyst was recovered and reused at least four times, maintaining its efficiency. (author)

Cis–Trans Amide Bond Rotamers in β-Peptoids and Peptoids: Evaluation of Stereoelectronic

DEFF Research Database (Denmark)

Laursen, Jonas Striegler; Engel-Andreasen, Jens; Fristrup, Peter

2013-01-01

to folding propensity. Thus, we here report an investigation of the effect of structural variations on the cis–trans amide bond rotamer equilibria in a selection of monomer model systems. In addition to various side chain effects, which correlated well with previous studies of α-peptoids, we present...... the synthesis and investigation of cis–trans isomerism in the first examples of peptoids and β-peptoids containing thioamide bonds as well as trifluoroacetylated peptoids and β-peptoids. These systems revealed an increase in the preference for cis-amides as compared to their parent compounds, and thus provide...

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

Directory of Open Access Journals (Sweden)

Katherine M. Byrd

2015-04-01

Full Text Available The conjugate addition reaction has been a useful tool in the formation of carbon–carbon bonds. The utility of this reaction has been demonstrated in the synthesis of many natural products, materials, and pharmacological agents. In the last three decades, there has been a significant increase in the development of asymmetric variants of this reaction. Unfortunately, conjugate addition reactions using α,β-unsaturated amides and lactams remain underdeveloped due to their inherently low reactivity. This review highlights the work that has been done on both diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams.

Structure-activity relationship in 34 trifluoromethylphenyl amides against Aedes aegypti

Science.gov (United States)

As part of our mission to discover new mosquito insecticides, 34 trifluoromethylphenyl amides were designed and synthesized. These compounds have trifluoromethyl- groups located in the ortho-, meta- or para- positions on the phenyl ring and have various substituents attached to the carbonyl carbon, ...

Straightforward uranium-catalyzed dehydration of primary amides to nitriles

International Nuclear Information System (INIS)

Enthaler, Stephan

2011-01-01

The efficient uranium-catalyzed dehydration of a variety of primary amides, using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) as a dehydration reagent, to the corresponding nitriles has been investigated. With this catalyst system, extraordinary catalyst activities and selectivities were feasible. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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.

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.

Occurrence, biological activities and {sup 13}C NMR data of amides from Piper (Piperaceae)

Energy Technology Data Exchange (ETDEWEB)

Nascimento, Jeferson C. do; Paula, Vanderlucia F. de [Universidade Estadual do Sudoeste da Bahia, Jequie, BA (Brazil). Dept. de Quimica e Exatas; David, Jorge M. [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Inst. de Quimica; David, Juceni P., E-mail: jmdavid@ufba.br [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Fac. de Farmacia

2012-07-01

This manuscript describes an update review with up to 285 references concerning the occurrence of amides from a variety of species of the genus Piper (Piperaceae). Besides addressing occurrence, this review also describes the biological activities attributed to extracts and pure compounds, a compiled {sup 13}C NMR data set, the main correlations between structural and NMR spectroscopic data of these compounds, and employment of hyphened techniques such as LC-MS, GC-MS and NMR for analysis of amides from biological samples and crude Piper extracts. (author)

Diverse amide analogs of sulindac for cancer treatment and prevention.

Science.gov (United States)

Mathew, Bini; Hobrath, Judith V; Connelly, Michele C; Kiplin Guy, R; Reynolds, Robert C

2017-10-15

Sulindac is a non-steroidal anti-inflammatory drug (NSAID) that has shown significant anticancer activity. Sulindac sulfide amide (1) possessing greatly reduced COX-related inhibition relative to sulindac displayed in vivo antitumor activity that was comparable to sulindac in a human colon tumor xenograft model. Inspired by these observations, a panel of diverse sulindac amide derivatives have been synthesized and their activity probed against three cancer cell lines (prostate, colon and breast). A neutral analog, compound 79 was identified with comparable potency relative to lead 1 and activity against a panel of lymphoblastic leukemia cell lines. Several new series also show good activity relative to the parent (1), including five analogs that also possess nanomolar inhibitory potencies against acute lymphoblastic leukemia cells. Several new analogs identified may serve as anticancer lead candidates for further development. Copyright © 2017 The Author(s). Published by Elsevier Ltd.. All rights reserved.

The amide III vibrational circular dichroism band as a probe to detect conformational preferences of alanine dipeptide in water.

Science.gov (United States)

Mirtič, Andreja; Merzel, Franci; Grdadolnik, Jože

2014-07-01

The conformational preferences of blocked alanine dipeptide (ADP), Ac-Ala-NHMe, in aqueous solution were studied using vibrational circular dichroism (VCD) together with density functional theory (DFT) calculations. DFT calculations of three most representative conformations of ADP surrounded by six explicit water molecules immersed in a dielectric continuum have proven high sensitivity of amide III VCD band shape that is characteristic for each conformation of the peptide backbone. The polyproline II (PII ) and αR conformation of ADP are associated with a positive VCD band while β conformation has a negative VCD band in amide III region. Knowing this spectral characteristic of each conformation allows us to assign the experimental amide III VCD spectrum of ADP. Moreover, the amide III region of the VCD spectrum was used to determine the relative populations of conformations of ADP in water. Based on the interpretation of the amide III region of VCD spectrum we have shown that dominant conformation of ADP in water is PII which is stabilized by hydrogen bonded water molecules between CO and NH groups on the peptide backbone. Copyright © 2014 Wiley Periodicals, Inc.

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.

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.

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.

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

Amide linkages mimic phosphates in RNA interactions with proteins and are well tolerated in the guide strand of short interfering RNAs

Energy Technology Data Exchange (ETDEWEB)

Mutisya, Daniel; Hardcastle, Travis; Cheruiyot, Samwel K.; Pallan, Pradeep S.; Kennedy, Scott D.; Egli, Martin; Kelley, Melissa L.; Smith, Anja van Brabant; Rozners, Eriks

2017-06-27

While the use of RNA interference (RNAi) in molecular biology and functional genomics is a well-established technology, in vivo applications of synthetic short interfering RNAs (siRNAs) require chemical modifications. We recently found that amides as non-ionic replacements for phosphodiesters may be useful modifications for optimization of siRNAs. Herein, we report a comprehensive study of systematic replacement of a single phosphate with an amide linkage throughout the guide strand of siRNAs. The results show that amides are surprisingly well tolerated in the seed and central regions of the guide strand and increase the silencing activity when placed between nucleosides 10 and 12, at the catalytic site of Argonaute. A potential explanation is provided by the first crystal structure of an amide-modified RNA–DNA with Bacillus halodurans RNase H1. The structure reveals how small changes in both RNA and protein conformation allow the amide to establish hydrogen bonding interactions with the protein. Molecular dynamics simulations suggest that these alternative binding modes may compensate for interactions lost due to the absence of a phosphodiester moiety. Our results suggest that an amide can mimic important hydrogen bonding interactions with proteins required for RNAi activity and may be a promising modification for optimization of biological properties of siRNAs.

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.

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.

Pd-Catalyzed Cross-Coupling Reactions of Amides and Aryl Mesylates

Science.gov (United States)

Dooleweerdt, Karin; Fors, Brett P.; Buchwald, Stephen L.

2010-01-01

A catalyst, based on a biarylphosphine ligand, for the Pd-catalyzed cross-coupling reactions of amides and aryl mesylates is described. This system allows an array of aryl and heteroaryl mesylates to be transformed into the corresponding N-arylamides in moderate to excellent yields. PMID:20420379

AmiD Is a Novel Peptidoglycan Amidase in Wolbachia Endosymbionts of Drosophila melanogaster

Directory of Open Access Journals (Sweden)

Miriam Wilmes

2017-08-01

Full Text Available Wolbachia endobacteria are obligate intracellular bacteria with a highly reduced genome infecting many arthropod and filarial species, in which they manipulate arthropod reproduction to increase their transmission and are essential for nematode development and survival. The Wolbachia genome encodes all enzymes required for the synthesis of the cell wall building block lipid II, although a peptidoglycan-like structure has not been detected. Despite the ability to synthesize lipid II, Wolbachia from arthropods and nematodes have only a subset of genes encoding enzymes involved in the periplasmic processing of lipid II and peptidoglycan recycling, with arthropods having two more than nematodes. We functionally analyzed the activity of the putative cell wall hydrolase AmiD from the Wolbachia endosymbiont of Drosophila melanogaster, an enzyme not encoded by the nematode endobacteria. Wolbachia AmiD has Zn2+-dependent amidase activity and cleaves intact peptidoglycan, monomeric lipid II and anhydromuropeptides, substrates that are generated during bacterial growth. AmiD may have been maintained in arthropod Wolbachia to avoid host immune recognition by degrading cell wall fragments in the periplasm. This is the first description of a wolbachial lipid II processing enzyme putatively expressed in the periplasm.

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.

Electron capture dissociation proceeds with a low degree of intramolecular migration of peptide amide hydrogens

DEFF Research Database (Denmark)

Rand, Kasper D; Adams, Christopher M; Zubarev, Roman A

2008-01-01

scrambling) that occurs during vibrational excitation of gas-phase ions. Unlike traditional collisional ion activation, electron capture dissociation (ECD) is not associated with substantial vibrational excitation. We investigated the extent of intramolecular backbone amide hydrogen (1H/2H) migration upon...... ECD using peptides with a unique selective deuterium incorporation. Our results show that only limited amide hydrogen migration occurs upon ECD, provided that vibrational excitation prior to the electron capture event is minimized. Peptide ions that are excessively vibrationally excited...

Decomposition of poly(amide-imide) film enameled on solid copper wire using atmospheric pressure non-equilibrium plasma.

Science.gov (United States)

Sugiyama, Kazuo; Suzuki, Katsunori; Kuwasima, Shusuke; Aoki, Yosuke; Yajima, Tatsuhiko

2009-01-01

The decomposition of a poly(amide-imide) thin film coated on a solid copper wire was attempted using atmospheric pressure non-equilibrium plasma. The plasma was produced by applying microwave power to an electrically conductive material in a gas mixture of argon, oxygen, and hydrogen. The poly(amide-imide) thin film was easily decomposed by argon-oxygen mixed gas plasma and an oxidized copper surface was obtained. The reduction of the oxidized surface with argon-hydrogen mixed gas plasma rapidly yielded a metallic copper surface. A continuous plasma heat-treatment process using a combination of both the argon-oxygen plasma and argon-hydrogen plasma was found to be suitable for the decomposition of the poly(amide-imide) thin film coated on the solid copper wire.

On the relationship between NMR-derived amide order parameters and protein backbone entropy changes.

Science.gov (United States)

Sharp, Kim A; O'Brien, Evan; Kasinath, Vignesh; Wand, A Joshua

2015-05-01

Molecular dynamics simulations are used to analyze the relationship between NMR-derived squared generalized order parameters of amide NH groups and backbone entropy. Amide order parameters (O(2) NH ) are largely determined by the secondary structure and average values appear unrelated to the overall flexibility of the protein. However, analysis of the more flexible subset (O(2) NH  entropy than that reported by the side chain methyl axis order parameters, O(2) axis . A calibration curve for backbone entropy vs. O(2) NH is developed, which accounts for both correlations between amide group motions of different residues, and correlations between backbone and side chain motions. This calibration curve can be used with experimental values of O(2) NH changes obtained by NMR relaxation measurements to extract backbone entropy changes, for example, upon ligand binding. In conjunction with our previous calibration for side chain entropy derived from measured O(2) axis values this provides a prescription for determination of the total protein conformational entropy changes from NMR relaxation measurements. © 2015 Wiley Periodicals, Inc.

Fatty Amides from Crude Rice Bran Oil as Green Corrosion Inhibitors

Directory of Open Access Journals (Sweden)

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.

Fluorine walk: The impact of fluorine in quinolone amides on their activity against African sleeping sickness.

Science.gov (United States)

Berninger, Michael; Erk, Christine; Fuß, Antje; Skaf, Joseph; Al-Momani, Ehab; Israel, Ina; Raschig, Martina; Güntzel, Paul; Samnick, Samuel; Holzgrabe, Ulrike

2018-05-25

Human African Trypanosomiasis, also known as African sleeping sickness, is caused by the parasitic protozoa of the genus Trypanosoma. If there is no pharmacological intervention, the parasites can cross the blood-brain barrier (BBB), inevitably leading to death of the patients. Previous investigation identified the quinolone amide GHQ168 as a promising lead compound having a nanomolar activity against T. b. brucei. Here, the role of a fluorine substitution at different positions was investigated in regard to toxicity, pharmacokinetics, and antitrypanosomal activity. This 'fluorine walk' led to new compounds with improved metabolic stability and consistent activity against T. b. brucei. The ability of the new quinolone amides to cross the BBB was confirmed using an 18 F-labelled quinolone amide derivative by means of ex vivo autoradiography of a murine brain. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

AMID: Accurate Magnetic Indoor Localization Using Deep Learning

Directory of Open Access Journals (Sweden)

Namkyoung Lee

2018-05-01

Full Text Available Geomagnetic-based indoor positioning has drawn a great attention from academia and industry due to its advantage of being operable without infrastructure support and its reliable signal characteristics. However, it must overcome the problems of ambiguity that originate with the nature of geomagnetic data. Most studies manage this problem by incorporating particle filters along with inertial sensors. However, they cannot yield reliable positioning results because the inertial sensors in smartphones cannot precisely predict the movement of users. There have been attempts to recognize the magnetic sequence pattern, but these attempts are proven only in a one-dimensional space, because magnetic intensity fluctuates severely with even a slight change of locations. This paper proposes accurate magnetic indoor localization using deep learning (AMID, an indoor positioning system that recognizes magnetic sequence patterns using a deep neural network. Features are extracted from magnetic sequences, and then the deep neural network is used for classifying the sequences by patterns that are generated by nearby magnetic landmarks. Locations are estimated by detecting the landmarks. AMID manifested the proposed features and deep learning as an outstanding classifier, revealing the potential of accurate magnetic positioning with smartphone sensors alone. The landmark detection accuracy was over 80% in a two-dimensional environment.

Direct Synthesis of Medium-Bridged Twisted Amides via a Transannular Cyclization Strategy

Science.gov (United States)

Szostak, Michal; Aubé, Jeffrey

2009-01-01

The sequential RCM to construct a challenging medium-sized ring followed by a transannular cyclization across a medium-sized ring delivers previously unattainable twisted amides from simple acyclic precursors. PMID:19708701

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.)

Using non-invasive molecular spectroscopic techniques to detect unique aspects of protein Amide functional groups and chemical properties of modeled forage from different sourced-origins.

Science.gov (United States)

Ji, Cuiying; Zhang, Xuewei; Yu, Peiqiang

2016-03-05

The non-invasive molecular spectroscopic technique-FT/IR is capable to detect the molecular structure spectral features that are associated with biological, nutritional and biodegradation functions. However, to date, few researches have been conducted to use these non-invasive molecular spectroscopic techniques to study forage internal protein structures associated with biodegradation and biological functions. The objectives of this study were to detect unique aspects and association of protein Amide functional groups in terms of protein Amide I and II spectral profiles and chemical properties in the alfalfa forage (Medicago sativa L.) from different sourced-origins. In this study, alfalfa hay with two different origins was used as modeled forage for molecular structure and chemical property study. In each forage origin, five to seven sources were analyzed. The molecular spectral profiles were determined using FT/IR non-invasive molecular spectroscopy. The parameters of protein spectral profiles included functional groups of Amide I, Amide II and Amide I to II ratio. The results show that the modeled forage Amide I and Amide II were centered at 1653 cm(-1) and 1545 cm(-1), respectively. The Amide I spectral height and area intensities were from 0.02 to 0.03 and 2.67 to 3.36 AI, respectively. The Amide II spectral height and area intensities were from 0.01 to 0.02 and 0.71 to 0.93 AI, respectively. The Amide I to II spectral peak height and area ratios were from 1.86 to 1.88 and 3.68 to 3.79, respectively. Our results show that the non-invasive molecular spectroscopic techniques are capable to detect forage internal protein structure features which are associated with forage chemical properties. Copyright © 2015 Elsevier B.V. All rights reserved.

