WorldWideScience

Sample records for amides

  1. Reliable determination of amidicity in acyclic amides and lactams.

    Science.gov (United States)

    Glover, Stephen A; Rosser, Adam A

    2012-07-06

    Two independent computational methods have been used for determination of amide resonance stabilization and amidicities relative to N,N-dimethylacetamide for a wide range of acyclic and cyclic amides. The first method utilizes carbonyl substitution nitrogen atom replacement (COSNAR). The second, new approach involves determination of the difference in amide resonance between N,N-dimethylacetamide and the target amide using an isodesmic trans-amidation process and is calibrated relative to 1-aza-2-adamantanone with zero amidicity and N,N-dimethylacetamide with 100% amidicity. Results indicate excellent coherence between the methods, which must be regarded as more reliable than a recently reported approach to amidicities based upon enthalpies of hydrogenation. Data for acyclic planar and twisted amides are predictable on the basis of the degrees of pyramidalization at nitrogen and twisting about the C-N bonds. Monocyclic lactams are predicted to have amidicities at least as high as N,N-dimethylacetamide, and the β-lactam system is planar with greater amide resonance than that of N,N-dimethylacetamide. Bicyclic penam/em and cepham/em scaffolds lose some amidicity in line with the degree of strain-induced pyramidalization at the bridgehead nitrogen and twist about the amide bond, but the most puckered penem system still retains substantial amidicity equivalent to 73% that of N,N-dimethylacetamide.

  2. Incorporation of different crystallizable amide blocks in segmented poly(ester amide)s

    NARCIS (Netherlands)

    Lips, P.A.M.; Broos, R.; Heeringen, van M.J.M.; Dijkstra, P.J.; Feijen, J.

    2005-01-01

    High molecular weight segmented poly(ester amide)s were prepared by melt polycondensation of dimethyl adipate, 1,4-butanediol and a symmetrical bisamide-diol based on ε-caprolactone and 1,2-diaminoethane or 1,4-diaminobutane. FT-IR and WAXD analysis revealed that segmented poly(ester amide)s based

  3. 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...

  4. 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...

  5. Nucleoside phosphorylation in amide solutions

    Science.gov (United States)

    Schoffstall, A. M.; Kokko, B.

    1978-01-01

    The paper deals with phosphorylation in possible prebiotic nonaqueous solvents. To this end, phosphorylation of nucleosides using inorganic phosphates in amide solutions is studied at room and elevated temperatures. Reaction proceeds most readily in formamide and N-methylformamide. Products obtained at elevated temperature are nucleotides, nucleoside 2',3'-cyclic phosphates, and when the phosphate concentration is high, nucleoside diphosphates. At room temperature, adenosine afforded a mixture of nucleotides, but none of the cyclic nucleotide. Conditions leading to the highest relative percentage of cyclic nucleotide involve the use of low concentrations of phosphate and an excess of nucleoside.

  6. Biocompatibility and degradation of aliphatic segmented poly(ester amide)s : in vitro and in vivo evaluation

    NARCIS (Netherlands)

    Lips, PAM; van Luyn, MJA; Chiellini, F; Brouwer, LA; Velthoen, IW; Dijkstra, PJ; Feijen, J

    2006-01-01

    Aliphatic segmented poly(ester amide)s, comprising a crystallizable amide phase and a flexible amorphous ester phase, were investigated for potential use in biomedical applications. By varying the amide content and the type of crystallizable amide segments, the polymer's thermal and mechanical prope

  7. 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.

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

    Science.gov (United States)

    Geerts, Roy; Kuijer, Patrick; van Ginkel, Cornelis G; Plugge, Caroline M

    2014-07-01

    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 N-[3-(dimethylamino)propyl] cocoamide and its hydrolysis product N,N-dimethyl-1,3-propanediamine, respectively. In mixed culture, both strains accomplished complete mineralization of N-[3-(dimethylamino)propyl] cocoamide. Aeromonas hydrophila PK3 was enriched with N-(1-ethylpiperazine) tall oil amide and subsequently isolated using agar plates containing dodecanoate. N-(2-Aminoethyl)piperazine, the hydrolysis product of N-(1-ethylpiperazine) tall oil amide, was not degraded. The aerobic biodegradation pathway for primary and secondary fatty acid amides of P. aeruginosa and A. hydrophila involved initial hydrolysis of the amide bond producing ammonium, or amines, where the fatty acids formed were immediately metabolized. Complete mineralization of secondary fatty acid amides depended on the biodegradability of the released amine. Tertiary fatty acid amides were not transformed by P. aeruginosa or A. hydrophila. These strains were able to utilize all tested primary and secondary fatty acid amides independent of the amine structure and fatty acid. Read-across of previous reported ready biodegradability results of primary and secondary fatty acid amides is justified based on the broad substrate specificity and the initial hydrolytic attack of the two isolates PK1 and PK3.

  9. Synthesis and Characterization of Poly(ether amide)s Containing Bisphthalazinone and Ether Linkages

    Institute of Scientific and Technical Information of China (English)

    Cheng LIU; Shou Hai ZHANG; Ming Jing WANG; Qi Zhen LIANG; Xi Gao JIAN

    2005-01-01

    A novel aromatic diacid, 4, 4'-bis[2-(4-carboxyphenyl)phthalazin-1-one-4-yl]-bisphenyl ether Ⅲ, containing bisphthalazinone and ether linkages was prepared from nucleophilic substitution of p-chlorobenzonitrile with the bisphenol-like monomer Ⅰ, followed by alkaline hydrolysis of the intermediate dinitrile Ⅱ. A series of poly(ether amide)s containing bisphthalazinone and ether linkages derived from diacid Ⅲ and aromatic diamines were synthesized by one-step solution condensation polymerization using triphenyl phosphite and pyridine as condensing agents. Moreover, the properties of poly(ether amide)s including thermal stability,solubility and crystallinity were also studied.

  10. 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.

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

    Science.gov (United States)

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

    2016-10-04

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

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

    Science.gov (United States)

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

    2012-06-21

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

  13. 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.

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

    Science.gov (United States)

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

    2015-07-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-07-15

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

  16. Preparation of amidated derivatives of carboxymethylcellulose.

    Science.gov (United States)

    Taubner, Tomáš; Synytsya, Andriy; Čopíková, Jana

    2015-01-01

    Carboxymethylcellulose (CMC) was selected as substrate for amidation based on previous results described for monocarboxy cellulose (MCC) with the aim to prepare highly substituted products. In comparison with MCC containing uronic carboxyl groups at C-6 position, O-carboxymethyl groups in CMC should be more accessible for reagents because they are more distant from the polysaccharide chain. Two-step way of amidation was based on the esterification of CMC carboxyls by reaction with methanol and further amino-de-alkoxylation (aminolysis) of the obtained methyl ester with amidation reagents (n-alkylamines, hydrazine and hydroxylamine). Purity and substitution degree of the products were monitored by the vibration spectroscopic methods (FTIR and Raman) and organic elemental analysis. Analytical methods confirmed the preparation of highly or moderately substituted N-alkylamides, hydrazide and hydroxamic acid of CMC.

  17. Synthesis of Calix[4]resorcinarene Amide Derivatives

    Institute of Scientific and Technical Information of China (English)

    Chao Guo YAN; Yun GE

    2004-01-01

    Three different synthetic routes were developed to introduce carbamoyloxy functional groups at the upper periphery of two calix[4]resorcinarenes. By treating activated esters 2a-b with excess corresponding amine such as 3-(dimethylamino)propylamine 3, α-phenethylamine 4 and triethylenetetramine 5, six amide derivatives 6a~8b were obtained in high yield (Route 1). The pyridine-linked amide derivatives 9a-b were prepared by using acid chloride intermediate (Route 2). The amide derivatives 10a-b were obtained in moderate yields by direct alkylation of phenolic hydroxyl groups of 1a-b with N,N-dipropylchloroacetoamide in the presence of K2CO3/KI in acetone (Route 3).

  18. 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.

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

    Science.gov (United States)

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

    2012-09-19

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

  20. 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.

  1. Variation of protein backbone amide resonance by electrostatic field

    OpenAIRE

    Sharley, John N.

    2015-01-01

    Amide resonance is found to be sensitive to electrostatic field with component parallel or antiparallel the amide C-N bond. This effect is linear and without threshold in the biologically plausible electrostatic field range -0.005 to 0.005 au. Variation of amide resonance varies Resonance-Assisted Hydrogen Bonding such as occurs in the hydrogen bonded chains of backbone amides of protein secondary structures such as beta sheet and alpha helix, varying the stability of the secondary structure....

  2. 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 c

  3. Efficient Amide Based Halogenide Anion Receptors

    Institute of Scientific and Technical Information of China (English)

    Hong Xing WU; Feng Hua LI; Hai LIN; Shou Rong ZHU; Hua Kuan LIN

    2005-01-01

    In this paper, we present the synthesis and anion recognition properties of the amide based phenanthroline derivatives 1, 2 and 3. In all cases 1:1 receptor: anion complexes were observed. The receptors were found to be selective for fluoride and chloride respectively over other putative anionic guest species.