Amide linkages mimic phosphates in RNA interactions with proteins and are well tolerated in the guide strand of short interfering RNAs.

Science.gov (United States)

Mutisya, Daniel; Hardcastle, Travis; Cheruiyot, Samwel K; Pallan, Pradeep S; Kennedy, Scott D; Egli, Martin; Kelley, Melissa L; Smith, Anja van Brabant; Rozners, Eriks

2017-08-21

While the use of RNA interference (RNAi) in molecular biology and functional genomics is a well-established technology, in vivo applications of synthetic short interfering RNAs (siRNAs) require chemical modifications. We recently found that amides as non-ionic replacements for phosphodiesters may be useful modifications for optimization of siRNAs. Herein, we report a comprehensive study of systematic replacement of a single phosphate with an amide linkage throughout the guide strand of siRNAs. The results show that amides are surprisingly well tolerated in the seed and central regions of the guide strand and increase the silencing activity when placed between nucleosides 10 and 12, at the catalytic site of Argonaute. A potential explanation is provided by the first crystal structure of an amide-modified RNA-DNA with Bacillus halodurans RNase H1. The structure reveals how small changes in both RNA and protein conformation allow the amide to establish hydrogen bonding interactions with the protein. Molecular dynamics simulations suggest that these alternative binding modes may compensate for interactions lost due to the absence of a phosphodiester moiety. Our results suggest that an amide can mimic important hydrogen bonding interactions with proteins required for RNAi activity and may be a promising modification for optimization of biological properties of siRNAs. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Effect of hydration on the amide I band in the binary solvents dioxane-D2O and dioxane-H2O

International Nuclear Information System (INIS)

Kobayashi, M.; Kobayashi, M.

1980-01-01

Hydration of amides in aqueous solutions has been studied by measuring the infrared spectra of amides (benzamide, p-methoxybenzamide, and ropionamide) in dioxane-D 2 O and dioxane-H 2 O mixtures. The absorption due to the C=O stretching (or amide I band) exhibited a very remarkable red shift accompanied by a characteristic change of the band shape as the water content in the medium increased. The spectral change is attributed to the change of the hydration state at the carbonyl oxygen. In the aqueous mixtures, amide molecules participate in an equilibrium among various states of hydration. The weighted mean frequency of the ν/sub C = O/ absorption, anti ν/sub C = O/, varied in proportion to the water contained in the medium. The difference between the anti ν/sub C = O/ value in pure water and that in pure dioxane,Δ anti ν, was used as a measure of the maximum degree of hydration. It was larger for propionamide than for the aromatic amides, suggesting that the steric effect of the substituents is of major importance in hydration. The isotope effect, Δ anti ν/sub D 2 O//Δ anti ν/sub H 2 O/, in the range from 1.4 to 1.6 for all cases examined, indicated that stronger hydration of amides occurred with D 2 O than with H 2 O

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

Directory of Open Access Journals (Sweden)

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.

In vitro evaluation of N-methyl amide tripeptidomimetics as substrates for the human intestinal di-/tri-peptide transporter hPEPT1

DEFF Research Database (Denmark)

Andersen, Rikke; Nielsen, Carsten Uhd; Begtrup, Mikael

2006-01-01

application of N-methyl amide bioisosteres as peptide bond replacements in tripeptides in order to decrease degradation by peptidases and yet retain affinity for and transport via hPEPT1. Seven structurally diverse N-methyl amide tripeptidomimetics were selected based on a principal component analysis...... of structural properties of 6859 N-methyl amide tripeptidomimetics. In vitro extracellular degradation of the selected tripeptidomimetics as well as affinity for and transepithelial transport via hPEPT1 were investigated in Caco-2 cells. Decreased apparent degradation was observed for all tripeptidomimetics...... to be substrates for hPEPT1 than tripeptidomimetics with charged side chains. The results of the present study indicate that the N-methyl amide peptide bond replacement approach for increasing bioavailability of tripeptidomimetic drug candidates is not generally applicable to all tripeptides. Nevertheless...

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...

Mammalian peptidylglycine alpha-amidating monooxygenase (PAM) mRNA expression can be modulated by the La autoantigen

DEFF Research Database (Denmark)

Brenet, Fabienne; Dussault, Nadège; Borch, Jonas

2005-01-01

Peptidylglycine alpha-amidating monooxygenase (PAM; EC 1.14.17.3) catalyzes the COOH-terminal alpha-amidation of peptidylglycine substrates, yielding amidated products. We have previously reported a putative regulatory RNA binding protein (PAM mRNA-BP) that binds specifically to the 3' untranslated...... region (UTR) of PAM-mRNA. Here, the PAM mRNA-BP was isolated and revealed to be La protein using affinity purification onto a 3' UTR PAM RNA, followed by tandem mass spectrometry identification. We determined that the core binding sequence is approximately 15-nucleotides (nt) long and is located 471 nt...... downstream of the stop codon. Moreover, we identified the La autoantigen as a protein that specifically binds the 3' UTR of PAM mRNA in vivo and in vitro. Furthermore, La protein overexpression caused a nuclear retention of PAM mRNAs and resulted in the down-regulation of endogenous PAM activity. Most...

New screening strategy and analysis for identification of allosteric modulators for glucagon-like peptide-1 receptor using GLP-1 (9-36) amide.

Science.gov (United States)

Nakane, Atsushi; Gotoh, Yusuke; Ichihara, Junji; Nagata, Hidetaka

2015-12-15

The glucagon-like peptide-1 receptor (GLP-1R) is an important physiologic regulator of insulin secretion and a major therapeutic target for diabetes mellitus. GLP-1 (7-36) amide (active form of GLP-1) is truncated to GLP-1 (9-36) amide, which has been described as a weak agonist of GLP-1R and the major form of GLP-1 in the circulation. New classes of positive allosteric modulators (PAMs) for GLP-1R may offer improved therapeutic profiles. To identify these new classes, we developed novel and robust primary and secondary high-throughput screening (HTS) systems in which PAMs were identified to enhance the GLP-1R signaling induced by GLP-1 (9-36) amide. Screening enabled identification of two compounds, HIT-465 and HIT-736, which possessed new patterns of modulation of GLP-1R. We investigated the ability of these compounds to modify GLP-1R signaling enhanced GLP-1 (9-36) amide- and/or GLP-1 (7-36) amide-mediated cyclic adenosine monophosphate (cAMP) accumulation. These compounds also had unique profiles with regard to allosteric modulation of multiple downstream signaling (PathHunter β-arrestin signaling, PathHunter internalization signaling, microscopy-based internalization assay). We found allosteric modulation patterns to be obviously different among HIT-465, HIT-736, and Novo Nordisk compound 2. This work may enable the design of new classes of drug candidates by targeting modulation of GLP-1 (7-36) amide and GLP-1 (9-36) amide. Copyright © 2015 Elsevier Inc. All rights reserved.

Design and optimization of selective azaindole amide M1 positive allosteric modulators.

Science.gov (United States)

Davoren, Jennifer E; O'Neil, Steven V; Anderson, Dennis P; Brodney, Michael A; Chenard, Lois; Dlugolenski, Keith; Edgerton, Jeremy R; Green, Michael; Garnsey, Michelle; Grimwood, Sarah; Harris, Anthony R; Kauffman, Gregory W; LaChapelle, Erik; Lazzaro, John T; Lee, Che-Wah; Lotarski, Susan M; Nason, Deane M; Obach, R Scott; Reinhart, Veronica; Salomon-Ferrer, Romelia; Steyn, Stefanus J; Webb, Damien; Yan, Jiangli; Zhang, Lei

2016-01-15

Selective activation of the M1 receptor via a positive allosteric modulator (PAM) is a new approach for the treatment of the cognitive impairments associated with schizophrenia and Alzheimer's disease. A novel series of azaindole amides and their key pharmacophore elements are described. The nitrogen of the azaindole core is a key design element as it forms an intramolecular hydrogen bond with the amide N-H thus reinforcing the bioactive conformation predicted by published SAR and our homology model. Representative compound 25 is a potent and selective M1 PAM that has well aligned physicochemical properties, adequate brain penetration and pharmacokinetic (PK) properties, and is active in vivo. These favorable properties indicate that this series possesses suitable qualities for further development and studies. Copyright © 2015 Elsevier Ltd. All rights reserved.

The influence of chirality in the amide side chain on the carbonyl orientation in rotational isomers of 3-carbamoylpyridinium halides

NARCIS (Netherlands)

Bastiaansen, L.A.M.; Vermeulen, T.J.M.; Buck, H.M.; Smeets, W.J.J.; Kanters, J.A.

1988-01-01

The direction of the carbonyl orientation in solid amide rotamers of 3-(N-methyl-N-a-methylbenzylcarbamoyl)-1,2,4-trimethylpyridinium iodide is governed by the (R)- or (S)-chirality in the amide side chain; X-ray structures and c.d. spectra are correlated.

Uranium and plutonium extraction by N,N-dialkyl-amides using multistage mixer-settler extractors

Energy Technology Data Exchange (ETDEWEB)

Ban, Y.; Hotoku, S.; Tsutsui, N.; Suzuki, A.; Tsubata, Y.; Matsumura, T.

2016-07-01

N,N-Dialkyl-amides (mono-amides) are known as extractants for U and Pu, and many studies have been carried out mainly by single-stage batch method. We have focused on two mono amides: N,N-di(2-ethylhexyl)-2,2-dimethylpropanamide (DEHDMPA) and N,N-di(2-ethylhexyl)butanamide (DEHBA), and proposed a multistage extraction process for recovering U and Pu by these mono-amides. A continuous counter-current experiment was carried out to demonstrate the validity of this process. This process consisted of two cycles, and the first cycle and the second cycle employed DEHDMPA and DEHBA as extractants, respectively. The feed solution for the first cycle was 5.1 mol/dm{sup 3} (M) nitric acid containing 0.92 M U, 1.6 mM Pu, and 0.6 mM Np. The raffinate collected in the first cycle was used as the feed for the second cycle. The ratios of U recovered in the U fraction and U-Pu fraction were 99.1% and 0.8%, respectively, and the ratios of U in the used solvents were <0.04%. The ratio of Pu recovered in the U-Pu fraction was 99.7%, and the ratio of Pu in the used solvents was in the order of 10{sup -3} - 10{sup -4}%. The concentration ratio of U with respect to Pu in the U-Pu fraction was 9, and this indicated that Pu was not isolated. The decontamination factor of U with respect to Pu in the U fraction was obtained as 4.5*10{sup 5}. These results supported the validity of the proposed process. (authors)

Analytical applications of resins containing amide and polyamine functional groups

International Nuclear Information System (INIS)

Orf, G.M.

1977-01-01

Resins are prepared by chemically bonding N,N-dialkylamides and polyamine functional groups to Amberlite XAD-4. These resins are applied to the concentration of metal ions from dilute aqueous solution and the rapid separation of metal ions by high-speed liquid chromatography with continuous on-line detection of the eluent stream. A dibutyl amide resin is used for the separation of uranium(VI), thorium(IV), and zirconium(IV) from each other and several other metal ions. Uranium(VI) and thorium(IV) are determined in the presence of large excesses of foreign metal ions and anions. A practical application of the amide resin is studied by determining uranium in low grade uranium ores. The amide resin is also used for the selective concentration of gold(III) from seawater. A triethylenetetramine resin is used for the separation of copper(II) from equal molar amounts and large excesses of nickel(II), cobalt(II), zinc(II), cadmium(II), iron(III) and aluminum(III). Copper(II), nickel(II), zinc(II), cobalt(II) and cadmium(II) are determined in the presence of large excesses of calcium(II) and magnesium(II). The resin was found to be selective for silver(I) and mercury(II) at low pH values and a rapid separation of equal molar amounts of copper(II) and silver(I) was performed. The resin was also found to have an affinity for anionic metal complexes such as iron(III)-tartrate when the resin is in the hydrogen form. A study of the retention of the anions chromium(III)-tartrate and dichromate at various pH values was performed to better understand the anion exchange properties of the resin. Triethylenetetramine resins were also prepared from polystyrene gel to make a resin with higher capacities for copper

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.

Antimicrobial and allelopathic potential of the amides isolated from the roots of Ottonia martiana miq., piperaceae

International Nuclear Information System (INIS)

Cunico, Miriam Machado; Dias, Josiane G.; Miguel, Marilis D.; Miguel, Obdulio Gomes; Auer, Celso Garcia; Cocco, Lilian C.; Lopes, Andre R.; Yamamoto, Carlos I.; Monache, Franco Delle

2006-01-01

Two amides, piperovatine and isopiperlonguminine, were isolated from the roots of Ottonia martiana Miq., a herbaceous shrub commonly used in folk medicine in the treatment of toothache. The crude extract (CE) and isolated compounds were submitted to bioautography and allelopathic assay. The bioautograms allowed the detection of compounds with antibacterial activity and the identification of the bioactive substance piperovatine. The CE and amides exhibited an allelopathic effect on Lactuca sativa (lettuce) seedling growth but did not affect the seeds' germinability. (author)

Hydrolysis of Ibuprofen Nitrile and Ibuprofen Amide and Deracemisation of Ibuprofen Using Nocardia corallina B-276

OpenAIRE

Myrna Solís-Oba; Norberto Manjarrez; Aida Solís; Ricardo Lievano; Herminia Inés Pérez

2012-01-01

A novel application of whole cells of Nocardia corallina B-276 for the deracemisation of ibuprofen is reported. This microorganism successfully hydrolysed ibuprofen nitrile to ibuprofen amide, and ibuprofen amide to ibuprofen, using a suspension of cells in a potassium phosphate buffer solution (0.1 M, pH = 7.0). These results can be explained by the presence of NHase and amidase enzymes, but the reactions are not enantioselective and low ee values were obtained. However, (R)-ibuprofen was is...

Determination of Backbone Amide Hydrogen Exchange Rates of Cytochrome c Using Partially Scrambled Electron Transfer Dissociation Data

Science.gov (United States)

Hamuro, Yoshitomo; E, Sook Yen

2018-05-01

The technological goal of hydrogen/deuterium exchange-mass spectrometry (HDX-MS) is to determine backbone amide hydrogen exchange rates. The most critical challenge to achieve this goal is obtaining the deuterium incorporation in single-amide resolution, and gas-phase fragmentation may provide a universal solution. The gas-phase fragmentation may generate the daughter ions which differ by a single amino acid and the difference in deuterium incorporations in the two analogous ions can yield the deuterium incorporation at the sub-localized site. Following the pioneering works by Jørgensen and Rand, several papers utilized the electron transfer dissociation (ETD) to determine the location of deuterium in single-amide resolution. This paper demonstrates further advancement of the strategy by determining backbone amide hydrogen exchange rates, instead of just determining deuterium incorporation at a single time point, in combination with a wide time window monitoring. A method to evaluate the effects of scrambling and to determine the exchange rates from partially scrambled HDX-ETD-MS data is described. All parent ions for ETD fragmentation were regio-selectively scrambled: The deuterium in some regions of a peptide ion was scrambled while that in the other regions was not scrambled. The method determined 31 backbone amide hydrogen exchange rates of cytochrome c in the non-scrambled regions. Good fragmentation of a parent ion, a low degree of scrambling, and a low number of exchangeable hydrogens in the preceding side chain are the important factors to determine the exchange rate. The exchange rates determined by the HDX-MS are in good agreement with those determined by NMR. [Figure not available: see fulltext.

Determination of Backbone Amide Hydrogen Exchange Rates of Cytochrome c Using Partially Scrambled Electron Transfer Dissociation Data.