  4. ACRYLATE-AMIDE FOAM CARDIOVASCULAR PROSTHESES.

    Science.gov (United States)

    thoracic and abdominal aorta. The use of a composite construction utilizing acrylate-amide foam is being evaluated in prostheses for mitral valve ...bleeding. The success of the initial experimental work has led to a clinical trial in which 99 replacement , bypass, or patch-angioplasty procedures... replacement , superior vena cava patch venoplasty, and esophageal replacement . (Author)

  5. Platinum catalysed hydrolytic amidation of unactivated nitriles

    NARCIS (Netherlands)

    Cobley, Christopher J.; Heuvel, Marco van den; Abbadi, Abdelilah; Vries, Johannes G. de

    2000-01-01

    The platinum(II) complex, [(Me2PO··H··OPMe2)PtH(PMe2OH)], efficiently catalyses the direct conversion of unactivated nitriles to N-substituted amides with both primary and secondary amines. Possible mechanisms for this reaction are discussed and evidence for initial amidine formation is reported. Is

  6. Tertiary fatty amides as diesel fuel substitutes

    Energy Technology Data Exchange (ETDEWEB)

    Serdari, Aikaterini; Lois, Euripides; Stournas, Stamoulis [National Technical Univ. of Athens, Dept. of Chemical Engineering, Athens (Greece)

    2000-07-01

    This paper presents experimental results regarding the impact of adding different tertiary amides of fatty acids to mineral diesel fuel; an assessment of the behaviour of these compounds as possible diesel fuel extenders is also included. Measurements of cetane number, cold flow properties (cloud point, pour point and CFPP), density, kinematic viscosity, flash point and distillation temperatures are reported, while initial experiments concerning the effects on particulate emissions are also described. Most of the examined tertiary fatty amides esters have very good performance and they can be easily prepared from fatty acids (biomass). Such compounds or their blends could be used as mineral diesel fuel or even fatty acid methylesters (FAME, biodiesel) substitutes or extenders. (Author)

  7. An amidated carboxymethylcellulose hydrogel for cartilage regeneration.

    Science.gov (United States)

    Leone, Gemma; Fini, Milena; Torricelli, Paola; Giardino, Roberto; Barbucci, Rolando

    2008-08-01

    An amidic derivative of carboxymethylcellulose was synthesized (CMCA). The new polysaccharide was obtained by converting a large percentage of carboxylic groups ( approximately 50%) of carboxymethylcellulose into amidic groups rendering the macromolecule quite similar to hyaluronan. Then, the polysaccharide (CMCA) was crosslinked. The behavior of CMCA hydrogel towards normal human articular chondrocytes (NHAC) was in vitro studied monitoring the cell proliferation and synthesis of extra cellular matrix (ECM) components and compared with a hyaluronan based hydrogel (Hyal). An extracellular matrix rich in cartilage-specific collagen and proteoglycans was secreted in the presence of hydrogels. The injectability of the new hydrogels was also analysed. An experimental in vivo model was realized to study the effect of CMCA and Hyal hydrogels in the treatment of surgically created partial thickness chondral defects in the rabbit knee. The preliminary results pointed out that CMCA hydrogel could be considered as a potential compound for cartilage regeneration.

  8. Amide-based Fluorescent Macrocyclic Anion Receptors

    Institute of Scientific and Technical Information of China (English)

    ZENG, Zhen-Ya(曾振亚); XU, Kuo-Xi(徐括喜); HE, Yong-Bing(何永炳); LIU, Shun-Ying(刘顺英); WU, Jin-Long(吴进龙); WEI, Lan-Hua(隗兰华); MENG, Ling-Zhi(孟令芝)

    2004-01-01

    Two fluorescent anion receptors (1 and 2) based on amide macrocycle were synthesized and corresponding fluorescence quenching induced by anion complexation was observed in different degree. Receptors form 1: 1 complexes with anions by hydrogen bonding interactions. Receptor 1 bound anions in the order of F->Cl->H2PO4->CH3COO->>Br-, I- and receptor 2 showed high selectivity to F- over other anions.

  9. 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.

  10. 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.

  11. 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.

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

    Science.gov (United States)

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

    2015-08-06

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

  13. New Umami Amides: Structure-Taste Relationship Studies of Cinnamic Acid Derived Amides and the Natural Occurrence of an Intense Umami Amide in Zanthoxylum piperitum.

    Science.gov (United States)

    Frerot, Eric; Neirynck, Nathalie; Cayeux, Isabelle; Yuan, Yoyo Hui-Juan; Yuan, Yong-Ming

    2015-08-19

    A series of aromatic amides were synthesized from various acids and amines selected from naturally occurring structural frameworks. These synthetic amides were evaluated for umami taste in comparison with monosodium glutamate. The effect of the substitution pattern of both the acid and the amine parts on umami taste was investigated. The only intensely umami-tasting amides were those made from 3,4-dimethoxycinnamic acid. The amine part was more tolerant to structural changes. Amides bearing an alkyl- or alkoxy-substituted phenylethylamine residue displayed a clean umami taste as 20 ppm solutions in water. Ultraperformance liquid chromatography coupled with a high quadrupole-Orbitrap mass spectrometer (UPLC/MS) was subsequently used to show the natural occurrence of these amides. (E)-3-(3,4-Dimethoxyphenyl)-N-(4-methoxyphenethyl)acrylamide was shown to occur in the roots and stems of Zanthoxylum piperitum, a plant of the family Rutaceae growing in Korea, Japan, and China.

  14. Synthesis of Novel Poly(aryl ether amide)s Containing the Phthalazinone Moiety

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-amin- ophenoxy)phenyl](2H)phthalazin-1-one and 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)-3,5-dimethylphenyl](2H)phthalazin-1-one were successfully synthesized from readily available heterocyclic bisphenol-like monomers in two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety were successfully prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents.

  15. SYNTHESIS, CHARACTERIZATION OF CHIRAL POLY(ESTER AMIDE)S DERIVED FROM L-ISOLEUCINE

    Institute of Scientific and Technical Information of China (English)

    Xing-He Fan; Jing-Lun Zhou; Xiao-Fang Chen; Xin-Hua Wan; Qi-Feng Zhou

    2004-01-01

    A series of new optically active aromatic poly(ester amide)s containing a chiral group in the side chain prepared from the p-toluenesulfonic acid salt of o,o'-bis(leucyl)-hexanediol (TS-+LHD+TS-) and p-phthaloyl chloride and styrene-2,5-dicarbonyl chloride styrene have been synthesized by interfacial polymerization. The structure of the monomer is elucidated by FT-IR and elemental analysis. The thermal properties of the polymers were studied by DSC and TGA. The chiroptical properties of the above polymer have also been studied by circular dichroism (CD) spectroscopy. Results indicated that these polymers form helical structures.

  16. Variation of protein backbone amide resonance by electrostatic field

    CERN Document Server

    Sharley, John N

    2015-01-01

    Amide resonance is found to be sensitive to electrostatic field with component parallel or antiparallel the amide C-N bond. This effect is linear and without threshold in the biologically plausible electrostatic field range -0.005 to 0.005 au. Variation of amide resonance varies Resonance Assisted Hydrogen Bonding such as occurs in the hydrogen bonded chains of backbone amides of protein secondary structures such as beta sheet and non-polyproline helix such as alpha helix, varying the stability of the secondary structure. The electrostatic properties including permittivity of amino acid residue sidegroups influence the electrostatic field component parallel or antiparallel the C-N bond of each amide. The significance of this factor relative to other factors in protein folding depends on the magnitude of electrostatic field component parallel or antiparallel the C-N bond of each amide, and preliminary protein-scale calculations of the magnitude of these components suggest this factor warrants investigation in ...

  17. 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.

  18. AMID: autonomous modeler of intragenic duplication.

    Science.gov (United States)

    Kummerfeld, Sarah K; Weiss, Anthony S; Fekete, Alan; Jermiin, Lars S

    2003-01-01

    Intragenic duplication is an evolutionary process where segments of a gene become duplicated. While there has been much research into whole-gene or domain duplication, there have been very few studies of non-tandem intragenic duplication. The identification of intragenically replicated sequences may provide insight into the evolution of proteins, helping to link sequence data with structure and function. This paper describes a tool for autonomously modelling intragenic duplication. AMID provides: identification of modularly repetitive genes; an algorithm for identifying repeated modules; and a scoring system for evaluating the modules' similarity. An evaluation of the algorithms and use cases are presented.

  19. 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.

  20. Synthesis and characterisation of uniform bisester tetra-amide segments

    NARCIS (Netherlands)

    Krijgsman, J.; Husken, D.; Gaymans, R.J.

    2003-01-01

    The synthesis and characterisation of a new type of high melting and fast crystallising amide units that can be used for copolymerisation have been studied. These bisester tetra-amide or TxTxT-dimethyl segments (T is a terephthalic unit and x=(CH2)n (n=2–8)) can be synthesised in a two-step reaction

  1. Synthesis of Novel Extractants——Amide Podands

    Institute of Scientific and Technical Information of China (English)

    TANGHong-bin; ZHUWen-bin; YEGuo-an; ZHUZhi-xuan; CHENWen-jun

    2003-01-01

    Amide podands which are used as a novel extractants are widely concerned recently. In the early stage, the studies were focused on the amide potands substituted with short-chain alky group, and for avoiding the formation of the second organic phase, aromatic, halogenated or higher alcohol compound must be used as diluents.

  2. 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 no tempera...

  3. Understanding the Amide-II Vibrations in β-Peptides.

    Science.gov (United States)

    Zhao, Juan; Wang, Jianping

    2015-11-25

    In this work, the vibrational characteristics of the amide-II modes in β-peptides in five helical conformations, namely, 8-, 10-, 12-, 14-, and 10/12-helices, have been examined. Remarkable conformational dependence of the amide-II spectral profile is obtained by ab initio computations as well as modeling analysis. Intramolecular hydrogen-bonding interaction and its influence on backbone structure and on the amide-II local-mode transition frequencies and intensities are examined. Through-space and through-bond contributions of the amide-II vibrational couplings are analyzed, and it was found that hydrogen-bonding interaction is not a determining factor for the coupling strength. The results reported here provide useful benchmarks for understanding experimental amide-II infrared spectra of β-peptides and suggest the potential application of this mode on monitoring the structures and dynamics of β-peptides.

  4. Retinobenzoic acids. 4. Conformation of aromatic amides with retinoidal activity. Importance of trans-amide structure for the activity.

    Science.gov (United States)

    Kagechika, H; Himi, T; Kawachi, E; Shudo, K

    1989-10-01

    N-Methylation of two retinoidal amide compounds, 4-[(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl)carbamoyl]benz oic acid (3, Am80) and 4-[[(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2- naphthalenyl)carbonyl]amino]benzoic acid (5, Am580), resulted in the disappearance of their potent differentiation-inducing activity on human promyelocytic leukemia cell line HL-60. Studies with 1H NMR and UV spectroscopy indicated that large conformational differences exist between the active secondary amides and the inactive N-methyl amides. From a comparison of the spectroscopic results of these amides with those of stilbene derivatives, the conformations of the active amides are expected to resemble that of (E)-stilbene, whereas the inactive amides resemble the Z isomer: 3 (Am80) and 5 (Am580) have a trans-amide bond and their whole structures are elongated, while the N-methylated compounds [4 (Am90) and 6 (Am590)] have a cis-amide bond, resulting in the folding of the two benzene rings. These structures in the crystals were related to those in solution by 13C NMR spectroscopic comparison between the two phases (solid and solution).

  5. Synthesis of novel poly(aryl ether amide)s containing the phthalazinone moiety

    Institute of Scientific and Technical Information of China (English)

    CHENG, Lin(程琳); JIAN, Xi- Gao(蹇锡高)

    2000-01-01

    Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4- [ 4-( 4-aminophenoxy ) phenyl ]-( 2H )-phtha-lazin-1-one and 1, 2-dihydro-2-( 4-aminophenyl)-4-[ 4-( 4-aminophenoxy)-3, 5-dimethylphenyl]-(2H)-phthalazin-1-one were successfully synthesized using readily available heterocyclic bisphenol-like monomers through two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety with inherent viscosities of 1.16-1.67 dL/g were prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in a variety of solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc),dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidinone (NMP), and pyridine. The polymers had high glass transition tenperatured(Tg) in the 291-329℃ range.

  6. 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.

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

    Science.gov (United States)

    Hu, Feng; Lalancette, Roger; Szostak, Michal

    2016-04-11

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

  8. 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.

  9. 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.

  10. Poly(amide-graft-acrylate) interfacial compounds

    Science.gov (United States)

    Zamora, Michael Perez

    Graft copolymers with segments of dissimilar chemistries have been shown to be useful in a variety of applications as surfactants, compatibilizers, impact modifiers, and surface modifiers. The most common route to well defined graft copolymers is through the use of macromonomers, polymers containing a reactive functionality and thus capable of further polymerization. However, the majority of the studies thus far have focused on the synthesis of macromonomers capable of reacting with vinyl monomers to form graft copolymers. This study focused on the synthesis of macromonomers capable of participating in condensation polymerizations. A chain transfer functionalization method was utilized. Cysteine was evaluated as a chain transfer agent for the synthesis of amino acid functionalized poly(acrylate) and poly(methacrylate) macromonomers. Low molar mass, functionalized macromonomers were produced. These macromonomers were proven to be capable of reacting with amide precursors to form poly(amide-g-acrylate) graft copolymers. Macromonomers and graft copolymers were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) spectroscopy, elemental analysis (EA), inductively coupled plasma (ICP), and differential scanning calorimetry (DSC). The second part of this research involved poly(dimethacrylate) dental restorative materials. Volumetric shrinkage during the cure of these resins results in a poor interface between the resin and the remaining tooth structure, limiting the lifetime of these materials. Cyclic anhydrides were incorporated into common monomer compositions used in dental applications. Volume expansion from the ring opening hydrolysis of these anhydrides was shown to be feasible. The modified dental resins were characterized by swelling, extraction and ultraviolet spectroscopy (UV), and density measurements. Linear poLymers designed to model the crosslinked dental resins were

  11. 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.

  12. Copper/N,N-Dimethylglycine Catalyzed Goldberg Reactions Between Aryl Bromides and Amides, Aryl Iodides and Secondary Acyclic Amides

    Directory of Open Access Journals (Sweden)

    Liqin Jiang

    2014-08-01

    Full Text Available An efficient and general copper-catalyzed Goldberg reaction at 90–110 °C between aryl bromides and amides providing the desired products in good to excellent yields has been developed using N,N-dimethylglycine as the ligand. The reaction is tolerant toward a wide range of amides and a variety of functional group substituted aryl bromides. In addition, hindered, unreactive aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, are efficiently coupled with aryl iodides through this simple and cheap copper/N,N-dimethylglycine catalytic system.

  13. 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...

  14. 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##

  15. SYNTHESIS AND BIOLOGICAL ACTIVITY OF AMIDE DERIVATIVES OF GINKGOLIDE A

    Institute of Scientific and Technical Information of China (English)

    LI-HONG HU; ZHONG-LIANG CHEN; YU-YUAN XIE

    2001-01-01

    Amide derivatives of ginkgolide A were prepared and evaluated for their in vitro ability to inhibit the PAF-induced aggregation of rabbit platelets. They showed less activities than their parent compound ginkgolide A.

  16. Amid the Economic Rubble,Shangkong will Rise

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    @@ Two years ago, bankers and policymakers were arguing heatedly over whether New York or London was the world's premier financial centre. Amid the post-crisis rubble that covers both cities, those arguments now look terribly passé.

  17. 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.

  18. Artists with Arthritis Create Beauty amid Pain

    Institute of Scientific and Technical Information of China (English)

    Alan; Mozes; 蔡峥伟

    2000-01-01

    得此来稿,我们曾犹豫再三,是否刊用此文。因为,其内容给人的第一印象颇有点离奇。Artists with Arthritis Create Beauty amid Pain,怎么可能呢?细读之下,你也许会觉得,此文虽是一家之言,但也并非荒唐。尤其是本文的收尾句,笔锋一转,抖出了妙言: ...in addition to the emotional support such stories can give RA patients,there are now new drug options that far surpass the treatment choices Renoir faced. 此句是否可译:除了此类故事能够给患风湿病者一种情感上的支持之外,现在可选的新药要比Renoir(雷诺阿,法国印象派画家。主要作品有《包厢》、《游船上的午餐》、《浴女》等。)时代强得多。

  19. 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.

  20. Cations bind only weakly to amides in aqueous solutions.

    Science.gov (United States)

    Okur, Halil I; Kherb, Jaibir; Cremer, Paul S

    2013-04-01

    We investigated salt interactions with butyramide as a simple mimic of cation interactions with protein backbones. The experiments were performed in aqueous metal chloride solutions using two spectroscopic techniques. In the first, which provided information about contact pair formation, the response of the amide I band to the nature and concentration of salt was monitored in bulk aqueous solutions via attenuated total reflection Fourier transform infrared spectroscopy. It was found that molar concentrations of well-hydrated metal cations (Ca(2+), Mg(2+), Li(+)) led to the rise of a peak assigned to metal cation-bound amides (1645 cm(-1)) and a decrease in the peak associated with purely water-bound amides (1620 cm(-1)). In a complementary set of experiments, the effect of cation identity and concentration was investigated at the air/butyramide/water interface via vibrational sum frequency spectroscopy. In these studies, metal ion-amide binding led to the ordering of the adjacent water layer. Such experiments were sensitive to the interfacial partitioning of cations in either a contact pair with the amide or as a solvent separated pair. In both experiments, the ordering of the interactions of the cations was: Ca(2+) > Mg(2+) > Li(+) > Na(+) ≈ K(+). This is a direct cationic Hofmeister series. Even for Ca(2+), however, the apparent equilibrium dissociation constant of the cation with the amide carbonyl oxygen was no tighter than ∼8.5 M. For Na(+) and K(+), no evidence was found for any binding. As such, the interactions of metal cations with amides are far weaker than the analogous binding of weakly hydrated anions.

  1. Iron(III) Chloride mediated reduction of Bis(1-isoquinolylcarbonyl)amide to an Amide

    Indian Academy of Sciences (India)

    Rojalin Sahu; Papuli Chaliha; Vadivelu Manivannan

    2016-01-01

    In methanol, FeCl3 reacted readily with L1H (L1H = bis(1-isoquinolylcarbonyl)amide) and afforded a complex having the formula [Fe(L2)Cl2] (1) {L2− = -((1-isoquinolyl)(methoxy)methyl)isoquinoline-1-carboxamide ion}. This reaction involves reduction of one of the two carbonyl groups present in L1H to (methoxy)methyl group. A plausible mechanism for the conversion of L1H to L2− has been proposed. Determination of molecular structure of 1 confirmed this conversion. Fe(III) ion is surrounded by three nitrogen atoms of the ligand and two chloride ions, imparting a rare distorted trigonal bipyramidal N3Cl2 coordination environment.

  2. Mechanism of fluorescence quenching of tyrosine derivatives by amide group

    Science.gov (United States)

    Wiczk, Wiesław; Rzeska, Alicja; Łukomska, Joanna; Stachowiak, Krystyna; Karolczak, Jerzy; Malicka, Joanna; Łankiewicz, Leszek

    2001-06-01

    The difference between fluorescence lifetimes of the following amino acids: phenylalanine (Phe), tyrosine (Tyr), ( O-methyl)tyrosine (Tyr(Me)), (3-hydroxy)tyrosine (Dopa), (3,4-dimethoxy)phenylalanine (Dopa(Me) 2) and their amides was used to testify the mechanism of fluorescence quenching of aromatic amino acids by the amide group. On the basis of the Marcus theory of photoinduced electron transfer parabolic relationships between ln kET and ionization potentials reduced by energy of excitation ( IP-E ∗0,0) for the above-mentioned amino acids were obtained. This finding indicates the occurrence of photoinduced electron transfer from the excited chromophore group to the amide group.

  3. 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.

  4. Chiral separation of amides using supercritical fluid chromatography.

    Science.gov (United States)

    Xiang, Yanqiao; Dunetz, Joshua R; Lovdahl, Michael

    2013-06-07

    Nine amide derivatives bearing α-stereocenters as well as different substitutions on the amide nitrogen were synthesized via an n-propanephosphonic acid cyclic anhydride (T3P)-mediated coupling, and their enantiomeric pairs were separated using supercritical fluid chromatography (SFC). Five polysaccharide-based chiral stationary phases (CSPs), Chiralcel OD-H, and OJ-H, and Chiralpak AD-H, AS-H and IC columns were explored for the chiral separation of these compounds. None of the compounds could be resolved on all five columns, and no single column could separate all nine pairs of enantiomers. Comparatively, the IC and OD-H columns showed the best results for this group of amides, yielding baseline separations for eight of nine pairs. The type of polar functional group and aromatic substitution in the CSPs and the substitutions on the amide nitrogen had a significant impact on the enantiomeric resolution of the compounds in the interaction between the analyte and the stationary phases. The potential separation mechanism and the effect of substitutions in the CSPs and amide solutes on the separation are discussed. The effects of the organic modifiers, modifier composition, mobile phase additives, and temperature were investigated for the separation of these amides on the IC or the OD-H column. Baseline resolution was achieved under optimized chromatographic conditions using an IC or an OD-H column. Linearity, reproducibility, and limit of quantitation were also demonstrated for the compound 9. Approximately three-fold improvement in signal-to-noise was observed using a SFC system with better instrument design.