Science.gov (United States)

Hamuro, Yoshitomo; E, Sook Yen

2018-05-01

The technological goal of hydrogen/deuterium exchange-mass spectrometry (HDX-MS) is to determine backbone amide hydrogen exchange rates. The most critical challenge to achieve this goal is obtaining the deuterium incorporation in single-amide resolution, and gas-phase fragmentation may provide a universal solution. The gas-phase fragmentation may generate the daughter ions which differ by a single amino acid and the difference in deuterium incorporations in the two analogous ions can yield the deuterium incorporation at the sub-localized site. Following the pioneering works by Jørgensen and Rand, several papers utilized the electron transfer dissociation (ETD) to determine the location of deuterium in single-amide resolution. This paper demonstrates further advancement of the strategy by determining backbone amide hydrogen exchange rates, instead of just determining deuterium incorporation at a single time point, in combination with a wide time window monitoring. A method to evaluate the effects of scrambling and to determine the exchange rates from partially scrambled HDX-ETD-MS data is described. All parent ions for ETD fragmentation were regio-selectively scrambled: The deuterium in some regions of a peptide ion was scrambled while that in the other regions was not scrambled. The method determined 31 backbone amide hydrogen exchange rates of cytochrome c in the non-scrambled regions. Good fragmentation of a parent ion, a low degree of scrambling, and a low number of exchangeable hydrogens in the preceding side chain are the important factors to determine the exchange rate. The exchange rates determined by the HDX-MS are in good agreement with those determined by NMR. Graphical Abstract ᅟ.

Determination of Backbone Amide Hydrogen Exchange Rates of Cytochrome c Using Partially Scrambled Electron Transfer Dissociation Data

Science.gov (United States)

Hamuro, Yoshitomo; E, Sook Yen

2018-03-01

The technological goal of hydrogen/deuterium exchange-mass spectrometry (HDX-MS) is to determine backbone amide hydrogen exchange rates. The most critical challenge to achieve this goal is obtaining the deuterium incorporation in single-amide resolution, and gas-phase fragmentation may provide a universal solution. The gas-phase fragmentation may generate the daughter ions which differ by a single amino acid and the difference in deuterium incorporations in the two analogous ions can yield the deuterium incorporation at the sub-localized site. Following the pioneering works by Jørgensen and Rand, several papers utilized the electron transfer dissociation (ETD) to determine the location of deuterium in single-amide resolution. This paper demonstrates further advancement of the strategy by determining backbone amide hydrogen exchange rates, instead of just determining deuterium incorporation at a single time point, in combination with a wide time window monitoring. A method to evaluate the effects of scrambling and to determine the exchange rates from partially scrambled HDX-ETD-MS data is described. All parent ions for ETD fragmentation were regio-selectively scrambled: The deuterium in some regions of a peptide ion was scrambled while that in the other regions was not scrambled. The method determined 31 backbone amide hydrogen exchange rates of cytochrome c in the non-scrambled regions. Good fragmentation of a parent ion, a low degree of scrambling, and a low number of exchangeable hydrogens in the preceding side chain are the important factors to determine the exchange rate. The exchange rates determined by the HDX-MS are in good agreement with those determined by NMR. [Figure not available: see fulltext.

Effective representation of amide III, II, I, and A modes on local vibrational modes: Analysis of ab initio quantum calculation results.

Science.gov (United States)

Hahn, Seungsoo

2016-10-28

The Hamiltonian matrix for the first excited vibrational states of a protein can be effectively represented by local vibrational modes constituting amide III, II, I, and A modes to simulate various vibrational spectra. Methods for obtaining the Hamiltonian matrix from ab initio quantum calculation results are discussed, where the methods consist of three steps: selection of local vibrational mode coordinates, calculation of a reduced Hessian matrix, and extraction of the Hamiltonian matrix from the Hessian matrix. We introduce several methods for each step. The methods were assessed based on the density functional theory calculation results of 24 oligopeptides with four different peptide lengths and six different secondary structures. The completeness of a Hamiltonian matrix represented in the reduced local mode space is improved by adopting a specific atom group for each amide mode and reducing the effect of ignored local modes. The calculation results are also compared to previous models using C=O stretching vibration and transition dipole couplings. We found that local electric transition dipole moments of the amide modes are mainly bound on the local peptide planes. Their direction and magnitude are well conserved except amide A modes, which show large variation. Contrary to amide I modes, the vibrational coupling constants of amide III, II, and A modes obtained by analysis of a dipeptide are not transferable to oligopeptides with the same secondary conformation because coupling constants are affected by the surrounding atomic environment.

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.

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.

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.

Determination of Equine Cytochrome c Backbone Amide Hydrogen/Deuterium Exchange Rates by Mass Spectrometry Using a Wider Time Window and Isotope Envelope.

Science.gov (United States)

Hamuro, Yoshitomo

2017-03-01

A new strategy to analyze amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) data is proposed, utilizing a wider time window and isotope envelope analysis of each peptide. While most current scientific reports present HDX-MS data as a set of time-dependent deuteration levels of peptides, the ideal HDX-MS data presentation is a complete set of backbone amide hydrogen exchange rates. The ideal data set can provide single amide resolution, coverage of all exchange events, and the open/close ratio of each amide hydrogen in EX2 mechanism. Toward this goal, a typical HDX-MS protocol was modified in two aspects: measurement of a wider time window in HDX-MS experiments and deconvolution of isotope envelope of each peptide. Measurement of a wider time window enabled the observation of deuterium incorporation of most backbone amide hydrogens. Analysis of the isotope envelope instead of centroid value provides the deuterium distribution instead of the sum of deuteration levels in each peptide. A one-step, global-fitting algorithm optimized exchange rate and deuterium retention during the analysis of each amide hydrogen by fitting the deuterated isotope envelopes at all time points of all peptides in a region. Application of this strategy to cytochrome c yielded 97 out of 100 amide hydrogen exchange rates. A set of exchange rates determined by this approach is more appropriate for a patent or regulatory filing of a biopharmaceutical than a set of peptide deuteration levels obtained by a typical protocol. A wider time window of this method also eliminates false negatives in protein-ligand binding site identification. Graphical Abstract ᅟ.

Study of the UV Light Conversion of Feruloyl Amides from Portulaca oleracea and Their Inhibitory Effect on IL-6-Induced STAT3 Activation.

Science.gov (United States)

Hwang, Joo Tae; Kim, Yesol; Jang, Hyun-Jae; Oh, Hyun-Mee; Lim, Chi-Hwan; Lee, Seung Woong; Rho, Mun-Chual

2016-06-30

Two new feruloyl amides, N-cis-hibiscusamide (5) and (7'S)-N-cis-feruloylnormetanephrine (9), and eight known feruloyl amides were isolated from Portulaca oleracea L. and the geometric conversion of the ten isolated feruloyl amides by UV light was verified. The structures of the feruloyl amides were determined based on spectroscopic data and comparison with literature data. The NMR data revealed that the structures of the isolated compounds showed cis/trans-isomerization under normal laboratory light conditions. Therefore, cis and trans-isomers of feruloyl amides were evaluated for their convertibility and stability by UV light of a wavelength of 254 nm. After 96 h of UV light exposure, 23.2%-35.0% of the cis and trans-isomers were converted to trans-isomers. Long-term stability tests did not show any significant changes. Among all compounds and conversion mixtures collected, compound 6 exhibited the strongest inhibition of IL-6-induced STAT3 activation in Hep3B cells, with an IC50 value of 0.2 μM. This study is the first verification of the conversion rates and an equilibrium ratio of feruloyl amides. These results indicate that this natural material might provide useful information for the treatment of various diseases involving IL-6 and STAT3.

Plasma-enabled sensing of urea and related amides on polyaniline

Czech Academy of Sciences Publication Activity Database

Puliyalil, H.; Slobodian, P.; Sedlacik, M.; Benlikaya, R.; Říha, Pavel; Ostrikov, K.; Cvelbar, U.

2016-01-01

Roč. 10, č. 2 (2016), s. 265-272 ISSN 2095-0179 Grant - others:Ministerstvo školství, mládeže a tělovýchovy (MŠMT)(CZ) LO1504 Institutional support: RVO:67985874 Keywords : gas sensing * urea * PANI * amides * plasma Subject RIV: BK - Fluid Dynamics Impact factor: 1.712, year: 2016

Mosher Amides: Determining the Absolute Stereochemistry of Optically-Active Amines

Science.gov (United States)

Allen, Damian A.; Tomaso, Anthony E., Jr.; Priest, Owen P.; Hindson, David F.; Hurlburt, Jamie L.

2008-01-01

The use of chiral reagents for the derivatization of optically-active amines and alcohols for the purpose of determining their enantiomeric purity or absolute configuration is a tool used by many chemists. Among the techniques used, Mosher's amide and Mosher's ester analyses are among the most reliable and one of the most often used. Despite this,…

Nanoporous amide networks based on tetraphenyladamantane for selective CO2capture

KAUST Repository

Zulfiqar, Sonia; Mantione, Daniele; El Tall, Omar; Sarwar, Muhammad Ilyas; Ruipé rez, Fernando; Rothenberger, Alexander; Mecerreyes, David

2016-01-01

Reduction of anthropogenic CO2 emissions and CO2 separation from post-combustion flue gases are among the imperative issues in the spotlight at present. Hence, it is highly desirable to develop efficient adsorbents for mitigating climate change with possible energy savings. Here, we report the design of a facile one pot catalyst-free synthetic protocol for the generation of three different nitrogen rich nanoporous amide networks (NANs) based on tetraphenyladamantane. Besides the porous architecture, CO2 capturing potential and high thermal stability, these NANs possess notable CO2/N2 selectivity with reasonable retention while increasing the temperature from 273 K to 298 K. The quantum chemical calculations also suggest that CO2 interacts mainly in the region of polar amide groups (-CONH-) present in NANs and this interaction is much stronger than that with N2 thus leading to better selectivity and affirming them as promising contenders for efficient gas separation. © The Royal Society of Chemistry 2016.

Nanoporous amide networks based on tetraphenyladamantane for selective CO2capture

KAUST Repository

Zulfiqar, Sonia

2016-04-19

Reduction of anthropogenic CO2 emissions and CO2 separation from post-combustion flue gases are among the imperative issues in the spotlight at present. Hence, it is highly desirable to develop efficient adsorbents for mitigating climate change with possible energy savings. Here, we report the design of a facile one pot catalyst-free synthetic protocol for the generation of three different nitrogen rich nanoporous amide networks (NANs) based on tetraphenyladamantane. Besides the porous architecture, CO2 capturing potential and high thermal stability, these NANs possess notable CO2/N2 selectivity with reasonable retention while increasing the temperature from 273 K to 298 K. The quantum chemical calculations also suggest that CO2 interacts mainly in the region of polar amide groups (-CONH-) present in NANs and this interaction is much stronger than that with N2 thus leading to better selectivity and affirming them as promising contenders for efficient gas separation. © The Royal Society of Chemistry 2016.

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.

Antifungal Amide Alkaloids from the Aerial Parts of Piper flaviflorum and Piper sarmentosum.

Science.gov (United States)

Shi, Yan-Ni; Liu, Fang-Fang; Jacob, Melissa R; Li, Xing-Cong; Zhu, Hong-Tao; Wang, Dong; Cheng, Rong-Rong; Yang, Chong-Ren; Xu, Min; Zhang, Ying-Jun

2017-01-01

Sixty-three amide alkaloids, including three new, piperflaviflorine A ( 1 ), piperflaviflorine B ( 2 ), and sarmentamide D ( 4 ), and two previously synthesized ones, (1 E ,3 S )-1-cinnamoyl-3- hydroxypyrrolidine ( 3 ) and N -[7'-(4'-methoxyphenyl)ethyl]-2-methoxybenzamide ( 5 ), were isolated from the aerial parts of Piper flaviflorum and Piper sarmentosum. Their structures were elucidated by detailed spectroscopic analysis and, in case of 3 , by single-crystal X-ray diffraction. Most of the isolates were tested for their antifungal and antibacterial activities. Ten amides ( 6 - 15 ) showed antifungal activity against Cryptococcus neoformans ATCC 90 113 with IC 50 values in the range between 4.7 and 20.0 µg/mL. Georg Thieme Verlag KG Stuttgart · New York.

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.

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.

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

Directory of Open Access Journals (Sweden)

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.

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...

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.

A simple enantioconvergent and chemoenzymatic synthesis of optically active α-substituted amides

NARCIS (Netherlands)

Szymanski, Wiktor; Westerbeek, Alja; Janssen, Dick B.; Feringa, Ben L.

2011-01-01

Simple and efficient: The combination of an enzymatic, enantioinverting reaction with simple follow-up processes allows the transformation of readily available racemic compounds into versatile chiral α-substituted amides. These important building blocks are prepared in high overall yield and

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.

Determination of the secondary structure content of proteins in aqueous solutions from their amide I and amide II infrared bands. Comparison between classical and partial least-squares methods

International Nuclear Information System (INIS)

Dousseau, F.; Pezolet, M.

1990-01-01

A method for estimating protein secondary structure from infrared spectra has been developed. The infrared spectra of H 2 O solutions of 13 proteins of known crystal structure have been recorded and corrected for the spectral contribution of water in the amide I and II region by using the algorithm of Dousseau et al. This calibration set of proteins has been analyzed by using either a classical least-squares (CLS) method or the partial least-squares (PLS) method. The pure-structure spectra calculated by the classical least-squares method are in good agreement with spectra of poly(L-lysine) in the α-helix, β-sheet, and undefined conformations. The results show that the best agreement between the secondary structure determined by X-ray crystal-lography and that predicted by infrared spectroscopy is obtained when both the amide I and II bands are used to generate the calibration set, when the PLS method is used, and when it is assumed that the secondary structure of proteins is composed of only four types of structure: ordered and disordered α-helices, β-sheet, and undefined conformation. Attempts to include turns in the secondary structure estimation have led to a loss of accuracy. The spectra of the calibration proteins were also recorded in 2 H 2 O solution. After correction for the contribution of the combination band of 2 H 2 O in the amide I' band region, the spectra were analyzed with PLS, but the results were not as good as for the spectra obtained in H 2 O, especially for the α-helical conformation

Targeted Lipidomics in Drosophila melanogaster Identifies Novel 2-Monoacylglycerols and N-acyl Amides

Science.gov (United States)

Takacs, Sara M.; Stuart, Jordyn M.; Basnet, Arjun; Raboune, Siham; Widlanski, Theodore S.; Doherty, Patrick; Bradshaw, Heather B.

2013-01-01

Lipid metabolism is critical to coordinate organ development and physiology in response to tissue-autonomous signals and environmental cues. Changes to the availability and signaling of lipid mediators can limit competitiveness, adaptation to environmental stressors, and augment pathological processes. Two classes of lipids, the N-acyl amides and the 2-acyl glycerols, have emerged as important signaling molecules in a wide range of species with important signaling properties, though most of what is known about their cellular functions is from mammalian models. Therefore, expanding available knowledge on the repertoire of these lipids in invertebrates will provide additional avenues of research aimed at elucidating biosynthetic, metabolic, and signaling properties of these molecules. Drosophila melanogaster is a commonly used organism to study intercellular communication, including the functions of bioactive lipids. However, limited information is available on the molecular identity of lipids with putative biological activities in Drosophila. Here, we used a targeted lipidomics approach to identify putative signaling lipids in third instar Drosophila larvae, possessing particularly large lipid mass in their fat body. We identified 2-linoleoyl glycerol, 2-oleoyl glycerol, and 45 N-acyl amides in larval tissues, and validated our findings by the comparative analysis of Oregon-RS, Canton-S and w1118 strains. Data here suggest that Drosophila represent another model system to use for the study of 2-acyl glycerol and N-acyl amide signaling. PMID:23874457

How Secondary and Tertiary Amide Moieties are Molecular Stations for Dibenzo-24-crown-8 in [2]Rotaxane Molecular Shuttles?

Science.gov (United States)

Riss-Yaw, Benjamin; Morin, Justine; Clavel, Caroline; Coutrot, Frédéric

2017-11-21

Interlocked molecular machines like [2]rotaxanes are intriguing aesthetic molecules. The control of the localization of the macrocycle, which surrounds a molecular axle, along the thread leads to translational isomers of very different properties. Although many moieties have been used as sites of interactions for crown ethers, the very straightforwardly obtained amide motif has more rarely been envisaged as molecular station. In this article, we report the use of secondary and tertiary amide moieties as efficient secondary molecular station in pH-sensitive molecular shuttles. Depending on the N -substitution of the amide station, and on deprotonation or deprotonation-carbamoylation, the actuation of the molecular machinery differs accordingly to very distinct interactions between the axle and the DB24C8.

Synthesis, antiproliferative and antibacterial activity of new amides of salinomycin.

Science.gov (United States)

Antoszczak, Michał; Maj, Ewa; Stefańska, Joanna; Wietrzyk, Joanna; Janczak, Jan; Brzezinski, Bogumil; Huczyński, Adam

2014-04-01

A series of 11 novel amides of salinomycin were synthesized for the first time. All the obtained compounds were found to show potent antiproliferative activity against human cancer cell lines including the drug-resistant cancer cells. Four new salinomycin derivatives revealed good antibacterial activity against clinical isolates of methicillin-resistant Staphylococcus epidermidis (MRSE). Copyright © 2014 Elsevier Ltd. All rights reserved.

Amide group anchored glucose oxidase based anodic catalysts for high performance enzymatic biofuel cell

Science.gov (United States)

Chung, Yongjin; Ahn, Yeonjoo; Kim, Do-Heyoung; Kwon, Yongchai

2017-01-01

A new enzyme catalyst is formed by fabricating gold nano particle (GNP)-glucose oxidase (GOx) clusters that are then attached to polyethyleneimine (PEI) and carbon nanotube (CNT) with cross-linkable terephthalaldehyde (TPA) (TPA/[CNT/PEI/GOx-GNP]). Especially, amide bonds belonging to TPA play an anchor role for incorporating rigid bonding among GNP, GOx and CNT/PEI, while middle size GNP is well bonded with thiol group of GOx to form strong GNP-GOx cluster. Those bonds are identified by chemical and electrochemical characterizations like XPS and cyclic voltammogram. The anchording effect of amide bonds induces fast electron transfer and strong chemical bonding, resulting in enhancements in (i) catalytic activity, (ii) amount of immobilized GOx and (ii) performance of enzymatic biofuel cell (EBC) including the catalyst. Regarding the catalytic activity, the TPA/[CNT/PEI/GOx-GNP] produces high electron transfer rate constant (6 s-1), high glucose sensitivity (68 μA mM-1 cm-2), high maximum current density (113 μA cm-2), low charge transfer resistance (17.0 Ω cm2) and long-lasting durability while its chemical structure is characterized by XPS confirming large portion of amide bond. In EBC measurement, it has high maximum power density (0.94 mW cm-2) compatible with catalytic acitivity measurements.

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.

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)

New amides from seeds of Silybum marianum with potential antioxidant and antidiabetic activities.

Science.gov (United States)

Qin, Ning-Bo; Jia, Cui-Cui; Xu, Jun; Li, Da-Hong; Xu, Fan-Xing; Bai, Jiao; Li, Zhan-Lin; Hua, Hui-Ming

2017-06-01

Two new amide compounds, mariamides A and B (1-2), were obtained together with fourteen known compounds from the seeds of milk thistle (Silybum marianum). Their structures were established on the basis of extensive 1D and 2D NMR analyses, as well as HR-ESI-MS data. Most of the compounds showed significant antioxidant activities than positive control in ABTS and FRAP assays. However, only amide compounds 1-4 showed moderate DPPH radical scavenging activity and compounds 7 and 16 showed the most potent activity against DPPH. Most of the compounds showed moderate to stronger α-glucosidase inhibitory activities. Nevertheless, only flavonoids showed strong PTP1B inhibitory activities. These results indicate a use of milk thistle seed extracts as promising antioxidant and antidiabetic agents. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Copper sulfate-pentahydrate-1,10-phenanthroline catalyzed amidations of alkynyl bromides. Synthesis of heteroaromatic amine substituted ynamides.

Science.gov (United States)

Zhang, Yanshi; Hsung, Richard P; Tracey, Michael R; Kurtz, Kimberly C M; Vera, Eymi L

2004-04-01

A practical cross-coupling of amides with alkynyl bromides using catalytic CuSO(4).5H(2)O and 1,10-phenanthroline is described here. This catalytic protocol is more environmentally friendly than the use of CuCN or copper halides and provides a general entry for syntheses of ynamides including various new sulfonyl and heteroaromatic amine substituted ynamides. Given the interest in ynamides, this N-alkynylation of amides should be significant for the future of ynamides in organic synthesis.

Identification and in vitro analysis of the GatD/MurT enzyme-complex catalyzing lipid II amidation in Staphylococcus aureus.

Directory of Open Access Journals (Sweden)

Daniela Münch

2012-01-01

Full Text Available The peptidoglycan of Staphylococcus aureus is characterized by a high degree of crosslinking and almost completely lacks free carboxyl groups, due to amidation of the D-glutamic acid in the stem peptide. Amidation of peptidoglycan has been proposed to play a decisive role in polymerization of cell wall building blocks, correlating with the crosslinking of neighboring peptidoglycan stem peptides. Mutants with a reduced degree of amidation are less viable and show increased susceptibility to methicillin. We identified the enzymes catalyzing the formation of D-glutamine in position 2 of the stem peptide. We provide biochemical evidence that the reaction is catalyzed by a glutamine amidotransferase-like protein and a Mur ligase homologue, encoded by SA1707 and SA1708, respectively. Both proteins, for which we propose the designation GatD and MurT, are required for amidation and appear to form a physically stable bi-enzyme complex. To investigate the reaction in vitro we purified recombinant GatD and MurT His-tag fusion proteins and their potential substrates, i.e. UDP-MurNAc-pentapeptide, as well as the membrane-bound cell wall precursors lipid I, lipid II and lipid II-Gly₅. In vitro amidation occurred with all bactoprenol-bound intermediates, suggesting that in vivo lipid II and/or lipid II-Gly₅ may be substrates for GatD/MurT. Inactivation of the GatD active site abolished lipid II amidation. Both, murT and gatD are organized in an operon and are essential genes of S. aureus. BLAST analysis revealed the presence of homologous transcriptional units in a number of gram-positive pathogens, e.g. Mycobacterium tuberculosis, Streptococcus pneumonia and Clostridium perfringens, all known to have a D-iso-glutamine containing PG. A less negatively charged PG reduces susceptibility towards defensins and may play a general role in innate immune signaling.

Glucagon-like peptide 1 (7-36) amide stimulates exocytosis in human pancreatic beta-cells by both proximal and distal regulatory steps in stimulus-secretion coupling

DEFF Research Database (Denmark)

Gromada, J; Bokvist, K; Ding, W G

1998-01-01

The effect of glucagon-like peptide 1(7-36) amide [GLP-1(7-36) amide] on membrane potential, whole-cell ATP-sensitive potassium channel (K[ATP]) and Ca2+ currents, cytoplasmic Ca2+ concentration, and exocytosis was explored in single human beta-cells. GLP-1(7-36) amide induced membrane...... depolarization that was associated with inhibition of whole-cell K(ATP) current. In addition, GLP-1(7-36) amide (and forskolin) produced greater than fourfold potentiation of Ca2+-dependent exocytosis. The latter effect resulted in part (40%) from acceleration of Ca2+ influx through voltage-dependent (L-type) Ca......2+ channels. More importantly, GLP-1(7-36) amide (via generation of cyclic AMP and activation of protein kinase A) potentiated exocytosis at a site distal to a rise in the cytoplasmic Ca2+ concentration. Photorelease of caged cAMP produced a two- to threefold potentiation of exocytosis when...

Benchmarking lithium amide versus amine bonding by charge density and energy decomposition analysis arguments.

Science.gov (United States)

Engelhardt, Felix; Maaß, Christian; Andrada, Diego M; Herbst-Irmer, Regine; Stalke, Dietmar

2018-03-28

Lithium amides are versatile C-H metallation reagents with vast industrial demand because of their high basicity combined with their weak nucleophilicity, and they are applied in kilotons worldwide annually. The nuclearity of lithium amides, however, modifies and steers reactivity, region- and stereo-selectivity and product diversification in organic syntheses. In this regard, it is vital to understand Li-N bonding as it causes the aggregation of lithium amides to form cubes or ladders from the polar Li-N covalent metal amide bond along the ring stacking and laddering principle. Deaggregation, however, is more governed by the Li←N donor bond to form amine adducts. The geometry of the solid state structures already suggests that there is σ- and π-contribution to the covalent bond. To quantify the mutual influence, we investigated [{(Me 2 NCH 2 ) 2 (C 4 H 2 N)}Li] 2 ( 1 ) by means of experimental charge density calculations based on the quantum theory of atoms in molecules (QTAIM) and DFT calculations using energy decomposition analysis (EDA). This new approach allows for the grading of electrostatic Li + N - , covalent Li-N and donating Li←N bonding, and provides a way to modify traditional widely-used heuristic concepts such as the -I and +I inductive effects. The electron density ρ ( r ) and its second derivative, the Laplacian ∇ 2 ρ ( r ), mirror the various types of bonding. Most remarkably, from the topological descriptors, there is no clear separation of the lithium amide bonds from the lithium amine donor bonds. The computed natural partial charges for lithium are only +0.58, indicating an optimal density supply from the four nitrogen atoms, while the Wiberg bond orders of about 0.14 au suggest very weak bonding. The interaction energy between the two pincer molecules, (C 4 H 2 N) 2 2- , with the Li 2 2+ moiety is very strong ( ca. -628 kcal mol -1 ), followed by the bond dissociation energy (-420.9 kcal mol -1 ). Partitioning the interaction energy

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

Ab initio molecular orbital and infrared spectroscopic study of the conformation of secondary amides: derivatives of formanilide, acetanilide and benzylamides

Science.gov (United States)

Ilieva, S.; Hadjieva, B.; Galabov, B.

1999-09-01

Ab initio molecular orbital calculations at HF/4-31G level and infrared spectroscopic data for the frequencies are applied to analyse the grouping in a series model aromatic secondary amides: formanilide; acetanilide; o-methylacetanilide; 2,6-dimethylformanilide, 2,6-dimethylacetanilide; N-benzylacetamide and N-benzylformamide. The theoretical and experimental data obtained show that the conformational state of the molecules studied is determined by the fine balance of several intramolecular factors: resonance effect between the amide group and the aromatic ring, steric interaction between various substituents around the -NH-CO- grouping in the aromatic ring, conjugation between the carbonyl bond and the nitrogen lone pair as well as direct field influences inside the amide group.

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.

Measurement of Lactate Content and Amide Proton Transfer Values in the Basal Ganglia of a Neonatal Piglet Hypoxic-Ischemic Brain Injury Model Using MRI.

Science.gov (United States)

Zheng, Y; Wang, X-M

2017-04-01

As amide proton transfer imaging is sensitive to protein content and intracellular pH, it has been widely used in the nervous system, including brain tumors and stroke. This work aimed to measure the lactate content and amide proton transfer values in the basal ganglia of a neonatal piglet hypoxic-ischemic brain injury model by using MR spectroscopy and amide proton transfer imaging. From 58 healthy neonatal piglets (3-5 days after birth; weight, 1-1.5 kg) selected initially, 9 piglets remained in the control group and 43 piglets, in the hypoxic-ischemic brain injury group. Single-section amide proton transfer imaging was performed at the coronal level of the basal ganglia. Amide proton transfer values of the bilateral basal ganglia were measured in all piglets. The ROI of MR spectroscopy imaging was the right basal ganglia, and the postprocessing was completed with LCModel software. After hypoxic-ischemic insult, the amide proton transfer values immediately decreased, and at 0-2 hours, they remained at their lowest level. Thereafter, they gradually increased and finally exceeded those of the control group at 48-72 hours. After hypoxic-ischemic insult, the lactate content increased immediately, was maximal at 2-6 hours, and then gradually decreased to the level of the control group. The amide proton transfer values were negatively correlated with lactate content ( r = -0.79, P < .05). This observation suggests that after hypoxic-ischemic insult, the recovery of pH was faster than that of lactate homeostasis. © 2017 by American Journal of Neuroradiology.

Lithium amide (LiNH2) under pressure.

Science.gov (United States)

Prasad, Dasari L V K; Ashcroft, N W; Hoffmann, Roald

2012-10-11

Static high pressure lithium amide (LiNH(2)) crystal structures are predicted using evolutionary structure search methodologies and intuitive approaches. In the process, we explore the relationship of the structure and properties of solid LiNH(2) to its molecular monomer and dimer, as well as its valence-isoelectronic crystalline phases of methane, water, and ammonia all under pressure. A NaNH(2) (Fddd) structure type is found to be competitive for the ground state of LiNH(2) above 6 GPa with the P = 1 atm I4[overline] phase. Three novel phases emerge at 11 (P4[overline]2(1)m), 13 (P4(2)/ncm), and 46 GPa (P2(1)2(1)2(1)), still containing molecular amide anions, which begin to form N-H···N hydrogen bonds. The P2(1)2(1)2(1) phase remains stable over a wide pressure range. This phase and another Pmc2(1) structure found at 280 GPa have infinite ···(H)N···H···N(H)···H polymeric zigzag chains comprising symmetric N···H···N hydrogen bonds with one NH bond kept out of the chain, an interesting general feature found in many of our high pressure (>280 GPa) LiNH(2) structures, with analogies in high pressure H(2)O-ices. All the predicted low enthalpy LiNH(2) phases are calculated to be enthalpically stable with respect to their elements but resist metallization with increasing pressure up to several TPa. The possibility of Li sublattice melting in the intermediate pressure range structures is raised.

Characterization of the peptidylglycine α-amidating monooxygenase (PAM) from the venom ducts of neogastropods, Conus bullatus and Conus geographus.

Science.gov (United States)

Ul-Hasan, Sabah; Burgess, Daniel M; Gajewiak, Joanna; Li, Qing; Hu, Hao; Yandell, Mark; Olivera, Baldomero M; Bandyopadhyay, Pradip K

2013-11-01

Cone snails, genus Conus, are predatory marine snails that use venom to capture their prey. This venom contains a diverse array of peptide toxins, known as conotoxins, which undergo a diverse set of posttranslational modifications. Amidating enzymes modify peptides and proteins containing a C-terminal glycine residue, resulting in loss of the glycine residue and amidation of the preceding residue. A significant fraction of peptides present in the venom of cone snails contain C-terminal amidated residues, which are important for optimizing biological activity. This study describes the characterization of the amidating enzyme, peptidylglycine α-amidating monooxygenase (PAM), present in the venom duct of cone snails, Conus bullatus and Conus geographus. PAM is known to carry out two functions, peptidyl α-hydroxylating monooxygenase (PHM) and peptidylamido-glycolate lyase (PAL). In some animals, such as Drosophila melanogaster, these two functions are present in separate polypeptides, working as individual enzymes. In other animals, such as mammals and in Aplysia californica, PAM activity resides in a single, bifunctional polypeptide. Using specific oligonucleotide primers and reverse transcription-polymerase chain reaction we have identified and cloned from the venom duct cDNA library, a cDNA with 49% homology to PAM from A. californica. We have determined that both the PHM and PAL activities are encoded in one mRNA polynucleotide in both C. bullatus and C. geographus. We have directly demonstrated enzymatic activity catalyzing the conversion of dansyl-YVG-COOH to dansyl-YV-NH2 in cloned cDNA expressed in Drosophila S2 cells. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

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.

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)

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

Amide proton solvent protection in amylin fibrils probed by quenched hydrogen exchange NMR.