  5. Studies on the amide compounds ofMirabilis. Jalapa. L

    Institute of Scientific and Technical Information of China (English)

    SHEN; XuWei

    2001-01-01

    Mirabilis himalaica(Edgew.)Heinerl Var. Chinensis Heimerl belonging to the genus Mirabilis are used in chinese medicine as a remedy for various diseases[1].Its chemical constituents,however, have not been reported so far. we have carried out a detailed chemical investigatigation of the seeds and have isolated two new amides along with three known compounds.  The known compounds were identified by comparing their spectral data with those of authentic samples or with those reported in literature as daucosterol[2], bsitoserol[2], boeravinone E[3], in the present note, the structural elucidation of two new amides is reported.  ……

  6. Study on Alternating Copolymerization of Polyester-amides

    Institute of Scientific and Technical Information of China (English)

    WEI Wen-liang; LI Jian-mei; ZHU Fang-liang

    2002-01-01

    The preparing methods, choice of catalysts and reaction kinetics of one of the monomers, diesteramide(DEA), of polyester-amides were investigated in details. The chemical structure of DEA was analyzed. And the Polyester-amides (PEA) were obtained by melt copolymerization with DEA. It is shown that DEA can be synthesized by DMT and hexamethylene diamine with the catalyst EX - 1 or EX - 2. The relationship between reaction rate of synthesizing monomer and concentration of hexamethylene diamine is first order kinetic relation.

  7. Studies on the amide compounds ofMirabilis. Jalapa. L

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Mirabilis himalaica(Edgew.)Heinerl Var. Chinensis Heimerl belonging to the genus Mirabilis are used in chinese medicine as a remedy for various diseases[1].Its chemical constituents,however, have not been reported so far. we have carried out a detailed chemical investigatigation of the seeds and have isolated two new amides along with three known compounds. The known compounds were identified by comparing their spectral data with those of authentic samples or with those reported in literature as daucosterol[2], bsitoserol[2], boeravinone E[3], in the present note, the structural elucidation of two new amides is reported.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  9. 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

    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...

  10. 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- . 721.10176... Substances § 721.10176 Amides, peanut-oil, N- . (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amides, peanut-oil, N- (PMN P-04-144; CAS No....

  11. 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...

  12. 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)...

  13. 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...

  14. 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- . 721.10191 Section... Substances § 721.10191 Amides, coco, N- . (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amides, coco, N- (PMN P-06-262; CAS No. 851544-20-2)...

  15. 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- , acrylates. 721... Substances § 721.10192 Amides, coco, N- , acrylates. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amides, coco, N- , acrylates (PMN...

  16. Polyurethane elastomers with amide chain extenders of uniform length

    NARCIS (Netherlands)

    Schuur, van der Martijn; Noordover, Bart; Gaymans, Reinoud 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): hexame

  17. Intramolecular Amide Hydrolysis in N-Methylmaleamic Acid Revisited

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The intramolecular amide hydrolysis of N-methylmaleamic acid have been revisited by use of density functional theory and inclusion of solvent effects. The results indicate that concerted reaction mechanism is favored over stepwise reaction mechanism. This is in agreement with the previous theoretical study. Sovlent effects have significant influence on the reaction barrier.

  18. Modeling the amide I bands of small peptides

    NARCIS (Netherlands)

    Jansen, Thomas la Cour; Dijkstra, Arend G.; Watson, Tim M.; Hirst, Jonathan D.; Knoester, Jasper

    2006-01-01

    In this paper different floating oscillator models for describing the amide I band of peptides and proteins are compared with density functional theory (DFT) calculations. Models for the variation of the frequency shifts of the oscillators and the nearest-neighbor coupling between them with respect

  19. Method for enhancing amidohydrolase activity of fatty acid amide hydrolase

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. KNH2-KH: a metal amide-hydride solid solution.

    Science.gov (United States)

    Santoru, Antonio; Pistidda, Claudio; Sørby, Magnus H; Chierotti, Michele R; Garroni, Sebastiano; Pinatel, Eugenio; Karimi, Fahim; Cao, Hujun; Bergemann, Nils; Le, Thi T; Puszkiel, Julián; Gobetto, Roberto; Baricco, Marcello; Hauback, Bjørn C; Klassen, Thomas; Dornheim, Martin

    2016-09-27

    We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2(-) ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.

  1. 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

  2. Synthesis, structure, and reactivity of tris(amidate) mono(amido) and tetrakis(amidate) complexes of group 4 transition metals.

    Science.gov (United States)

    Payne, Philippa R; Thomson, Robert K; Medeiros, Diane M; Wan, Geoff; Schafer, Laurel L

    2013-11-28

    The syntheses of a series of tris(amidate) mono(amido) titanium and zirconium complexes are reported. The binding motif of the amidate ligand has been determined to depend on the size of the metal centre for these sterically demanding N,O-chelating ligands; the larger zirconium metal centre supports three κ(2)-(N,O) bound amidate ligands while the titanium analogue has one ligand bound in a κ(1)-(O) fashion to alleviate steric strain. Reactivity studies indicate that, despite high steric crowding about the tris(amidate) mono(amido) zirconium metal centre, transamination of the reactive dimethylamido ligand can be achieved using aniline. This complex is also an active precatalyst for intramolecular alkene hydroamination, in which protonolysis of one amidate ligand in the presence of excess amine is observed as an initiation step prior to catalytic turnover. Eight-coordinate homoleptic κ(2)-amidate complexes of zirconium and hafnium have also been prepared.

  3. 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

    2012-01-03

    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 (18)O-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 (O(2)) to deliver the amide oxygen from O(2). This understanding was used to develop a straightforward protocol for the preparation of (18)O-labeled amides in peptides by simply performing the umpolung amide synthesis reaction under an atmosphere of 18O2.

  4. 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.

  5. Amide I'-II' 2D IR spectroscopy provides enhanced protein secondary structural sensitivity.

    Science.gov (United States)

    Deflores, Lauren P; Ganim, Ziad; Nicodemus, Rebecca A; Tokmakoff, Andrei

    2009-03-11

    We demonstrate how multimode 2D IR spectroscopy of the protein amide I' and II' vibrations can be used to distinguish protein secondary structure. Polarization-dependent amide I'-II' 2D IR experiments on poly-l-lysine in the beta-sheet, alpha-helix, and random coil conformations show that a combination of amide I' and II' diagonal and cross peaks can effectively distinguish between secondary structural content, where amide I' infrared spectroscopy alone cannot. The enhanced sensitivity arises from frequency and amplitude correlations between amide II' and amide I' spectra that reflect the symmetry of secondary structures. 2D IR surfaces are used to parametrize an excitonic model for the amide I'-II' manifold suitable to predict protein amide I'-II' spectra. This model reveals that the dominant vibrational interaction contributing to this sensitivity is a combination of negative amide II'-II' through-bond coupling and amide I'-II' coupling within the peptide unit. The empirically determined amide II'-II' couplings do not significantly vary with secondary structure: -8.5 cm(-1) for the beta sheet, -8.7 cm(-1) for the alpha helix, and -5 cm(-1) for the coil.

  6. Enzymatic synthesis of fatty amides from palm olein.

    Science.gov (United States)

    Al-Mulla, Emad A Jaffar; Yunus, Wan Md Zin Wan; Ibrahim, Nor Azowa Bt; Rahman, Mohd Zaki A

    2010-01-01

    Fatty amides have been successfully synthesized from palm olein and urea by a one-step lipase catalyzed reaction. The use of immobilized lipase as the catalyst for the preparation reaction provides an easy isolation of the enzyme from the products and other components in the reaction mixture. The fatty amides were characterized using Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance ((1)H NMR) technique and elemental analysis. The highest conversion percentage (96%) was obtained when the process was carried out for 36 hours using urea to palm oil ratio of 5.2: 1.0 at 40 degrees C. The method employed offers several advantages such as renewable and abundant of the raw material, simple reaction procedure, environmentally friendly process and high yield of the product.

  7. In vivo behavior of hydrogel beads based on amidated pectins.

    Science.gov (United States)

    Munjeri, O; Collett, J H; Fell, J T; Sharma, H L; Smith, A M

    1998-01-01

    Radio-labeled hydrogel beads, based on amidated pectin, have been produced by adding droplets of an amidated pectin solution to calcium chloride. Incorporation of model drugs into the beads and measurement of the dissolution rate showed that the properties of the beads were unaffected by the incorporation of the radiolabel. The labeled beads were used to carry out an in vivo study of their behavior in the gastrointestinal tract using human volunteers. The volunteers were given the beads after an overnight fast and images were obtained at frequent intervals during transit through the upper gastrointestinal tract and the colon. The beads exhibited rapid gastric emptying and proceeded to pass through the small intestine individually before regrouping at the ileo-caecal junction. Once in the colon, the beads again proceeded as individuals and evidence of the degradation of the beads was observed.

  8. Halo substituent effects on intramolecular cycloadditions involving furanyl amides.

    Science.gov (United States)

    Padwa, Albert; Crawford, Kenneth R; Straub, Christopher S; Pieniazek, Susan N; Houk, K N

    2006-07-21

    Intramolecular Diels-Alder reactions involving a series of N-alkenyl-substituted furanyl amides were investigated. Stable functionalized oxanorbornenes were formed in high yield upon heating at 80-110 degrees C. The cycloaddition reactions include several bromo-substituted furanyl amides, and these systems were found to proceed at a much faster rate and in higher yield than without substitution. This effect was observed by incorporating a halogen in the 3- or 5-position of the furan ring and appears to be general. The origin of increased cycloaddition rates for halo-substituted furans has been investigated with quantum mechanical calculations. The success of these reactions is attributed to increases in reaction exothermicities; this both decreases activation enthalpies and increases barriers to retrocycloadditions. Halogen substitution on furan increases reactant energy and stabilizes the product, which is attributed to the preference of electronegative halogens to be attached to a more highly alkylated and therefore more electropositive framework.

  9. Simulations of the temperature dependence of amide I vibration.

    Science.gov (United States)

    Kaminský, Jakub; Bouř, Petr; Kubelka, Jan

    2011-01-13

    For spectroscopic studies of peptide and protein thermal denaturation it is important to single out the contribution of the solvent to the spectral changes from those originated in the molecular structure. To obtain insights into the origin and size of the temperature solvent effects on the amide I spectra, combined molecular dynamics and density functional simulations were performed with the model N-methylacetamide molecule (NMA). The computations well reproduced frequency and intensity changes previously observed in aqueous NMA solutions. An empirical correction of vacuum frequencies in single NMA molecule based on the electrostatic potential of the water molecules provided superior results to a direct density functional average obtained for a limited number of solute-solvent clusters. The results thus confirm that the all-atom quantum and molecular mechanics approach captures the overall influence of the temperature dependent solvent properties on the amide I spectra and can improve the accuracy and reliability of molecular structural studies.