Directory of Open Access Journals (Sweden)

Andrei T Alexandrescu

Full Text Available Amylin is an endocrine hormone that accumulates in amyloid plaques in patients with advanced type 2 diabetes. The amyloid plaques have been implicated in the destruction of pancreatic β-cells, which synthesize amylin and insulin. To better characterize the secondary structure of amylin in amyloid fibrils we assigned the NMR spectrum of the unfolded state in 95% DMSO and used a quenched hydrogen-deuterium exchange technique to look at amide proton solvent protection in the fibrils. In this technique, partially exchanged fibrils are dissolved in 95% DMSO and information about amide proton occupancy in the fibrils is determined from DMSO-denatured monomers. Hydrogen exchange lifetimes at pH 7.6 and 37°C vary between ∼5 h for the unstructured N-terminus to 600 h for amide protons in the two β-strands that form inter-molecular hydrogen bonds between amylin monomers along the length of the fibril. Based on the protection data we conclude that residues A8-H18 and I26-Y37 comprise the two β-strands in amylin fibrils. There is variation in protection within the β-strands, particularly for strand β1 where only residues F15-H18 are strongly protected. Differences in protection appear to be due to restrictions on backbone dynamics imposed by the packing of two-layers of C2-symmetry-related β-hairpins in the protofilament structure, with strand β1 positioned on the surface and β2 in the interior.

Radiolabeled biotin amides from triazenyl precursors: synthesis, binding, and in-vivo properties

International Nuclear Information System (INIS)

Kortylewicz, Z.P.; Baranowska-Kortylewicz, J.; Adelstein, S.J.; Carmel, A.D.; Kassis, A.I.

1994-01-01

The synthesis of N-(4-[ 127/125/123 I]iodobenzyl)biotin amides 4a - 4c performed by the direct decomposition of N-[4-(3',3'-dimethyltriazenyl)benzyl]biotin amide with sodium iodide in the presence of CF 3 COOH is described. Iodinated in this way biotin formed a stable complex with avidin (K d = 2.84 ± 0.45 x 10 -15 M, n = 3.9 ± 0.6) which dissociated in the presence of excess native biotin with a rate constant of 0.034 ± 0.006 hr -1 . Blood clearance studies and the lack of thyroid uptake indicated that this compound was not deiodinated in vivo and behaved in circulation much like native biotin. This aryltriazene precursor method is suitable for labeling with short-lived radiohalides. It can be used to produce no-carrier-added derivatives of biotin for use in biologic studies and assays involving avidin or streptavidin. (author)

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.

[Effects of nitriles and amides on the growth and the nitrile hydratase activity of the Rhodococcus sp. strain gt1].

Science.gov (United States)

Maksimov, A Iu; Kuznetsova, M V; Ovechkina, G V; Kozlov, S V; Maksimova, Iu G; Demakov, V A

2003-01-01

Effects of some nitriles and amides, as well as glucose and ammonium, on the growth and the nitrile hydratase (EC 4.2.1.84) activity of the Rhodococcus sp. strain gt1 isolated from soil were studied. The activity of nitrile hydratase mainly depended on carbon and nitrogen supply to cells. The activity of nitrile hydratase was high in the presence of glucose and ammonium at medium concentrations and decreased at concentrations of glucose more than 0.3%. Saturated unsubstituted aliphatic nitriles and amides were found to be a good source of nitrogen and carbon. However, the presence of nitriles and amides in the medium was not absolutely necessary for the expression of the activity of nitrile hydratase isolated from the Rhodococcus sp. strain gt1.

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.

Increased CEST specificity for amide and fast-exchanging amine protons using exchange-dependent relaxation rate.

Science.gov (United States)

Zhang, Xiao-Yong; Wang, Feng; Xu, Junzhong; Gochberg, Daniel F; Gore, John C; Zu, Zhongliang

2018-02-01

Chemical exchange saturation transfer (CEST) imaging of amides at 3.5 ppm and fast-exchanging amines at 3 ppm provides a unique means to enhance the sensitivity of detection of, for example, proteins/peptides and neurotransmitters, respectively, and hence can provide important information on molecular composition. However, despite the high sensitivity relative to conventional magnetic resonance spectroscopy (MRS), in practice, CEST often has relatively poor specificity. For example, CEST signals are typically influenced by several confounding effects, including direct water saturation (DS), semi-solid non-specific magnetization transfer (MT), the influence of water relaxation times (T 1w ) and nearby overlapping CEST signals. Although several editing techniques have been developed to increase the specificity by removing DS, semi-solid MT and T 1w influences, it is still challenging to remove overlapping CEST signals from different exchanging sites. For instance, the amide proton transfer (APT) signal could be contaminated by CEST effects from fast-exchanging amines at 3 ppm and intermediate-exchanging amines at 2 ppm. The current work applies an exchange-dependent relaxation rate (R ex ) to address this problem. Simulations demonstrate that: (1) slowly exchanging amides and fast-exchanging amines have distinct dependences on irradiation powers; and (2) R ex serves as a resonance frequency high-pass filter to selectively reduce CEST signals with resonance frequencies closer to water. These characteristics of R ex provide a means to isolate the APT signal from amines. In addition, previous studies have shown that CEST signals from fast-exchanging amines have no distinct features around their resonance frequencies. However, R ex gives Lorentzian lineshapes centered at their resonance frequencies for fast-exchanging amines and thus can significantly increase the specificity of CEST imaging for amides and fast-exchanging amines. Copyright © 2017 John Wiley & Sons

Rhodium(III)-catalyzed regioselective C2-amidation of indoles with N-(2,4,6-trichlorobenzoyloxy)amides and its synthetic application to the development of a novel potential PPARγ modulator.

Science.gov (United States)

Shi, Jingjing; Zhao, Guanguan; Wang, Xiaowei; Xu, H Eric; Yi, Wei

2014-09-21

A new and efficient method for the direct regioselective C2-amidation of various functionalized indoles with several N-(2,4,6-trichlorobenzoyloxy)amides via Rh(iii)-catalyzed C-H activation/N-O cleavage/C-N formation using the pyrimidyl group as a readily installable and removable directing group has been developed. With this method, a variety of valuable 2-amido indoles can be easily prepared under mild conditions with broad functional group tolerance and excellent region-/site-specificities. Application of this strategy to the synthesis of target compound as a novel PPARγ modulator was also demonstrated. The results from biological evaluation showed that compound had a partial PPARγ agonistic activity and a strong PPARγ binding affinity with an IC50 value of 120.0 nM, along with a less pronounced adipocyte differentiation ability compared to the currently marketed anti-diabetic drug rosiglitazone, suggesting that further development of such a compound might be of great interest.

2,4-dimethoxybenzyl: An amide protecting group for 2-acetamido glycosyl donors

DEFF Research Database (Denmark)

Kelly, N.M.; Jensen, Knud Jørgen

2001-01-01

2,4-Dimethoxybenzyl (Dmob) was used as an amide protecting group for 2-acetamido glycosyl donors. The N-Dmob group was introduced by imine formation between 2,4-dimethoxybenzaldehyde and d-glucosamine, followed by per-O-acylation, reduction to form the amine, and finally N-acetylation to give 1...

Amide proton transfer imaging of high intensity focused ultrasound-treated tumor tissue

NARCIS (Netherlands)

Hectors, S.J.C.G.; Jacobs, I.; Strijkers, G.J.; Nicolay, K.

2014-01-01

Purpose: In this study, the suitability of amide proton transfer (APT) imaging as a biomarker for the characterization of high intensity focused ultrasound (HIFU)-treated tumor tissue was assessed. Methods: APT imaging was performed on tumor-bearing mice before (n=15), directly after (n=15) and at 3

Amide Proton Transfer Imaging of High Intensity Focused Ultrasound-Treated Tumor Tissue

NARCIS (Netherlands)

Hectors, Stefanie J. C. G.; Jacobs, Igor; Strijkers, Gustav J.; Nicolay, Klaas

2014-01-01

PurposeIn this study, the suitability of amide proton transfer (APT) imaging as a biomarker for the characterization of high intensity focused ultrasound (HIFU)-treated tumor tissue was assessed. MethodsAPT imaging was performed on tumor-bearing mice before (n=15), directly after (n=15) and at 3

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...

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.

Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines.

Science.gov (United States)

Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

2017-07-06

The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

A General and Simple Diastereoselective Reduction by L-Selectride: Efficient Synthesis of Protected (4S,5S-Dihydroxy Amides

Directory of Open Access Journals (Sweden)

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.

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.

[Comparative metabolism of three amide alkaloids from Piper longum in five different species of liver microsomes].

Science.gov (United States)

He, Huan; Guo, Wei-Wei; Chen, Xiao-Qing; Zhao, Hai-Yu; Wu, Xia

2016-08-01

Piperine, piperlonguminine and pellitorine are three major amide alkaloids from Piper longum, showing a variety of pharmacological activities. In order to investigate the different metabolism pathways of these compounds in five species of liver microsomes in vitro, the data of full mass spectrum, and MS2, MS3 spectra of these three alkaloids were collected and analyzed by using ultra-high-performance liquid chromatography coupled with a LTQ-orbitrap mass spectrometer (UHPLC-LTQ-Orbitrap MS); gragment ion information was collected and combined with fragmentation regularities of mass spectra and accurate mass spectrometry data of metabolites, to compare the metabolism difference of three amide alkaloids in liver microsomes of human, rhesus monkey, Beagle dogs, rats and mice. 3 metabolites of piperine, 2 metabolites of piperlonguminine and 1 metabolite of pellitorine were identified quickly. The results showed that the major metabolic pathways of these amide alkaloids in liver microsomes were methylenedioxy group demethylation and oxidation reaction, and metabolic rates were different between species. This study provides basis for further research on in vivo metabolism of piperine analogues from Piper longum. Copyright© by the Chinese Pharmaceutical Association.

Part 1: Notch-sparing γ-secretase inhibitors: The identification of novel naphthyl and benzofuranyl amide analogs.

Science.gov (United States)

Lu, Dai; Wei, Han-Xun; Zhang, Jing; Gu, Yongli; Osenkowski, Pamela; Ye, Wenjuan; Selkoe, Dennis J; Wolfe, Michael S; Augelli-Szafran, Corinne E

2016-05-01

γ-Secretase is one of two proteases directly involved in the production of the amyloid β-peptide (Aβ), which is pathogenic in Alzheimer's disease. Inhibition of γ-secretase to suppress the production of Aβ should not block processing of one of its alternative substrates, Notch1 receptors, as interference with Notch1 signaling leads to severe toxic effects. In the course of our studies to identify γ-secretase inhibitors with selectivity for APP over Notch, 1 [3-(benzyl(isopropyl)amino)-1-(naphthalen-2-yl)propan-1-one] was found to inhibit γ-secretase-mediated Aβ production without interfering with γ-secretase-mediated Notch processing in purified enzyme assays. As 1 is chemically unstable, efforts to increase the stability of this compound led to the identification of 2 [naphthalene-2-carboxylic acid benzyl-isopropyl-amide] which showed similar biological activity to compound 1. Synthesis and evaluation of a series of amide analogs resulted in benzofuranyl amide analogs that showed promising Notch-sparing γ-secretase inhibitory effects. This class of compounds may serve as a novel lead series for further study in the development of γ-secretase inhibitors. Copyright © 2016 Elsevier Ltd. All rights reserved.

Determination of carbofuran on hydrophilic interaction liquid chromatography using TSK gel amide 80 as stationary phase

International Nuclear Information System (INIS)

A Kurnia; LW Lim; T Takeuchi

2016-01-01

The hydrophilic interaction liquid chromatography (HILIC) coupled to environmental friendly capillary liquid chromatography was employed to investigate retention behavior of carbofuran. Aim of this research is to investigate retention behavior of carbofuran using TSK gel amide 80 as stationary phase. Several condition was conducted to investigate retention behavior of carbofuran such as comparison study of TSK gel amide 80 with other polar column, comparison study retention behavior of carbofuran on various system wavelength, water content effect in HILIC mode, effect of buffer concentration on HILIC mode, and analytical performance. Results showed that TSK gel imidazole was superior compare to other polar stationary phase on determine carbofuran, wavelength 251 and 254 nm was resulting higher absorbance for carbofuran than others, increase of water content on mobile phase was decrease the retention time, also increase buffer salt concentration was decrease the retention time and according to analysis performance that is the accuracy was 101±10,1, the LOD 0.66 ppm while LOQ 2.22 ppm. As conclusions that TSK gel amide 80 was offering good determine on carbofuran even using capillary liquid chromatography with 10 cm length of column. (author)

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

Rh(III-catalyzed directed C–H bond amidation of ferrocenes with isocyanates

Directory of Open Access Journals (Sweden)

Satoshi Takebayashi

2012-10-01

Full Text Available [RhCp*(OAc2(H2O] [Cp* = pentamethylcyclopentadienyl] catalyzed the C–H bond amidation of ferrocenes possessing directing groups with isocyanates in the presence of 2 equiv/Rh of HBF4·OEt2. A variety of disubstituted ferrocenes were prepared in high yields, or excellent diastereoselectivities.

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

Science.gov (United States)

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.

Photophysical studies on the interaction of amides with Bovine Serum Albumin (BSA) in aqueous solution: Fluorescence quenching and protein unfolding

International Nuclear Information System (INIS)

Kumaran, R.; Ramamurthy, P.

2014-01-01

Addition. of amides containing a H-CO(NH 2 ) or CH 3 -CO(NH 2 ) framework to BSA results in a fluorescence quenching. On the contrary, fluorescence enhancement with a shift in the emission maximum towards the blue region is observed on the addition of dimethylformamide (DMF) (H-CON(CH 3 ) 2 ). Fluorescence quenching accompanied initially with a shift towards the blue region and a subsequent red shift in the emission maximum of BSA is observed on the addition of formamide (H-CO(NH 2 )), whereas a shift in the emission maximum only towards the red region results on the addition of acetamide (CH 3 -CONH 2 ). Steady state emission spectral studies reveal that amides that possess a free NH 2 and N(CH 3 ) 2 moiety result in fluorescence quenching and enhancement of BSA respectively. The 3D contour spectral studies of BSA with formamide exhibit a shift in the emission towards the red region accompanied with fluorescence quenching, which indicates that the tryptophan residues of the BSA are exposed to a more polar environment. Circular Dichroism (CD) studies of BSA with amides resulted in a gradual decrease in the α-helical content of BSA at 208 nm, which confirms that there is a conformational change in the native structure of BSA. Time-resolved fluorescence studies illustrate that the extent of buried trytophan moieties exposed to the aqueous phase on the addition of amides follows the order DMF 2 hydrogen and the carbonyl oxygen of amide form a concerted hydrogen-bonding network with the carbonyl oxygen and the amino moieties of amino acids respectively is established from fluorescence methods. -- Highlights: • The manuscript deals with the absorption, emission and fluorescence lifetime studies of Bovine Serum Albumin with amides in aqueous medium. • Fluorescence is correlated to the presence of fluorescing amino acid, tryptophan located in a heterogeneous environment. • This article provides an insight about the fluorescence spectral characteristics of a protein

Naturally occurring antifungal aromatic esters and amides

International Nuclear Information System (INIS)

Ali, M.S.; Shahnaz; Tabassum, S.; Ogunwande, I.A.; Pervez, M.K.