  10. 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.

  11. Cleavage of an amide bond by a ribozyme

    Science.gov (United States)

    Dai, X.; De Mesmaeker, A.; Joyce, G. F.; Miller, S. L. (Principal Investigator)

    1995-01-01

    A variant form of a group I ribozyme, optimized by in vitro evolution for its ability to catalyze magnesium-dependent phosphoester transfer reactions involving DNA substrates, also catalyzes the cleavage of an unactivated alkyl amide when that linkage is presented in the context of an oligodeoxynucleotide analog. Substrates containing an amide bond that joins either two DNA oligos, or a DNA oligo and a short peptide, are cleaved in a magnesium-dependent fashion to generate the expected products. The first-order rate constant, kcat, is 0.1 x 10(-5) min-1 to 1 x 10(-5) min-1 for the DNA-flanked substrates, which corresponds to a rate acceleration of more than 10(3) as compared with the uncatalyzed reaction.

  12. Potent and orally efficacious benzothiazole amides as TRPV1 antagonists.

    Science.gov (United States)

    Besidski, Yevgeni; Brown, William; Bylund, Johan; Dabrowski, Michael; Dautrey, Sophie; Harter, Magali; Horoszok, Lucy; Hu, Yin; Johnson, Dean; Johnstone, Shawn; Jones, Paul; Leclerc, Sandrine; Kolmodin, Karin; Kers, Inger; Labarre, Maryse; Labrecque, Denis; Laird, Jennifer; Lundström, Therese; Martino, John; Maudet, Mickaël; Munro, Alexander; Nylöf, Martin; Penwell, Andrea; Rotticci, Didier; Slaitas, Andis; Sundgren-Andersson, Anna; Svensson, Mats; Terp, Gitte; Villanueva, Huascar; Walpole, Christopher; Zemribo, Ronald; Griffin, Andrew M

    2012-10-01

    Benzothiazole amides were identified as TRPV1 antagonists from high throughput screening using recombinant human TRPV1 receptor and structure-activity relationships were explored to pinpoint key pharmacophore interactions. By increasing aqueous solubility, through the attachment of polar groups to the benzothiazole core, and enhancing metabolic stability, by blocking metabolic sites, the drug-like properties and pharmokinetic profiles of benzothiazole compounds were sufficiently optimized such that their therapeutic potential could be verified in rat pharmacological models of pain.

  13. Accumulation of hydroxycinnamic acid amides in winter wheat under snow.

    Science.gov (United States)

    Jin, Shigeki; Yoshida, Midori; Nakajima, Takashi; Murai, Akio

    2003-06-01

    It was found that the content of antifungal compounds p-coumaroylagmatine [1-(trans-4'-hydroxycinnamoylamino)-4-guanidinobutane] and p-coumaroyl-3-hydroxyagmatine [1-(trans-4'-hydroxycinnamoylamino)-3-hydroxy-4-guanidinobutane] in the crown of winter wheat (Triticum aestivum L. cv Chihokukomugi) significantly increased under snow cover. This finding suggests that the accumulation of these hydroxycinnamic acid amides was caused by winter stress and related to protecting the plant against snow mold under snow cover.

  14. Guidelines for Middle Managers for Thriving amid Continuous Change

    OpenAIRE

    2016-01-01

    This thesis suggests the much needed guidelines for middle managers for thriving amid continuous change. Middle managers, being an integral part of their organizations, needed a set of consolidated guidelines for thriving in the times of continuous change. Thriving requires high engagement, learning and growth as a response in stressful situations. The proposed guidelines include elements from literature and recommendations of the middle managers which came from co-creation sessions with midd...

  15. 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.

  16. 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; Szostak, Michal

    2015-04-14

    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.

  17. Synthesis, morphology and properties of segmented poly(ether ester amide)s comprising uniform glycine or β-alanine extended bisoxalamide hard segments

    NARCIS (Netherlands)

    Sijbrandi, N.J.; Kimenai, A.J.; Mes, E.P.C.; Broos, R.; Bar, G.; Rosenthal, M.; Odarchenko, Y.; Ivanov, D.A.; Feijen, J.; Dijkstra, P.J.

    2012-01-01

    Segmented poly(ether ester amide)s comprising glycine or β-alanine extended bisoxalamide hard segments are highly phase separated thermoplastic elastomers with a broad temperature independent rubber plateau. These materials with molecular weights, Mn, exceeding 30 × 103 g mol−1 are conveniently prep

  18. 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.

  19. Single-conformation infrared spectra of model peptides in the amide I and amide II regions: experiment-based determination of local mode frequencies and inter-mode coupling.

    Science.gov (United States)

    Buchanan, Evan G; James, William H; Choi, Soo Hyuk; Guo, Li; Gellman, Samuel H; Müller, Christian W; Zwier, Timothy S

    2012-09-07

    Single-conformation infrared spectra in the amide I and amide II regions have been recorded for a total of 34 conformations of three α-peptides, three β-peptides, four α/β-peptides, and one γ-peptide using resonant ion-dip infrared spectroscopy of the jet-cooled, isolated molecules. Assignments based on the amide NH stretch region were in hand, with the amide I/II data providing additional evidence in favor of the assignments. A set of 21 conformations that represent the full range of H-bonded structures were chosen to characterize the conformational dependence of the vibrational frequencies and infrared intensities of the local amide I and amide II modes and their amide I/I and amide II/II coupling constants. Scaled, harmonic calculations at the DFT M05-2X/6-31+G(d) level of theory accurately reproduce the experimental frequencies and infrared intensities in both the amide I and amide II regions. In the amide I region, Hessian reconstruction was used to extract local mode frequencies and amide I/I coupling constants for each conformation. These local amide I frequencies are in excellent agreement with those predicted by DFT calculations on the corresponding (13)C = (18)O isotopologues. In the amide II region, potential energy distribution analysis was combined with the Hessian reconstruction scheme to extract local amide II frequencies and amide II/II coupling constants. The agreement between these local amide II frequencies and those obtained from DFT calculations on the N-D isotopologues is slightly worse than for the corresponding comparison in the amide I region. The local mode frequencies in both regions are dictated by a combination of the direct H-bonding environment and indirect, "backside" H-bonds to the same amide group. More importantly, the sign and magnitude of the inter-amide coupling constants in both the amide I and amide II regions is shown to be characteristic of the size of the H-bonded ring linking the two amide groups. These amide I/I and

  20. Novel Synthesis of N-Substituted p-Hydroxybenzoic Amides on Soluble Polymer-Support

    Institute of Scientific and Technical Information of China (English)

    胡春玲; 陈祖兴; 杨桂春

    2003-01-01

    The synthesis of N-substituted p-hydroxybenzoic amides using a liquid phase approach is described. Poly(ethylene glycol)(PEG) and p-hydroxybenzoic acid were linked by oxalyl chloride to give compound 1, which was chlorinated by thionyl chloride, followed by amidation with NHR1R2 to yield compound 3. Hydrolysis of compound 3 gave the title amide 4.These crude library members were obtained in good yields with high purities.

  1. Fabrication and characterization of poly(amide-imides)/TiO₂ nanocomposite gas separation membranes

    OpenAIRE

    1996-01-01

    Nanosized Ti02 rich domains were generated in-situ within poly(amide-imide) (PAl) and 6F-poly(amide-imide) (6FPAl) by a sol-gel process. The composite films showed a high optical transparency. The morphology of the Ti02 rich domains was observed by transmission electron microscopy (TEM). The Ti02 rich domains were well dispersed within the poly(amide-imide) and 6F-poly(amide-imide) matrices and were 5 nm to 50 nm in size. Limited study was also carried out for the fabrication o...

  2. Three new amides from Streptomyces sp. H7372

    OpenAIRE

    Cheenpracha, Sarot; Borris,Robert P; Tran,Tammy T.; Jee,Jap Meng; Seow, Heng Fong; Cheah,Hwen-Yee; Ho,Coy Choke; Chang, Leng Chee

    2011-01-01

    Three new amides, methyl phenatate A (1), actiphenamide (2) and actiphenol 1-β-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(ΔAla-L-Val) (8) gave a clear zone of inhibition of Ras-Raf-1 interaction in the yeast two-hybrid assay which showed hi...

  3. N-Hydroxyimide Ugi Reaction toward α-Hydrazino Amides

    Science.gov (United States)

    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 high yields. This reaction displays N–N bond formation by cyclic imide migration in the Ugi reaction. Thus, N-hydroxyimide is added as a new acid component in the Ugi reaction and broadens the scaffold diversity. PMID:28220702

  4. Identification of nitrogen compounds and amides from spent hydroprocessing catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Choi, J.H.K.; Gray, M.R. (University of Alberta, Edmonton, AB (Canada). Dept. of Chemical Engineering)

    1991-06-01

    A spent commercial naphtha hydrotreating catalyst was analyzed to identify compounds which had accumulated on the catalyst surface during its active life. The catalyst was extracted with methylene chloride, methanol and pyridine to remove adsorbed organic material, which was rich in nitrogen and oxygen. A series of quinolones were identified in the methanol extract after enrichment with HCl-modified silica gel adsorption and subsequent silica gel chromatography. Tetra- and hexahydroquinolones with alkyl substituents up to C{sub 3} were identified. Similar amides have been identified in asphaltenes, and are very resistant to hydrogenation. Tetrahydroquinolines and piperidines were detected in the pyridine extract. 36 refs., 8 figs., 2 tabs.

  5. 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)

  6. Synthesis and structures of new helical,nanoscale ferrocenylphenyl amides

    Institute of Scientific and Technical Information of China (English)

    XU Yan; RAN Chunling; WANG Haixian; SONG Maoping

    2007-01-01

    Two novel ferrocenylphenyl-containing amides have been synthesized by reaction of ferrocenylbencarboxylchloride and 1,2-di-(o-aminophenoxy)ethane.A single crystal X-ray analysis shows that compound 3 crystallizes in the triclinic system,space group P-1,and compound 4 crystallizes in orthorhombic system,space group Pca21.There areintramolecular H-bonds in both the compounds,two H-bonds in compound 3 and one in compound 4.The dihedral angels of Cp-ring and phenyl ring range from 3.8° to 20.8°.