2010-01-01

During the search of antifungal natural products from terrestrial plants, a new long chained aromatic ester named grandiflorate along with spatazoate from Portulaca grandiflora and N-[2-methoxy-2-(4-methoxyphenyl) ethyl]-trans-cinnamide and aegeline from Solanum erianthum of Nigeria were isolated and tested against six fungal species. The known constituents have not been reported so far from mentioned investigated plants. Structures of the isolated compounds were elucidated with the aid of spectroscopic techniques including two dimensional NMR experiments. Among the compounds, the esters found more potent than amides against Candida albicans and Aspergillus flavus. The new compound grandiflorate gave response against all tested fungal species while aegeline was found to give lowest inhibition during this study. (author)

Naturally occurring antifungal aromatic esters and amides

Energy Technology Data Exchange (ETDEWEB)

Ali, M S; Shahnaz,; Tabassum, S; Ogunwande, I A; Pervez, M K [University of Karachi (Pakistan). HEJ Research Inst. of Chemistry, International Centre for Chemical and Biological Sciences

2010-08-15

During the search of antifungal natural products from terrestrial plants, a new long chained aromatic ester named grandiflorate along with spatazoate from Portulaca grandiflora and N-[2-methoxy-2-(4-methoxyphenyl) ethyl]-trans-cinnamide and aegeline from Solanum erianthum of Nigeria were isolated and tested against six fungal species. The known constituents have not been reported so far from mentioned investigated plants. Structures of the isolated compounds were elucidated with the aid of spectroscopic techniques including two dimensional NMR experiments. Among the compounds, the esters found more potent than amides against Candida albicans and Aspergillus flavus. The new compound grandiflorate gave response against all tested fungal species while aegeline was found to give lowest inhibition during this study. (author)

Potentiation of glucose-induced insulin release in islets by desHis1[Glu9]glucagon amide

DEFF Research Database (Denmark)

Kofod, Hans; Unson, C G; Merrifield, R B

1988-01-01

Glucagon and secretin and some of their hybrid analogs potentiate glucose-induced release of insulin from isolated mouse pancreatic islets. It was recently shown that the synthetic glucagon analog, desHis1[Glu9]glucagon amide, does not stimulate the formation of cyclic adenosine monophosphate...... in the rat hepatocyte membrane, but binds well to the glucagon receptor and is a good competitive antagonist of glucagon. In the present study the effect of this analog on isolated islets was examined. desHis1-[Glu9]glucagon amide at 3 x 10(-7) M, in the presence of 0.01 M D-glucose, increased the release...

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.

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.

Synthesis and biological activity of a new class of insecticides: the N-(5-aryl-1,3,4-thiadiazol-2-yl)amides.

Science.gov (United States)

Eckelbarger, Joseph D; Parker, Marshall H; Yap, Maurice Ch; Buysse, Ann M; Babcock, Jonathan M; Hunter, Ricky; Adelfinskaya, Yelena; Samaritoni, Jack G; Garizi, Negar; Trullinger, Tony K

2017-04-01

Optimization studies on a high-throughput screening (HTS) hit led to the discovery of a series of N-(6-arylpyridazin-3-yl)amides with insecticidal activity. It was hypothesized that the isosteric replacement of the pyridazine ring with a 1,3,4-thiadiazole ring could lead to more potent biological activity and/or a broader sap-feeding pest spectrum. The resulting N-(5-aryl-1,3,4-thiadiazol-2-yl)amides were explored as a new class of insecticides. Several methods for 2-amino-1,3,4-thiadiazole synthesis were used for the preparation of key synthetic intermediates. Subsequent coupling to variously substituted carboxylic acid building blocks furnished the final targets, which were tested for insecticidal activity against susceptible strains of Aphis gossypii (Glover) (cotton aphid), Myzus persicae (Sulzer) (green peach aphid) and Bemisia tabaci (Gennadius) (sweetpotato whitefly). Structure-activity relationship (SAR) studies on both the amide tail and the aryl A-ring of novel N-(5-aryl-1,3,4-thiadiazol-2-yl)amides led to a new class of insecticidal molecules active against sap-feeding insect pests. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

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.

The Migration Security in Russian Society amid Ethnic and Social Conflicts Aggravation

Directory of Open Access Journals (Sweden)

N А Tkacheva

2011-03-01

Full Text Available National security protection emerges as an indispensable factor for the development of personality, society, and state amid the increasing complexity of international migration processes. The article touches upon the peculiarities of ethnic and social relations between migrants and members of the host country providing insight into the novel category of "migration security".

Simple Synthesis Hydrogenated Castor Oil Fatty Amide Wax and Its Coating Characterization.

Science.gov (United States)

Yu, Xiuzhu; Wang, Ning; Zhang, Rui; Zhao, Zhong

2017-07-01

A simple method for incorporating amine groups in hydrogenated castor oil (HCO) to produce wax for beeswax or carnauba wax substitution in packaging and coating was developed. From the conversion rate of the products, HCO was reacted with ethanolamine at 150°C for 5 h, and the molar ratio of HCO and ethanolamine was 1:4. The hardness of the final product was seven times higher than that of beeswax, the cohesiveness of the final product was 1.3 times higher than that of beeswax and approximately one half of that of carnauba wax, and the melting point of the final product is 98°C. The Fourier transform Infrared spectroscopy showed that the amide groups were incorporated to form the amide products. In coating application, the results showed that the force of the final product coating cardboard was higher than that of beeswax and paraffin wax and less than that of carnauba wax. After 24 h soaking, the compression forces were decreased. HCO fatty acid wax can be an alternative wax for carnauba wax and beeswax in coating applications.

A new feruloyl amide derivative from the fruits of Tribulus terrestris.

Science.gov (United States)

Zhang, Xiaopo; Wei, Na; Huang, Jian; Tan, Yinfeng; Jin, Dejun

2012-01-01

A new feruloyl amide derivative, named tribulusamide C, was isolated from the fruits of Tribulus terrestris. Its structure was determined on the basis of spectroscopic analysis including IR, 1-D-, 2-D-NMR and HR-ESI-MS. The structure of tribulusamide C was characterised by a unit of pyrrolidine-2,5-dione, which distinguished it from other lignanamides previously isolated from the fruits of T. terrestris.

Inhibition of the α-carbonic anhydrase from Vibrio cholerae with amides and sulfonamides incorporating imidazole moieties.

Science.gov (United States)

De Vita, Daniela; Angeli, Andrea; Pandolfi, Fabiana; Bortolami, Martina; Costi, Roberta; Di Santo, Roberto; Suffredini, Elisabetta; Ceruso, Mariangela; Del Prete, Sonia; Capasso, Clemente; Scipione, Luigi; Supuran, Claudiu T

2017-12-01

We discovered novel and selective sulfonamides/amides acting as inhibitors of the α-carbonic anhydrase (CA, EC 4.2.1.1) from the pathogenic bacterium Vibrio cholerae (VchCA). This Gram-negative bacterium is the causative agent of cholera and colonises the upper small intestine where sodium bicarbonate is present at a high concentration. The secondary sulfonamides and amides investigated here were potent, low nanomolar VchCA inhibitors whereas their inhibition of the human cytosolic isoforms CA I and II was in the micromolar range or higher. The molecules represent an interesting lead for antibacterial agents with a possibly new mechanism of action, although their CA inhibition mechanism is unknown for the moment.

Development of dihydropyridone indazole amides as selective Rho-kinase inhibitors.

Science.gov (United States)

Goodman, Krista B; Cui, Haifeng; Dowdell, Sarah E; Gaitanopoulos, Dimitri E; Ivy, Robert L; Sehon, Clark A; Stavenger, Robert A; Wang, Gren Z; Viet, Andrew Q; Xu, Weiwei; Ye, Guosen; Semus, Simon F; Evans, Christopher; Fries, Harvey E; Jolivette, Larry J; Kirkpatrick, Robert B; Dul, Edward; Khandekar, Sanjay S; Yi, Tracey; Jung, David K; Wright, Lois L; Smith, Gary K; Behm, David J; Bentley, Ross; Doe, Christopher P; Hu, Erding; Lee, Dennis

2007-01-11

Rho kinase (ROCK1) mediates vascular smooth muscle contraction and is a potential target for the treatment of hypertension and related disorders. Indazole amide 3 was identified as a potent and selective ROCK1 inhibitor but possessed poor oral bioavailability. Optimization of this lead resulted in the discovery of a series of dihydropyridones, exemplified by 13, with improved pharmacokinetic parameters relative to the initial lead. Indazole substitution played a critical role in decreasing clearance and improving oral bioavailability.

Normalization of fasting glycaemia by intravenous GLP-1 ([7-36 amide] or [7-37]) in type 2 diabetic patients

DEFF Research Database (Denmark)

Nauck, M A; Weber, I; Bach, I

1998-01-01

(glucose-oxidase), insulin and C-peptide (ELISA) was measured during infusion and for 4 h thereafter. Indirect calorimetry was performed. Fasting hyperglycaemia was 11.7+/-0.9 [7-36 amide] and 11.3+/-0.9 mmol l(-1) [7-37]. GLP-1 infusions stimulated insulin secretion approximately 3-fold (insulin peak 168......Intravenous GLP-1 [7-36 amide] can normalize fasting hyperglycaemia in Type 2 diabetic patients. Whether GLP-1 [7-37] has similar effects and how quickly plasma glucose concentrations revert to hyperglycaemia after stopping GLP-1 is not known. Therefore, 8 patients with Type 2 diabetes (5 female, 3...... male; 65+/-6 years; BMI 34.3+/-7.9 kg m(-2); HbA1c 9.6+/-1.2%; treatment with diet alone (n=2), sulphonylurea (n=5), metformin (n=1)) were examined twice in randomized order. GLP-1 [7-36 amide] or [7-37] (1 pmol kg(-1)min(-1) were infused intravenously over 4 h in fasted subjects. Plasma glucose...

(S)-1-Aminoindane : synthesis by chirality transfer using (R)-phenylglycine amide as chiral auxiliary

NARCIS (Netherlands)

Uiterweerd, Patrick G.H.; Sluis, Marcel van der; Kaptein, Bernard; Lange, Ben de; Kellogg, Richard M.; Broxterman, Quirinus B.

2003-01-01

A practical asymmetric synthesis of nearly enantiomerically pure (S)-1-aminoindane has been developed. The key step involves the diastereoselective heterogeneous metal-catalyzed reduction of the ketimine of 1-indanone with the chiral auxiliary (R)-phenylglycine amide. The selectivity of the

Mechanistic Investigation of the Ruthenium–N-Heterocyclic-Carbene-Catalyzed Amidation of Alcohols and Amines

DEFF Research Database (Denmark)

Makarov, Ilya; Fristrup, Peter; Madsen, Robert

2012-01-01

The mechanism of the ruthenium–N-heterocyclic-carbene-catalyzed formation of amides from alcohols and amines was investigated by experimental techniques (Hammett studies, kinetic isotope effects) and by a computational study by using dispersion-corrected density functional theory (DFT/ M06...

Three new amides from streptomyces sp. H7372

Energy Technology Data Exchange (ETDEWEB)

Cheenpracha, Sarot; Borris, Robert P.; Tran, Tammy T.; Chang, Leng Chee, E-mail: lengchee@hawaii.ed [University of Hawaii Hilo, HI (United States). College of Pharmacy. Dept. of Pharmaceutical Sciences; Jee, Jap Meng; Seow, Heng Fong; Cheah, Hwen-Yee [Universiti Putra Malaysia, Selangor (Malaysia). Faculty of Medicine and Health Sciences. Department of Pathology. bImmunology Unit; Hoc, Coy Choke [University Malaysia Sabah (Malaysia). School of Science and Technology. Biotechnology Program

2011-07-01

Three new amides, methyl phenatate A (1), actiphenamide (2) and actiphenol 1-beta-D-glucopyranoside (3), along with thirteen known compounds, were isolated from the organic extract of a fermentation culture of Streptomyces sp. H7372. The structures were elucidated by spectroscopic methods including 1D- and 2D-NMR techniques, and MS analyses. Cycloheximide (6) and cyclo({Delta}Ala-L-Val) (8) gave a clear zone of inhibition of Ras-Raf-1 interaction in the yeast two hybrid assay which showed high potency with 10 and 25 mm clear ZOIs on SD His{sup -} and inactive on SD His{sup +} at 2.5 mug per disk, respectively. (author)

Catecholic amides as potential selective phosphodiesterase 4D inhibitors: Design, synthesis, pharmacological evaluation and structure-activity relationships.

Science.gov (United States)

Zhou, Zhong-Zhen; Ge, Bing-Chen; Chen, Yu-Fang; Shi, Xiu-Dong; Yang, Xue-Mei; Xu, Jiang-Ping

2015-11-15

In this study, a series of catechol-based amides (8a-n) with different amide linkers linking the catecholic moiety to the terminal phenyl ring was designed and synthesized as potent phosphodiesterase (PDE) 4D inhibitors. The inhibitory activities of these compounds were evaluated against the core catalytic domains of human PDE4 (PDE4CAT), full-length PDE4B1 and PDE4D7 enzymes, and other PDE family members. The results indicated the majority of compounds 8a-n displayed moderate to good inhibitory activities against PDE4CAT. Among these compounds, compound 8 j with a short amide linker (-CONHCH2-) displayed comparable PDE4CAT inhibitory activity (IC50=410 nM) with rolipram. More interestingly, compound 8 g, a potent and selective PDE4D inhibitor (IC50=94 nM), exhibited a 10-fold selectivity over the PDE4B subtypes and an over 1000-fold selectivity against other PDE family members. Docking simulations suggested that 8 g forms three extra H-bonds with the N-H of residue Asn487 and two water molecules. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Multifaceted catalytic hydrogenation of amides via diverse activation of a sterically confined bipyridine-ruthenium framework.

Science.gov (United States)

Miura, Takashi; Naruto, Masayuki; Toda, Katsuaki; Shimomura, Taiki; Saito, Susumu

2017-05-16

Amides are ubiquitous and abundant in nature and our society, but are very stable and reluctant to salt-free, catalytic chemical transformations. Through the activation of a "sterically confined bipyridine-ruthenium (Ru) framework (molecularly well-designed site to confine adsorbed H 2 in)" of a precatalyst, catalytic hydrogenation of formamides through polyamide is achieved under a wide range of reaction conditions. Both C=O bond and C-N bond cleavage of a lactam became also possible using a single precatalyst. That is, catalyst diversity is induced by activation and stepwise multiple hydrogenation of a single precatalyst when the conditions are varied. The versatile catalysts have different structures and different resting states for multifaceted amide hydrogenation, but the common structure produced upon reaction with H 2 , which catalyzes hydrogenation, seems to be "H-Ru-N-H."

Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides

Science.gov (United States)

Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which procee...

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....

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.

Synthesis, characterization and biological evaluation of novel α, β unsaturated amides.

Science.gov (United States)

Esmailzadeh, K; Housaindokht, M R; Moradi, A; Esmaeili, A A; Sharifi, Z

2016-05-15

Three derivatives of α,β unsaturated amides have been successfully synthesized via Ugi-four component (U-4CR) reaction. The interactions of the amides with calf thymus deoxyribonucleic acid (ct-DNA) have been investigated in the Tris-HCl buffer (pH=7.4) using viscometric, spectroscopic, thermal denaturation studies, and also molecular docking. By UV-Vis absorption spectroscopy studies, adding CT-DNA to the compound solution caused the hypochromism indicates that there are interactions between the compounds and DNA base pairs. In competitive fluorescence with methylene blue as an intercalator probe, adding compounds to DNA-MB solution caused an increase in emission spectra of the complex. This could be because of compound replacing, with similar binding mode of MB, between the DNA base pairs due to release of bonded MB molecules from DNA-MB complex. Thermal denaturation studies and viscometric experiments also indicated that all three investigated compounds bind to CT-DNA by non-classical intercalation mode. Additionally, molecular docking technique predicted partial intercalation binding mode for the compounds. Also, the highest binding energy was obtained for compound 5a. These results are in agreement with results obtained by empirical methods. Copyright © 2016 Elsevier B.V. All rights reserved.

Protein structure validation and refinement using amide proton chemical shifts derived from quantum mechanics

DEFF Research Database (Denmark)

Christensen, Anders Steen; Linnet, Troels Emtekær; Borg, Mikael

2013-01-01

We present the ProCS method for the rapid and accurate prediction of protein backbone amide proton chemical shifts - sensitive probes of the geometry of key hydrogen bonds that determine protein structure. ProCS is parameterized against quantum mechanical (QM) calculations and reproduces high level...

Vitamin E amides, a new class of vitamin E analogues with enhanced proapoptotic activity

Czech Academy of Sciences Publication Activity Database

Tomic-Vatic, A.; EyTina, J.; Chapmann, J.; Mahdavian, E.; Neužil, Jiří; Salvatore, B.A.

2005-01-01

Roč. 117, č. 2 (2005), s. 118-193 ISSN 0020-7136 Institutional research plan: CEZ:AV0Z5052915; CEZ:AV0Z50520514 Keywords : vitamin E amides * apoptosis * anticancer agents Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 4.700, year: 2005

Conformation-Specific IR and UV Spectroscopy of the Amino Acid Glutamine: Amide-Stacking and Hydrogen Bonding in AN Important Residue in Neurodegenerative Diseases

Science.gov (United States)

Walsh, Patrick S.; Dean, Jacob C.; Zwier, Timothy S.

2014-06-01

Glutamine plays an important role in several neurodegenerative diseases including Huntington's disease (HD) and Alzheimer's disease (AD). An intriguing aspect of the structure of glutamine is its incorporation of an amide group in its side chain, thereby opening up the possibility of forming amide-amide H-bonds between the peptide backbone and side chain. In this study the conformational preferences of two capped gluatamines Z(carboxybenzyl)-Glutamine-X (X=OH, NHMe) are studied under jet-cooled conditions in the gas phase in order to unlock the intrinsic structural motifs that are favored by this flexible sidechain. Conformational assignments are made by comparing the hydride stretch ( 3100-3700 cm-1) and amide I and II ( 1400-1800 cm-1) resonant ion-dip infrared spectra with predictions from harmonic frequency calculations. Assigned structures will be compared to previously published results on both natural and unnatural residues. Particular emphasis will be placed on the comparison between glutamine and unconstrained γ-peptides due to the similar three-carbon spacing between backbone and side chain in glutamine to the backbone spacing in γ-peptides. The ability of the glutamine side-chain to form amide stacked conformations will be a main focus, along with the prevalence of extended backbone type structures. W. H. James, III, C W. Müller, E. G. Buchanan, M. G. D. Nix, L. Guo, L. Roskop, M. S. Gordon, L. V. Slipchenko, S. H. Gellman, and T. S. Zwier, J. Am. Chem. Soc., 2009, 131(40), 14243-14245.

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.

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.

Diazonium modification of porous graphitic carbon with catechol and amide groups for hydrophilic interaction and attenuated reversed phase liquid chromatography.

Science.gov (United States)

Iverson, Chad D; Zhang, Ya; Lucy, Charles A

2015-11-27

Porous graphitic carbon (PGC) is an increasingly popular and attractive phase for HPLC on account of its chemical and thermal stability, and its unique separation mechanism. However, native PGC is strongly hydrophobic and in some instances excessively retentive. As part of our effort to build a library of hydrophilic covalently modified PGC phases, we functionalized PGC with catechol and amide groups by means of aryl diazonium chemistry to produce two new phases. Successful grafting was confirmed by X-ray photoelectron spectroscopy (XPS). Under HILIC conditions, the Catechol-PGC showed up to 5-fold increased retention relative to unmodified PGC and selectivity that differed from four other HILIC phases. Under reversed phase conditions, the Amide-PGC reduced the retentivity of PGC by almost 90%. The chromatographic performance of Catechol-PGC and Amide-PGC is demonstrated by separations of nucleobases, nucleosides, phenols, alkaline pharmaceuticals, and performance enhancing stimulants. These compounds had retention factors (k) ranging from 0.5 to 13. Copyright © 2015 Elsevier B.V. All rights reserved.

Dielectric relaxation studies of dilute solutions of amides

Energy Technology Data Exchange (ETDEWEB)

Malathi, M.; Sabesan, R.; Krishnan, S

2003-11-15

The dielectric constants and dielectric losses of formamide, acetamide, N-methyl acetamide, acetanilide and N,N-dimethyl acetamide in dilute solutions of 1,4-dioxan/benzene have been measured at 308 K using 9.37 GHz, dielectric relaxation set up. The relaxation time for the over all rotation {tau}{sub (1)} and that for the group rotation {tau}{sub (2)} of (the molecules were determined using Higasi's method. The activation energies for the processes of dielectric relaxation and viscous flow were determined by using Eyring's rate theory. From relaxation time behaviour of amides in non-polar solvent, solute-solvent and solute-solute type of molecular association is proposed.

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

High Performance Liquid Chromatographic Analysis of Phytoplankton Pigments Using a C16-Amide Column

Science.gov (United States)

A reverse-phase high performance liquid chromatographic (RP-HPLC) method was developed to analyze in a single run, most polar and non-polar chlorophylls and carotenoids from marine phytoplankton. The method is based on a RP-C16-Amide column and a ternary gradient system consistin...

A New Amide from the Stem Bark of Illiciumdifengpi and Its Anti-inflammatory Activity

Directory of Open Access Journals (Sweden)

Chuntong Li

2015-01-01

Full Text Available A new amide, named ( 2E, 4E-5-phenyl-N-(2-phenylethyl-2,4-pentadienamide (1 , together with one known amide, N -2-phenylet hylcinnamide (2 and two known ceramides, 2-​hydroxy-​N-​[(1S,​2R,​3E​-​2-​hydroxy-​1-​(hydroxymethyl​-​3-​heptadecenyl]​-pentadecanamide (3, 1-O-(β-D-glucopyranosyl-(2S,3R,4E,8E-2-[(2R-2-hydroxypentadecanoylamino]-4,8-octadecadiene-1,3-diol (4 were isolated from the stem bark of Illicium difengpi. The structures of the isolated compounds were elucidated by analyses of their 1H and 13C NMR, COSY, H S QC, HMBC spectr a and HR-ESI/MS mass spectrometric data. Anti-inflammatory assays with compounds 1‒4 were carried out, compounds 1 and 2 showed significant inhibitory effect on TNF- α release in LPS stimulated RAW 264.7 macrophages .

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.

Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

Science.gov (United States)

An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

Poly(amic acid)s and their poly(amide imide) counterparts containing azobenzene moieties: Characterization, imidization kinetics and photochromic properties

Energy Technology Data Exchange (ETDEWEB)

Konieczkowska, Jolanta [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland); Institute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice (Poland); Janeczek, Henryk [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland); Kozanecka-Szmigiel, Anna, E-mail: annak@if.pw.edu.pl [Faculty of Physics, Warsaw University of Technology, 75 Koszykowa Str., 00-662 Warszawa (Poland); Schab-Balcerzak, Ewa, E-mail: eschab-balcerzak@cmpw-pan.edu.pl [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland)

2016-09-01

We report on a series of novel photochromic poly(amide imide)s and their poly(amic acid) precursors bearing azobenzene chromophores as the side groups. The chemical structures of the polymers were designed so that they exhibited an enhanced thermal stability combined with a large and stable birefringence photogenerated by light of the wavelengths belonging to a wide spectral range. The polymers possessed rigidly attached azochromophores in the content of either one or two per a repeating unit, which in the latter case differed in their structures. The imidization kinetics of the poly(amic acid)s was investigated by differential scanning calorimetry and the kinetic parameters were estimated using Ozawa and Kissinger methods. Measurements of the selected physical properties of the polymers, such as solubility, supramolecular structure, linear absorption, thermal stability, glass transition and photochromic response were performed and used for determination of the structure-property relations. The measurements of photochromic properties showed a very efficient generation of optical anisotropy upon blue and violet irradiation, for both the poly(amide imide)s containing two different chromophores in the repeating unit and for their precursors. For these poly(amide imide)s and for their precursors an exceptionally slow decrease in the photoinduced optical anisotropy in the dark was also observed. - Highlights: • Three azopoly(amide imide)s were obtained from azopoly(amic acid)s. • Chosen physicochemical properties and photochromic responses were measured. • Desired optical response was found for polymers with two azo-dyes in repeating unit. • Structure-property relations were shown.

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)

Acute effects of glucagon-like peptide-1, GLP-1_{9-36 amide}, and exenatide on mesenteric blood flow, cardiovascular parameters, and biomarkers in healthy volunteers

DEFF Research Database (Denmark)

Hansen, Lasse Bremholm; Andersen, Ulrik B; Hornum, Mads

2017-01-01

arteries. GLP-1 significantly increased heart rate (two-way ANOVA, injection [P = 0.0162], time [P = 0.0038], and injection × time [P = 0.082]; Tukey post hoc GLP-1 vs. saline and GLP-19-36amide [P stroke volume compared to GLP-19-36 amide...... subcutaneous injections of GLP-1, GLP-19-36 amide (bioactive metabolite), exenatide (stable GLP-1 agonist), or saline on four separate days. Blood flow in mesenteric, celiac, and renal arteries was measured by Doppler ultrasound. Blood pressure, heart rate, cardiac output, and stroke volume were measured...

Synthesis and structure-activity relationship of α-keto amides as enterovirus 71 3C protease inhibitors.

Science.gov (United States)

Zeng, Debin; Ma, Yuying; Zhang, Rui; Nie, Quandeng; Cui, Zhengjie; Wang, Yaxin; Shang, Luqing; Yin, Zheng

2016-04-01

α-Keto amide derivatives as enterovirus 71 (EV71) 3C protease (3C(pro)) inhibitors have been synthesized and assayed for their biochemical and antiviral activities. structure-activity relationship (SAR) study indicated that small moieties were primarily tolerated at P1' and the introduction of para-fluoro benzyl at P2 notably improved the potency of inhibitor. Inhibitors 8v, 8w and 8x exhibited satisfactory activity (IC50=1.32±0.26μM, 1.88±0.35μM and 1.52±0.31μM, respectively) and favorable CC50 values (CC50>100μM). α-Keto amide may represent a good choice as a warhead for EV71 3C(pro) inhibitor. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Environmentally benign synthesis of amides and ureas via catalytic dehydrogenation coupling of volatile alcohols and amines in a Pd-Ag membrane reactor

KAUST Repository

Chen, Tao

2016-05-31

In this study, we report the direct synthesis of amides and ureas via the catalytic dehydrogenation of volatile alcohols and amines using the Milstein catalyst in a Pd-Ag/ceramic membrane reactor. A series of amides and ureas, which could not be synthesized in an open system by catalytic dehydrogenation coupling, were obtained in moderate to high yields via catalytic dehydrogenation of volatile alcohols and amines. This process could be monitored by the hydrogen produced. Compared to the traditional method of condensation, this catalytic system avoids the stoichiometric pre-activation or in situ activation of reagents, and is a much cleaner process with high atom economy. This methodology, only possible by employing the Pd-Ag/ceramic membrane reactor, not only provides a new environmentally benign synthetic approach of amides and ureas, but is also a potential method for hydrogen storage.

Environmentally benign synthesis of amides and ureas via catalytic dehydrogenation coupling of volatile alcohols and amines in a Pd-Ag membrane reactor

KAUST Repository

Chen, Tao; Zeng, Gaofeng; Lai, Zhiping; Huang, Kuo-Wei

2016-01-01

In this study, we report the direct synthesis of amides and ureas via the catalytic dehydrogenation of volatile alcohols and amines using the Milstein catalyst in a Pd-Ag/ceramic membrane reactor. A series of amides and ureas, which could not be synthesized in an open system by catalytic dehydrogenation coupling, were obtained in moderate to high yields via catalytic dehydrogenation of volatile alcohols and amines. This process could be monitored by the hydrogen produced. Compared to the traditional method of condensation, this catalytic system avoids the stoichiometric pre-activation or in situ activation of reagents, and is a much cleaner process with high atom economy. This methodology, only possible by employing the Pd-Ag/ceramic membrane reactor, not only provides a new environmentally benign synthetic approach of amides and ureas, but is also a potential method for hydrogen storage.

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...

Antifungal activity of natural and synthetic amides from Piper species

Energy Technology Data Exchange (ETDEWEB)

Marques, Joaquim V.; Oliveira, Alberto de; Kato, Massuo J., E-mail: majokato@iq.usp.b [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica; Raggi, Ludmila; Young, Maria C. [Instituto de Botanica, Sao Paulo, SP (Brazil). Secao de Fisiologia e Bioquimica de Plantas

2010-07-01

The antifungal leaves extract from Piper scutifolium was submitted to bioactivity-guided chromatographic separation against Cladosporium cladosporioides and C. sphaerospermum yielding piperine, piperlonguminine and corcovadine as the active principles which displayed a detection limit of 1 {mu}g. Structure-activity relationships were investigated with the preparation of twelve analogs having differences in the number of unsaturations, aromatic ring substituents and in the amide moiety. Analogs having a single double-bond and no substituent in the aromatic ring displayed higher activity, while N,N,-diethyl analogs displayed higher dose-dependent activity. (author)

Nitrosation of amides involves a pseudopericyclic 1,3-sigmatropic rearrangement.

Science.gov (United States)

Birney, David M

2004-03-04

Two possible pathways for the nitrosation of formamide and N-methyl formamide by nitrosonium ion (NO(+)) have been investigated at the B3LYP/6-31G(d,p) level. The key steps are pseudopericyclic 1,3-sigmatropic rearrangements to give the observed N-nitrosamides. The transition structures (8a and 8b) are close to planar on the amide moiety and have remarkably low barriers of only 6.6 and 4.8 kcal/mol from the lowest energy conformations of 6a and 6b, respectively. [reaction: see text

Synthesis of a hollow fiber type porous chelating resin containing the amide oxime group by radiation induced graft polymerization for the uranium recovery

International Nuclear Information System (INIS)

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

1986-01-01

A hollow fiber type porous chelating resin containing amide oxime as a functional group was synthesized and used as an adsorbent for the recovery of uranium. Hollow fiber type porous polyethylene was used as a base polymer. Acrylonitrile was grafted onto it by the radiation-induced graft polymerization. By changing the reaction time, four kinds of graft polymer were obtained. The degree of grafting ranged from 79 % to 127 %. Each resin was soaked in hydroxylamine solution, and the cyano group was converted to amide oxime group. By elemental analysis, the amount of nitrogen introduced on the graft polymer resin in amidoximation was determined to range from 4.3 mmol to 8.5 mmol per 1 g of base polymer. Most of the nitrogen is considered to belong to the amide oxime group. The pore radius, which was initially distributed broadly from about 500 A to 10000 A for the base polymer, was changed to about 1000 A with narrow distribution by the grafting. The pore volume was 1.2 ∼ 1.4 cm 3 per 1 gram of the amide oxime resin, which was about half of that of the initial base polymer. But the pore volume per 1 g base polymer of the amide oxime resin increased with an increase in the grafting degree, e.g. 4.5 cm 3 /g base polymer at 127 % of grafting degree. Specific surface area, which was 30 m 2 /g in base polymer, decreased with an increase in the grafting degree, e.g. 15 m 2 /g at 127 % of grafting degree. Both the amounts of the adsorbed hydrochloric acid and the adsorbed copper were about 1.5 times of the amount of nitrogen introduced in the amidoximation. The reason is considered to be caused by the formation of hydroxamic acid and amide from the measurements of the IR spectra. The amount of uranium adsorbed on the resin was 64 % of the amount of nitrogen introduced in the amidoximation. (author)

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...

Preparation of an amide group-connected graphene-polyaniline nanofiber hybrid and its application in supercapacitors.

Science.gov (United States)

Jianhua, Liu; Junwei, An; Yecheng, Zhou; Yuxiao, Ma; Mengliu, Li; Mei, Yu; Songmei, Li

2012-06-27

Polyaniline (PANI) nanofiber is grafted onto graphene to obtain a novel graphene-polyaniline (GP) hybrid. Graphene is activated using SOCl2 and reacts with PANI to form an amide group that intimately connects graphene and PANI. The existence of the amide group and its anchoring effect in the GP hybrid are confirmed and characterized by SEM, TEM, FT-IR, Raman, XPS and quantum chemistry analyses. Electrochemical tests reveal that the GP hybrid has high capacitance performances of 579.8 and 361.9 F g(-1) at current densities of 0.3 and 1 A g(-1). These values indicate superiority to materials interacted by van der Waals force. Long-term charge/discharge tests at high current densities show that the GP hybrid preserves 96% of its initial capacitance, demonstrating good electrochemical stability. The improved electrochemical performance suggests promising application of the GP hybrid in high-performance supercapacitors.