  7. Preparation and evaluation of some amide ether carboxylate surfactants

    Directory of Open Access Journals (Sweden)

    M.M.A. El-Sukkary

    2012-06-01

    Full Text Available A homologous series of new mild surfactants, namely: Alkyl amide ether carboxylates surfactants (AEC RCO–NHCH2CH2O (CH2CH2O6CH2COONa, were synthesized by esterification, amidation, ethoxylation and carboxymethylation reaction steps of fatty acids (Lauric, Myristic, palmitic, stearic, oleic or linoleic. The chemical structures of the prepared compounds were confirmed using different spectroscopic techniques, FTIR spectroscopy, mass spectra and HNMR. The surface properties including surface and interfacial tensions, foaming height, emulsification power, calcium ion stability, stability to hydrolysis and critical micelle concentration (cmc were determined. The study of their surface properties showed their stability in hard water and in acidic and alkaline media. These compounds have high calcium ion stability. The low foaming power could have an application in the dyeing auxiliary industry. The lower values of the interfacial tension values indicate the ability of using these surfactants in several applications as corrosion inhibitors and biocides. The data revealed various advantages and potentials as a main surfactant as well as co- surfactants.

  8. PREPARATION AND CHARACTERIZATION OF AMIDATED PECTIN BASED POLYMER ELECTROLYTE MEMBRANES

    Institute of Scientific and Technical Information of China (English)

    R.K.Mishra; A.Anis; S.Mondal; M.Dutt; A.K.Banthia

    2009-01-01

    The work presents the synthesis and characterization of ami dated pectin(AP)based polymer electrolyte membranes(PEM)crosslinked with glutaraldehyde(GA).The prepared membranes are characterized by Fourier transform infrared spectroscopy(FTIR),organic elemental analysis,X-ray diffraction studies(XRD),thermogravimetric analysis (TGA)and impedance spectroscopy.Mechanical properties of the membranes are evaluated by tensile tests.The degree of amidation(DA),molar and mass reaction yields(YM and YN)are calculated based on the results of organic elemental analysis.FTIR spectroscopy indicated the presence of primary and secondary amide absorption bands.XRD pattern of membranes clearly indicates that there is a considerable increase in crystallinity as compared to parent pectin.TGA studies indicate that AP is less thermally stable than reference pectin.A maximum room temperature conductivity of 1.098×10-3 Scm-1 is obtained in the membrane,which is designated as AP-3.These properties make them good candidates for low cost biopolymer electrolyte membranes for fuel cell applications.

  9. Amidated pectin based hydrogels: synthesis, characterization and cytocompatibility study.

    Science.gov (United States)

    Mishra, R K; Singhal, J P; Datt, M; Banthia, A K

    2007-01-01

    The design and development of pectin-based hydrogels were attempted through the chemical modification of pectin with diethanolamine (DA). Diethanolamine modified pectin (DAMP) was synthesized by the chemical modification of pectin with varying concentrations of DA (1:1,1:2,1:3 and 1:4) at 5 oC in methanol. The modified product was used for the preparation of the hydrogel with glutaraldehyde (GA) reagent. The prepared hydrogels were characterized by Fourier transform infrared (FTIR) spectroscopy; organic elemental analysis, and X-ray diffraction (XRD), and swelling, hemocompatibility and cytocompatibility studies of the prepared hydrogels were also done. FTIR spectroscopy indicated the presence of primary and secondary amide absorption bands. The XRD pattern of the DAMP hydrogel clearly indicated that there was a considerable increase in crystallinity as compared to parent pectin. The degree of amidation (DA) and molar and mass reaction yields (Ym and Yn) was calculated based on the results of organic elemental analysis. Drug release studies from the hydrogel membranes were also evaluated in a Franz's diffusion cell. The hydrogels demonstrated good water holding properties and were found to be compatible with B-16 melanoma cells and human blood.

  10. Collagen and component polypeptides: Low frequency and amide vibrations

    Science.gov (United States)

    Fontaine-Vive, F.; Merzel, F.; Johnson, M. R.; Kearley, G. J.

    2009-01-01

    Collagen is a fibrous protein, which exists widely in the human body. The biomechanical properties of collagen depend on its triple helix structure and the corresponding low frequency vibrations. We use first-principles, density functional theory methods and analytical force fields to investigate the molecular vibrations of a model collagen compound, the results being validated by comparison with published, inelastic neutron scattering data. The results from these atomistic simulations are used at higher frequency to study the Amide I and V vibrations and therefore the vibrational signature of secondary and tertiary structure formation. In addition to collagen, its component homopolymers, poly-glycine and poly-proline are also studied. The Amide V vibration of glycine is strongly modified in going from the single helix of poly-glycine II to the triple helix of collagen. The collagen models are hydrated and this work allows us to discuss the relative merits of density functional theory and force field methods when tackling complex, partially crystalline systems.

  11. 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.

  12. Stability of caffeic acid phenethyl amide (CAPA) in rat plasma.

    Science.gov (United States)

    Yang, John; Kerwin, Sean M; Bowman, Phillip D; Stavchansky, Salomon

    2012-05-01

    A validated C₁₈ reverse-phase HPLC method with UV detection at 320 nm was developed and used for the stability evaluation of caffeic acid phenethyl amide (CAPA) and caffeic acid phenethyl ester (CAPE) in rat plasma. CAPA is the amide derivative of CAPE, a naturally occurring polyphenolic compound that has been found to be active in a variety of biological pathways. CAPA has been shown to protect endothelial cells against hydrogen peroxide-induced oxidative stress to a similar degree to CAPE. CAPE has been reported to be rapidly hydrolyzed in rat plasma via esterase enzymes. CAPA is expected to display a longer half-life than CAPE by avoiding hydrolysis via plasma esterases. The stability of CAPA and CAPE in rat plasma was investigated at three temperatures. The half-lives for CAPA were found to be 41.5, 10 and 0.82 h at 25, 37 and 60 °C, respectively. The half-lives for CAPE were found to be 1.95, 0.35 and 0.13 h at 4, 25 and 37 °C, respectively. The energy of activation was found to be 22.1 kcal/mol for CAPA and 14.1 kcal/mol for CAPE. A more stable compound could potentially extend the beneficial effects of CAPE.

  13. Synthesis and Crystal Structure of a New Adamantane Amide Derivative

    Institute of Scientific and Technical Information of China (English)

    ZHOU Ying-Hua; LV Qi-Chun; ZHANG Qian; CHENG Yong; SHENG En-Hong

    2012-01-01

    A novel adamantane acyl amide derivative containing two phthalimido pendant groups(C31H31N3O5) has been synthesized,and its structure was characterized by elemental analysis,IR,1 H NMR spectra,and single-crystal X-ray diffraction.The crystal belongs to triclinic,space group P1 with a=7.3158(10),b=13.2405(18),c=14.378(2),α=72.419(2),β=84.496(2),γ=81.799(2)o,V=1312.0(3)3,Z=2,Dc=1.330 g/cm 3,μ=0.09 mm-1,Mr=525.59,F(000)=556,S=1.001,R=0.0523 and wR=0.0707 for 5901 unique reflections with 2363 observed ones(I〉2σ(I)).π-π stacking interactions(offset face-to-face) exist between the two rings of phthalimides from the neighboring molecules in the title crystal structure.The intermolecular dihedral angle between the two rings of neighboring phthalic amides is 6.26° and the distance is 4.008.

  14. Two enzymes which catalyze the amidation of peptide C-terminals are synthesized by a single mRNA. Peptide C mattan amid ka hanno wo shokubaisuru futatsu no koso wa ippon no mRNA yori goseisareru

    Energy Technology Data Exchange (ETDEWEB)

    Kato, I.; Yonekura, H.; Okamoto, H. (Tohoku Univ., Sendai (Japan))

    1991-10-25

    Recent findings by the authors are reviewed on the amidation that forms amid structure essential to physiological activities in C-terminals of peptide hormones such as oxytocin,VIP,PP. It is noted that the amidation had been considered to be catalyzed by peptidylglycine{alpha} -amidating monooxyganase ( PAM ) and that the authors investigated the PAM function by expression of PAM cDNA isolated from rat pituitary and its deletion mutant into COS-7 cells, reaching to the important findings of a singl PMA mRNA encoding two enzymes, namely one at 5 {prime} side, peptidylglicine {alpha} hydroxylase which catalyses the conversion of C-termianl glycine on peptide to the hydroxylated form ( the first step of amidation ),and another at 3{prime} side, {alpha}- hydroxylglycine amidating dealkylase which catalyzes the conversion of hydroxylated glycine to the amidated form ( the second step of amidation). 19 refs., 4 figs.

  15. 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...

  16. A General and Efficient CuBr2-Catalyzed N-Arylation of Secondary Acyclic Amides

    Institute of Scientific and Technical Information of China (English)

    王满刚; 于华; 尤心稳; 吴军; 商志才

    2012-01-01

    A general and efficient Cu(II)-catalyzed cross-coupling method is reported for the preparation of acyclic tertiary amides. Generally moderate to excellent yields and functional group tolerance were obtained with secondary acyclic amides and aryl halides as substrates in toluene.

  17. An azole, an amide and a limonoid from Vepris uguenensis (Rutaceae).

    Science.gov (United States)

    Cheplogoi, Peter K; Mulholland, Dulcie A; Coombes, Philip H; Randrianarivelojosia, Milijaona

    2008-04-01

    The limonoid derivative, methyl uguenenoate, the azole, uguenenazole, and the amide, uguenenonamide, together with the known furoquinoline alkaloids flindersiamine and maculosidine, and syringaldehyde have been isolated from the root of the East African Rutaceae Vepris uguenensis. While methyl uguenenoate and the furoquinoline alkaloids displayed mild antimalarial activity, the azole and amide were completely inactive.

  18. A nordehydroabietyl amide-containing chiral diene for rhodium-catalysed asymmetric arylation to nitroolefins.

    Science.gov (United States)

    Li, Ruikun; Wen, Zhongqing; Wu, Na

    2016-11-29

    A highly enantioselective rhodium catalysed asymmetric arylation (RCAA) of nitroolefins with arylboronic acids is presented using a newly developed, C1-symmetric, non-covalent interacted, phellandrene derived, nordehydroabietyl amide-containing chiral diene under mild conditions. Stereoelectronic effects were studied, suggesting an activation of the bound substrate through the secondary amide as a hydrogen-bond donor.

  19. On the temperature dependence of amide I frequencies of peptides in solution.

    Science.gov (United States)

    Amunson, Krista E; Kubelka, Jan

    2007-08-23

    The temperature dependence of the amide I vibrational frequencies of peptides in solution was investigated. In D2O, the amide I' bands of both an alpha-helical oligopeptide, the random-coil poly(L-lysine), and the simplest amide, N-methyl acetamide (NMA), exhibit linear frequency shifts of approximately 0.07 cm(-1)/degrees C with increasing temperature. Similar amide I frequency shifts are also observed for NMA in both polar (acetonitrile and DMSO) and nonpolar (1,4-dioxane) organic solvents, thus ruling out hydrogen-bonding strength as the cause of these effects. The experimental NMA amide I frequencies in the organic solvents can be accurately described by a simple theory based on the Onsager reaction field with temperature-dependent solvent dielectric properties and a solute molecular cavity. DFT-level calculations (BPW91/cc-pVDZ) for NMA with an Onsager reaction field confirm the significant contribution of the molecular cavity to the predicted amide I frequencies. Comparison of the computations to experimental data shows that the frequency-dependent response of the reaction field, taken into account by the index of refraction, is crucial for describing the amide I frequencies in polar solvents. The poor predictions of the model for the NMA amide I band in D2O might be due, in part, to the unknown temperature dependence of the refractive index of D2O in the mid-IR range, which was approximated by the available values in the visible region.

  20. Palladium-catalyzed Substitution of Ketone or Aldehyde Bearing Aryl Triflates by Amines or Amides

    Institute of Scientific and Technical Information of China (English)

    TAO Xiaochun; DAI Chunya; CAO Xiongjie; CAI Lisheng; PIKE Victor W

    2009-01-01

    Various aryl triflates, bearing ketone or aldehyde groups, were evaluated for palladium-mediated introduction of an amino group at the triflate position in the presence of various phosphine ligands. BINAP was best for secondary amines, MOP-type ligand for primary or small secondary amines and Xantphos for primary or cyclic secondary amides. No ligand was found effective for acyclic secondary amides.

  1. A case study on the myth of emission from aliphatic amides

    Science.gov (United States)

    Singh, Avinash Kumar; Das, Sreyashi; Datta, Anindya

    2016-12-01

    For several decades, aliphatic amidic compounds have been believed to be emissive. We report that this contention is incorrect and that the anomalous emission from amides originates in fluorescent impurities generated during their synthesis. In order to make this point, we have synthesized fluorescent compounds and have compared the absorption spectra with excitation spectra.

  2. 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.

  3. Robust trans-amide helical structure of oligomers of bicyclic mimics of β-proline: impact of positional switching of bridgehead substituent on amide cis-trans equilibrium.

    Science.gov (United States)

    Wang, Siyuan; Otani, Yuko; Liu, Xin; Kawahata, Masatoshi; Yamaguchi, Kentaro; Ohwada, Tomohiko

    2014-06-06

    Because homooligomers of 7-azabicyclo[2.2.1]heptane-2-endo-carboxylic acid, a bridged β-proline analogue with a substituent installed at the remote C4-bridgehead position, completely biased the amide cis-trans equilibrium to the cis-amide structure, we expected that introduction of a substituent at the C1-bridgehead position adjacent to the carboxylic acid moiety, rather than the remote C4-bridgehead position, would tip the cis-trans amide equilibrium toward trans-amide structure without the aid of hydrogen bonding. Thus, in this work we established an efficient synthetic route to an optically active bicyclic analogue of 1,1-disubstituted β-proline, bearing a substituent at the C1-bridgehead position. Crystallographic, spectroscopic, and computational studies showed that indeed oligomers of this analogue take a consistent helical structure involving all-trans-amide linkages, independently of the number of residues, from the dimer up to the octamer. Oligomers composed of (R)-β-amino acid units form an extended left-handed helix with about 2.7 residues per turn and an approximately 4.0 Å rise per residue, characterized by complete lack of main-chain hydrogen bonding. This unique helical structure shows some similarity in shape to the trans-amide-based polyproline II (PPII) helix. The present helix was stable in various kinds of solvents such as alcohols. The present work provided a fundamental structural basis for future applications.

  4. Fast acquisition of high resolution 4-D amide-amide NOESY with diagonal suppression, sparse sampling and FFT-CLEAN.

    Science.gov (United States)

    Werner-Allen, Jon W; Coggins, Brian E; Zhou, Pei

    2010-05-01

    Amide-amide NOESY provides important distance constraints for calculating global folds of large proteins, especially integral membrane proteins with beta-barrel folds. Here, we describe a diagonal-suppressed 4-D NH-NH TROSY-NOESY-TROSY (ds-TNT) experiment for NMR studies of large proteins. The ds-TNT experiment employs a spin state selective transfer scheme that suppresses diagonal signals while providing TROSY optimization in all four dimensions. Active suppression of the strong diagonal peaks greatly reduces the dynamic range of observable signals, making this experiment particularly suitable for use with sparse sampling techniques. To demonstrate the utility of this method, we collected a high resolution 4-D ds-TNT spectrum of a 23kDa protein using randomized concentric shell sampling (RCSS), and we used FFT-CLEAN processing for further reduction of aliasing artifacts - the first application of these techniques to a NOESY experiment. A comparison of peak parameters in the high resolution 4-D dataset with those from a conventionally-sampled 3-D control spectrum shows an accurate reproduction of NOE crosspeaks in addition to a significant reduction in resonance overlap, which largely eliminates assignment ambiguity. Likewise, a comparison of 4-D peak intensities and volumes before and after application of the CLEAN procedure demonstrates that the reduction of aliasing artifacts by CLEAN does not systematically distort NMR signals.

  5. Pyrrolic Amide: A New Hydrogen Bond Building Block for Self-assembly

    Institute of Scientific and Technical Information of China (English)

    YIN Zhen-Ming; LI Jian-Feng; HE Jia-Qi; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Molecular self-assembly has emerged as a powerful technology for the synthesis of nanostructured materials. In design of various molecular assemblies, hydrogen bonding is a preferably selected intra- or inter-molecular weak interaction in recent research by virtue of the directionality and specificity. The research for novel hydrogen bond building blocks that self-assembly into well defined structures is great important not only for gaining an understanding of the concepts of self-assembly but also for the design of new molecular materials. Pyrrolic amide moiety has one hydrogen bond acceptor (C =O) and two hydrogen bond donors (pyrrole NH and amide NH). By deliberately design, pyrrolic amide compounds would be new kinds hydrogen bond building blocks. So, pyrrolic amide compounds 1 ~ 6, which bear one, two or three pyrrolic amide moieties respectively, were designed and synthesized.

  6. Synthesis and antimicrobial activity of amide derivatives of polyether antibiotic-salinomycin.

    Science.gov (United States)

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

    2012-07-15

    For the first time a direct and practical approach to the synthesis of eight amide derivatives of polyether antibiotic-salinomycin is described. The structure of allyl amide (3a) has been determined using X-ray diffraction. Salinomycin and its amide derivatives have been screened for their in vitro antimicrobial activity against the typical gram-positive cocci, gram-negative rods and yeast-like organisms, as well as against a series of clinical isolates of methicillin-resistant Staphylococcus aureus and methicillin-sensitive S. aureus. Amides of salinomycin have been found to show a wide range of activities, from inactive at 256 μg/mL to active with MIC of 2 μg/mL, comparable with salinomycin. As a result, phenyl amide (3b) was found to be the most active salinomycin derivative against gram-positive bacteria, MRSA and MSSA.

  7. Structure-activity studies on the C-terminal amide of substance P.

    Science.gov (United States)

    Escher, E; Couture, R; Poulos, C; Pinas, N; Mizrahi, J; Theodoropoulos, D; Regoli, D

    1982-11-01

    Twelve C-terminal heptapeptide analogues of substance P have been synthesized by solid phase and by the classical solution method. The modifications concerned all the C-terminal primary amide of SP and should therefore help to understand the biological significance of this carboxamide, as evaluated by in vivo and in vitro bioassays. From the results it can be seen that not the slightest change of the two amide protons is tolerated without an important loss of activity: replacement of one or two amide protons with alkyl groups, extension of the amide to the hydrazide and its alkyl analogues, and exchange of the amide with an ester or a carboxylic acid all reduce the relative activity/affinity at least by 2-fold. It is not clear for what reason all these modifications produce such a drastic activity reduction.

  8. 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.

  9. Cu-catalyzed arylation of phosphinic amide facilitated by (±)-trans-cyclohexane-1,2-diamine

    Institute of Scientific and Technical Information of China (English)

    Juan Li; Song Lin Zhang; Chuan Zhou Tao; Yao Fu; Qing Xiang Guo

    2007-01-01

    Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-transcyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for synthesizing arylated phosphinic amides. Both kinetic measurement and theoretical calculation indicated that phosphinic amides were much less reactive than amides by about 10times in Cu-catalyzed cross coupling.

  10. Catalysis of a Flavoenzyme-Mediated Amide Hydrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Mukherjee, Tathagata; Zhang, Yang; Abdelwahed, Sameh; Ealick, Steven E.; Begley, Tadhg P. (Cornell); (TAM)

    2010-09-13

    A new pyrimidine catabolic pathway (the Rut pathway) was recently discovered in Escherichia coli K12. In this pathway, uracil is converted to 3-hydroxypropionate, ammonia, and carbon dioxide. The seven-gene Rut operon is required for this conversion. Here we demonstrate that the flavoenzyme RutA catalyzes the initial uracil ring-opening reaction to give 3-ureidoacrylate. This reaction, while formally a hydrolysis reaction, proceeds by an oxidative mechanism initiated by the addition of a flavin hydroperoxide to the C4 carbonyl. While peroxide-catalyzed amide hydrolysis has chemical precedent, we are not aware of a prior example of analogous chemistry catalyzed by flavin hydroperoxides. This study further illustrates the extraordinary catalytic versatility of the flavin cofactor.