(Z)-N,N-Dimethyl-2-[phen­yl(pyridin-2-yl)methyl­idene]hydrazinecarbothio­amide

Science.gov (United States)

Jayakumar, K.; Sithambaresan, M.; Prathapachandra Kurup, M. R.

2011-01-01

The title compound, C15H16N4S, exists in the Z conformation with the thionyl S atom lying cis to the azomethine N atom. The shortening of the N—N distance [1.3697 (17) Å] is due to extensive delocalization with the pyridine ring. The hydrazine–carbothio­amide unit is almost planar, with a maximum deviation of 0.013 (2) Å for the amide N atom. The stability of this conformation is favoured by the formation of an intra­molecular N—H⋯N hydrogen bond. The packing of the mol­ecules involves no classical inter­molecular hydrogen-bonding inter­actions; however, a C—H⋯π inter­action occurs. PMID:22199715

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.

Synthesis and antifungal evaluation of PCA amide analogues.

Science.gov (United States)

Qin, Chuan; Yu, Di-Ya; Zhou, Xu-Dong; Zhang, Min; Wu, Qing-Lai; Li, Jun-Kai

2018-04-18

To improve the physical and chemical properties of phenazine-1-carboxylic acid (PCA) and find higher antifungal compounds, a series of PCA amide analogues were designed and synthesized and their structures were confirmed by 1 H NMR, HRMS, and X-ray. Most compounds showed some antifungal activities in vitro. Particularly, compound 3d exhibited inhibition effect against Pyriculariaoryzac Cavgra with EC 50 value of 28.7 μM and compound 3q exhibited effect against Rhizoctonia solani with EC 50 value of 24.5 μM, more potently active than that of the positive control PCA with its EC 50 values of 37.3 μM (Pyriculariaoryzac Cavgra) and 33.2 μM (Rhizoctonia solani), respectively.

Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

CERN Document Server

Park, Y T; Kim, M S; Kwon, J H

2002-01-01

Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

Energy Technology Data Exchange (ETDEWEB)

Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee [Kyungpook National Univ., Daegu (Korea, Republic of)

2002-09-01

Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

International Nuclear Information System (INIS)

Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee

2002-01-01

Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed

One-pot synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines using supported gold and base as catalysts

DEFF Research Database (Denmark)

Kegnæs, Søren; Mielby, Jerrik Jørgen; Mentzel, Uffe Vie

2012-01-01

Synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines via intermediate formation of methyl esters is highly efficient and selective when using a catalytic system comprised of supported gold nanoparticles and added base in methanol.......Synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines via intermediate formation of methyl esters is highly efficient and selective when using a catalytic system comprised of supported gold nanoparticles and added base in methanol....

3D graphene preparation via covalent amide functionalization for efficient metal-free electrocatalysis in oxygen reduction

Science.gov (United States)

Ahmed, Mohammad Shamsuddin; Kim, Young-Bae

2017-02-01

3D and porous reduced graphene oxide (rGO) catalysts have been prepared with sp3-hybridized 1,4-diaminobutane (sp3-DABu, rGO-sp3-rGO) and sp2-hybridized 1,4-diaminobenzene (sp2-DABe, rGO-sp2-rGO) through a covalent amidation and have employed as a metal-free electrocatalyst for oxygen reduction reaction (ORR) in alkaline media. Both compounds have used as a junction between functionalized rGO layers to improve electrical conductivity and impart electrocatalytic activity to the ORR resulting from the interlayer charge transfer. The successful amidation and the subsequent reduction in the process of catalyst preparation have confirmed by X-ray photoelectron spectroscopy. A hierarchical porous structure is also confirmed by surface morphological analysis. Specific surface area and thermal stability have increased after successful the amidation by sp3-DABu. The investigated ORR mechanism reveals that both functionalized rGO is better ORR active than nonfunctionalized rGO due to pyridinic-like N content and rGO-sp3-rGO is better ORR active than rGO-sp2-rGO due to higher pyridinic-like N content and π-electron interaction-free interlayer charge transfer. Thus, the rGO-sp3-rGO has proven as an efficient metal-free electrocatalyst with better electrocatalytic activity, stability, and tolerance to the crossover effect than the commercially available Pt/C for ORR.

17O NMR Studies of the Solvation State of cissolidustrans Isomers of Amides and Model Protected Peptides

Science.gov (United States)

Gerothanassis; Vakka; Troganis

1996-06-01

17O shielding constants have been utilized to investigate solvation differences of the cissolidustrans isomers of N-methylformamide (NMF), N-ethylformamide (NEF), and tert-butylformamide (TBF) in a variety of solvents with particular emphasis on aqueous solution. Comparisons are also made with protected peptides of the formulas CH3CO-YOH, CH3CO-Y-NHR (Y = Pro, Sar), and CH3CO-Y-Z-NHR (Y = Pro; Z = D-Ala) selectively enriched in 17O at the acetyl oxygen atom. Hydration at the amide oxygen induces large and specific modifications of the 17O shielding constants, which are practically the same for the cis and trans isomers of NMF, NEF, and the protected peptides. For tert-butylformamide, the strong deshielding of the trans isomer compared to that of the cis isomer may be attributed to an out-of-plane (torsion-angle) deformation of the amide bond andsolidusor a significant reduction of solvation of the trans isomer due to steric inhibition of the bulky tert-butyl group. Good linear correlation between delta(17O) of amides and delta(17O) of acetone was found for different solvents which have varying dielectric constants and solvation abilities. Sum-over-states calculations, within the solvaton model, underestimate effects of the dielectric constant of the medium on 17O shielding, while finite-perturbation-theory calculations give good agreement with the experiment.

Structuring of Amide Cross-Linked Non-Bridged and Bridged Alkyl-Based Silsesquioxanes.

Science.gov (United States)

Nunes, S C; de Zea Bermudez, V

2018-02-06

The development of sophisticated organized materials exhibiting enhanced properties is a challenging topic of the domain of organic/inorganic hybrid materials. This review, composed of four sections, reports the work we have carried out over the last 10 years on the synthesis of amide cross-linked alkyl/siloxane hybrids by means of sol-gel chemistry and self-directed assembly/self-organization routes relying on weak interactions (hydrophobic interactions and hydrogen bonding). The various as-produced lamellar structures displaying a myriad of morphologies, often closely resembling those found in natural materials, are discussed. The major role played by the synthetic conditions (pH, water content, co-solvent(s) nature/concentration and dopant presence/concentration), the alkyl chains (length and presence of ramification or not) and the number of the amide cross-links present in the precursor, is evidenced. Examples of highly organized hybrids structures incorporating ionic species (alkali and alkaline earth metal salts) and optically-active centers (organic dyes and lanthanide ions) are described. A useful qualitative relationship deduced between the emission quantum yield of the ordered hybrid materials and the degree of order of the hydrogen-bonded network is highlighted. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of novel amides based on acridone scaffold with interesting antineoplastic activity.

Science.gov (United States)

Mahajan, Anand A; Rane, Rajesh A; Amritkar, Anish A; Naphade, Shital S; Miniyar, Pankaj B; Bangalore, Pavan Kumar; Karpoormath, Rajshekhar

2015-01-01

In search of novel cytotoxic agents based on acridone scaffold, twenty five derivatives of acridone-2- carboxamide were synthesized and evaluated against a panel of eleven cancer cell lines by using MTT assay. Amides, A5 and A8 (IC50 = 0.3 µM) exhibited good cytotoxicity against MCF7. Compound A22 (IC50 = 4.3 µM) was found to be selectively cytotoxic against cancer cell line MCF7 and KB403. Particularly, promising cytotoxic activities were shown by amides A6 (IC50 = 0.7 µM), A16 (IC50 = 6.3 µM), A8 (IC50 = 0.9 µM ), A21 (IC50 = 1.3 µM), A5 (IC50 = 2.9 µM), A8 (IC50 = 2.8 µM), A14 (IC50 = 0.8 µM), A9 (IC50 = 0.8 µM) and A8 (IC50 = 0.4 µM) against cell lines; PA1, WRL68, CaCO2, TK-10, K-562, PC-3, HOP-92, ECV-304 and UACC-257, respectively. The favorable cytotoxic profile and non-toxicity towards normal human cells displayed by the derivative revealed their potential for further anticancer drug developments.

Anti-nociceptive, anti-hyperalgesic and anti-arthritic activity of amides and extract obtained from Piper amalago in rodents.

Science.gov (United States)

da Silva Arrigo, Jucicléia; Balen, Eloise; Júnior, Ubirajara Lanza; da Silva Mota, Jonas; Iwamoto, Renan Donomae; Barison, Andersson; Sugizaki, Mario Mateus; Leite Kassuya, Cândida Aparecida

2016-02-17

Piper amalago (Piperaceae) has been used in folk medicine as an analgesic. This study aimed to evaluate the pharmacological effects of extract and pure amides obtained from P. amalago on pain to provide a pharmacological basis for their use in traditional medicine. This study evaluated the anti-nociceptive, anti-hyperalgesic, anti-arthritic and anti-depressive activities of the ethanolic extract of P. amalago (EEPA) and the amides N-[7-(3',4'-methylenedioxyphenyl)-2(Z),4(Z)-heptadienoyl] pyrrolidine (1) and N-[7-(3',4'-methylenedioxyphenyl)-2(E),4(E)-heptadienoyl] pyrrolidine (2) obtained from P. amalago in animal models. Mice treated daily with EEPA (100mg/kg, p.o.) were assayed for 20 days for knee edema (micrometer measurement), mechanical hyperalgesia (analgesiometer analysis), heat sensitivity and immobility (forced swim test) in the Complete Freund's Adjuvant (CFA) model. Cold (acetone test) and mechanical hyperalgesia (electronic von Frey analysis) responses were evaluated for 15 days in rats treated with oral EEPA (100mg/kg) in the spared nerve injury (SNI) model. Meanwhile, mice were evaluated for carrageenan-induced edema and mechanical hyperalgesia and for nociception using the formalin model after a single administration of EEPA (100mg/kg) or amides 1 and 2 (1mg/kg). Amides (1) and (2) were detected and isolated from the EEPA. The EEPA inhibited mechanical hyperalgesia, knee edema, and heat hyperalgesia, but not depressive-like behavior, induced by the intraplantar injection of CFA. When evaluated in the SNI model, the EEPA inhibited mechanical and cold hyperalgesia. The EEPA, 1 and 2 prevented the mechanical hyperalgesia induced by carrageenan and the anti-nociceptive effects in both phases of formalin nociception. The EEPA did not induce alterations in the open field test. The EEPA was effective for inhibition of pain and arthritic parameters but was not effective against depressive-like behavior; additionally, it did not alter locomotor activity. The

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.

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

Directory of Open Access Journals (Sweden)

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.

Papain-like protease (PLpro) inhibitory effects of cinnamic amides from Tribulus terrestris fruits.

Science.gov (United States)

Song, Yeong Hun; Kim, Dae Wook; Curtis-Long, Marcus John; Yuk, Heung Joo; Wang, Yan; Zhuang, Ningning; Lee, Kon Ho; Jeon, Kwon Seok; Park, Ki Hun

2014-01-01

Tribulus terrestris fruits are well known for their usage in pharmaceutical preparations and food supplements. The methanol extract of T. terrestris fruits showed potent inhibition against the papain-like protease (PLpro), an essential proteolylic enzyme for protection to pathogenic virus and bacteria. Subsequent bioactivity-guided fractionation of this extract led to six cinnamic amides (1-6) and ferulic acid (7). Compound 6 emerged as new compound possessing the very rare carbinolamide motif. These compounds (1-7) were evaluated for severe acute respiratory syndrome coronavirus (SARS-CoV) PLpro inhibitory activity to identify their potencies and kinetic behavior. Compounds (1-6) displayed significant inhibitory activity with IC50 values in the range 15.8-70.1 µM. The new cinnamic amide 6 was found to be most potent inhibitor with an IC50 of 15.8 µM. In kinetic studies, all inhibitors exhibited mixed type inhibition. Furthermore, the most active PLpro inhibitors (1-6) were proven to be present in the native fruits in high quantities by HPLC chromatogram and liquid chromatography with diode array detection and electrospray ionization mass spectrometry (LC-DAD-ESI/MS).

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...

Assessment of the amide-I local modes in gamma- and beta-turns of peptides.

Science.gov (United States)

Wang, Jianping

2009-07-14

The amide-I local modes, mainly the C[double bond, length as m-dash]O stretching vibrations, form the structural basis of femtosecond 2D IR spectroscopy in characterizing backbone structures and dynamics of peptides and proteins. In this work, a density functional theory (DFT) level of computational assessment of the amide-I local modes in oligomers mostly in the turn conformations was carried out. It is shown that local mode properties, including transition frequencies and transition dipole magnitudes and orientations, are slightly conformational dependent. However, the distributions of these properties in the peptide oligomers are narrow and have mean values almost identical to those from an isolated peptide monomer, justifying the prevalent use of a uniform local mode in modeling the 1D and 2D IR spectra. In addition, it is shown that the transition dipole magnitude and orientation of the peptide monomer predicted by the DFT calculations can be well approximated by electrostatic potential-based transition charge schemes, e.g. Merz-Singh-Kollman, CHELP, as well as CHELPG.

Synthesis, Characterization and Antimicrobial Evaluation of some Thiazole-Derived Carbamates, Semicarbazones, Amides and Carboxamide

International Nuclear Information System (INIS)

Balawi, N.A.A.; ALShaikh, M.A.A.; Alafeefy, A.M.; Khan, K.M.

2016-01-01

This study comprises the synthesis and characterization of twenty thiazole-derived carbamates (3a-e), N-substituted amides (8a-h) and carboxamide (10) from 2-aminothiazoles (1a, b) via nucleophilic substitution reactions with activated carbonyl compounds including, chloroformates (2a-d), acid chlorides (7a-e) and glutaric anhydride (9), respectively. Sequential hydrazinolysis of carbamate (3e) and condensation with a variety of aldehydes and ketones (5a d) afforded the corresponding semicarbazones (6a-d). Some selected synthesized compounds were subjected to in vitro antimicrobial evaluation against common pathogens including, Gram+ve bacteria Bacillus subtilis (NRRL B-543) and Staphylococcus aureus, Gram-ve bacteria Escherichia coli (NRRLB-21), yeasts-Candida albicans (NRRLY-477) and Saccharomyces cercvisiae (NRRL Y-567) and fungs Asperigillus niger (NRRL 599). Screening results revealed that most of the tested compounds possess good antimicrobial activity compared to standard drugs. The highest inhibitory effects against Gram-ve Escherichia coli, Gram+ve Staphylococcus aureus, yeast Candida albicans and fungus Aspergillus niger was displayed by amide (8g) bearing the thiophene moiety. (author)

An Effective Hg2+-Selective Fluorescent Chemosensor Based on a Calix[4]arene Bearing Four Dansyl Amides

Institute of Scientific and Technical Information of China (English)

LI Guang-Ke; LIU Min; YANG Guo-Qiang; CHEN Chuan-Feng; HUANG Zhi-Tang

2008-01-01

A new calix[4]arene-based fluorescent chemosensor bearing four dansyl amides on the upper rim (1) was con- veniently synthesized, which showed high sensitivity and selectivity toward Hg2+ over a wide range of metal ions in 50% aqueous acetonitrile. The complexation of Hg2+ ion induced a strong fluorescence quenching of 1 due to a well-defined electron transfer process from the dansyl group(s) to the metal center. Compared with compounds 2 and 3, tetradansyl amide substituted calix[4]arene 1 showed a preorganized and coordinated complexing site for metal ions. Moreover, the detection limit for Hg2. was found to be 3.41×10-6 mol·L-1, which might make 1 a po-tentially practical Hg2+-selective fluorescent sensor in aqueous system.

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....

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.