  11. Lead optimization studies of cinnamic amide EP2 antagonists.

    Science.gov (United States)

    Ganesh, Thota; Jiang, Jianxiong; Yang, Myung-Soon; Dingledine, Ray

    2014-05-22

    Prostanoid receptor EP2 can play a proinflammatory role, exacerbating disease pathology in a variety of central nervous system and peripheral diseases. A highly selective EP2 antagonist could be useful as a drug to mitigate the inflammatory consequences of EP2 activation. We recently identified a cinnamic amide class of EP2 antagonists. The lead compound in this class (5d) displays anti-inflammatory and neuroprotective actions. However, this compound exhibited moderate selectivity to EP2 over the DP1 prostanoid receptor (∼10-fold) and low aqueous solubility. We now report compounds that display up to 180-fold selectivity against DP1 and up to 9-fold higher aqueous solubility than our previous lead. The newly developed compounds also display higher selectivity against EP4 and IP receptors and a comparable plasma pharmacokinetics. Thus, these compounds are useful for proof of concept studies in a variety of models where EP2 activation is playing a deleterious role.

  12. SYNTHESIS AND MORPHOLOGICAL STRUCTURE OF POLY(PHENYLENE SULFIDE AMIDE)

    Institute of Scientific and Technical Information of China (English)

    WU Qixian; CHEN Yongrong; ZHOU Zuowan

    1995-01-01

    Poly(phenylene sulfide amide) (PPSA) has been synthesized by using sulfur as Ssource which reacts with dichlorobenzamide (DCBA) and alkali in polar organic solvent atthe atmospheric pressure. The polymer structures were determined by elemental analysis,FT-IR and 1H-NMR. It is shown that the yielded polymer has linear structure and itsstructure unit is -p-C6H4-CONH -p-C6H4-S-. The polymer morphology was studied byX-ray diffraction and polarized microscopy. The results show that PPSA is a crystallinepolymer and its spherulites are the aggregation of nontwisting lamella or micro-threadstructure. Under shearing force, these crystals are dispersed to form micro-fibrillarstructure. The decomposition kinetics of PPSA was also studied at different heating rates.The decomposition energy of PPSA is higher than that of PPS.

  13. Effect of Antimicrobial Peptide-Amide: Indolicidin on Biological Membranes

    Directory of Open Access Journals (Sweden)

    Attila Gergely Végh

    2011-01-01

    Full Text Available Indolicidin, a cationic antimicrobial tridecapeptide amide, is rich in proline and tryptophan residues. Its biological activity is intensively studied, but the details how indolicidin interacts with membranes are not fully understood yet. We report here an in situ atomic force microscopic study describing the effect of indolicidin on an artificial supported planar bilayer membrane of dipalmitoyl phosphatidylcholine (DPPC and on purple membrane of Halobacterium salinarum. Concentration dependent interaction of the peptide and membranes was found in case of DPPC resulting the destruction of the membrane. Purple membrane was much more resistant against indolicidin, probably due to its high protein content. Indolicidin preferred the border of membrane disks, where the lipids are more accessible. These data suggest that the atomic force microscope is a powerful tool in the study of indolicidin-membrane interaction.

  14. Polymer amide in the Allende and Murchison meteorites

    Science.gov (United States)

    McGeoch, Julie E. M.; McGeoch, Malcolm W.

    2015-11-01

    It has been proposed that exothermic gas phase polymerization of amino acids can occur in the conditions of a warm dense molecular cloud to form hydrophobic polymer amide (HPA) (McGeoch and McGeoch 2014). In a search for evidence of this presolar chemistry Allende and Murchison meteorites and a volcano control were diamond burr-etched and Folch extracted for potential HPA yielding 85 unique peaks in the meteorite samples via matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI TOF/MS). The amino acids after acid hydrolysis in Allende were below the level of detection but many of the Allende peaks via the more sensitive MALDI/TOF analysis could be fitted to a polymer combination of glycine, alanine, and alpha-hydroxyglycine with high statistical significance. A similar significant fit using these three amino acids could not be applied to the Murchison data indicating more complex polymer chemistry.

  15. Interacting Blends of Novel Unsaturated Polyester Amide Resin with Styrene

    Directory of Open Access Journals (Sweden)

    Hasmukh S. Patel

    2004-01-01

    Full Text Available Novel unsaturated poly (ester-amide resins (UPEAs were prepared by the reaction between an epoxy resin, namely diglycidyl ether of bisphenol–A (DGEBA and unsaturated aliphatic bisamic acids using a base catalyst. These UPEAs were then blended with a vinyl monomer namely, Styrene (STY. to produce a homogeneous resin syrup. The curing of these UPEAs-STY. resin blends was carried out by using benzoyl peroxide (BPO as a catalyst and was monitored by using a differential scanning calorimeter (DSC. The glass fibre reinforced composites (i.e. laminates of these UPEA-STY. resin blends were fabricated using the DSC data. The chemical, mechanical and electrical properties of the glass fibre composites have also been evaluated. The unreinforced cured samples of the UPEA-STY. resin blends were also analyzed by thermogravimetry (TGA.

  16. Interaction of Thioamides, Selenoamides, and Amides With Diiodine

    Directory of Open Access Journals (Sweden)

    Nick Hadjiliadis

    2006-12-01

    Full Text Available We review the results of our work on the iodine interaction with thioamides, selenoamides, and amides. Complexes with (i “spoke” or “extended spoke” structures, D⋅I2 and D⋅I2⋅I2, respectively, (D is the ligand donor (ii iodonium salts of {[D2−I]+[In]−} (n=3, 7 and {[D2−I]+[FeCl4]−} formulae and (iii disulfides of the categories (a [D-D], (b {[D-DH]+[I3]−} have been isolated and characterized. A compound of formula {[D2−I]+[I3]−[D⋅I2]} containing both types of complexes (i and (ii was also isolated. The interaction of diiodine with selenium analogs of the antithyroid drug 6-n-propyl-2-thiouracil (PTU, of formulae RSeU (6-alkyl-2-Selenouracil results in the formation of complexes with formulae [(RSeUI2]. All these results are correlated with the mechanism of action of antithyroid drugs. Finally, we review here our work on the diiodine interaction with the amides (LO.

  17. 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.

  18. Characteristic Conformation of Mosher’s Amide Elucidated Using the Cambridge Structural Database

    Directory of Open Access Journals (Sweden)

    Akio Ichikawa

    2015-07-01

    Full Text Available 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.

  19. Synergistic effects of amides from two piper species on generalist and specialist herbivores.

    Science.gov (United States)

    Richards, Lora A; Dyer, Lee A; Smilanich, Angela M; Dodson, Craig D

    2010-10-01

    Plants use a diverse mix of defenses against herbivores, including multiple secondary metabolites, which often affect herbivores synergistically. Chemical defenses also can affect natural enemies of herbivores via limiting herbivore populations or by affecting herbivore resistance to parasitoids. In this study, we performed feeding experiments to examine the synergistic effects of imides and amides (hereafter "amides") from Piper cenocladum and P. imperiale on specialist (Eois nympha, Geometridae) and generalist (Spodoptera frugiperda, Noctuidae) lepidopteran larvae. Each Piper species has three unique amides, and in each experiment, larvae were fed diets containing different concentrations of single amides or combinations of the three. The amides from P. imperiale had negative synergistic effects on generalist survival and specialist pupal mass, but had no effect on specialist survival. Piper cenocladum amides also acted synergistically to increase mortality caused by parasitoids, and the direct negative effects of mixtures on parasitoid resistance and pupal mass were stronger than indirect effects via changes in growth rate and approximate digestibility. Our results are consistent with plant defense theory that predicts different effects of plant chemistry on generalist versus adapted specialist herbivores. The toxicity of Piper amide mixtures to generalist herbivores are standard bottom-up effects, while specialists experienced the top-down mediated effect of mixtures causing reduced parasitoid resistance and associated decreases in pupal mass.

  20. 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.

  1. 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.

  2. New synthesis route for ternary transition metal amides as well as ultrafast amide-hydride hydrogen storage materials.

    Science.gov (United States)

    Cao, Hujun; Santoru, Antonio; Pistidda, Claudio; Richter, Theresia M M; Chaudhary, Anna-Lisa; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

    2016-04-14

    K2[Mn(NH2)4] and K2[Zn(NH2)4] were successfully synthesized via a mechanochemical method. The mixture of K2[Mn(NH2)4] and LiH showed excellent rehydrogenation properties. In fact, after dehydrogenation K2[Mn(NH2)4]-8LiH fully rehydrogenates within 60 seconds at ca. 230 °C and 5 MPa of H2. This is one of the fastest rehydrogenation rates in amide-hydride systems known to date. This work also shows a strategy for the synthesis of transition metal nitrides by decomposition of the mixtures of M[M'(NH2)n] (where M is an alkali or alkaline earth metal and M' is a transition metal) and metal hydrides.

  3. Acceleration of Amide Bond Rotation by Encapsulation in the Hydrophobic Interior of a Water-Soluble Supramolecular Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

    2008-04-08

    The hydrophobic interior cavity of a self-assembled supramolecular assembly exploits the hydrophobic effect for the encapsulation of tertiary amides. Variable temperature 1H NMR experiments reveal that the free energy barrier for rotation around the C-N amide bond is lowered by up to 3.6 kcal/mol upon encapsulation. The hydrophobic cavity of the assembly is able to stabilize the less polar transition state of the amide rotation process. Carbon-13 labeling studies showed that the {sup 13}C NMR carbonyl resonance increases with temperature for the encapsulated amides which suggests that the assembly is able to favor a twisted for of the amide.

  4. Probing the production of amidated peptides following genetic and dietary copper manipulations.

    Directory of Open Access Journals (Sweden)

    Ping Yin

    Full Text Available Amidated neuropeptides play essential roles throughout the nervous and endocrine systems. Mice lacking peptidylglycine α-amidating monooxygenase (PAM, the only enzyme capable of producing amidated peptides, are not viable. In the amidation reaction, the reactant (glycine-extended peptide is converted into a reaction intermediate (hydroxyglycine-extended peptide by the copper-dependent peptidylglycine-α-hydroxylating monooxygenase (PHM domain of PAM. The hydroxyglycine-extended peptide is then converted into amidated product by the peptidyl-α-hydroxyglycine α-amidating lyase (PAL domain of PAM. PHM and PAL are stitched together in vertebrates, but separated in some invertebrates such as Drosophila and Hydra. In addition to its luminal catalytic domains, PAM includes a cytosolic domain that can enter the nucleus following release from the membrane by γ-secretase. In this work, several glycine- and hydroxyglycine-extended peptides as well as amidated peptides were qualitatively and quantitatively assessed from pituitaries of wild-type mice and mice with a single copy of the Pam gene (PAM(+/- via liquid chromatography-mass spectrometry-based methods. We provide the first evidence for the presence of a peptidyl-α-hydroxyglycine in vivo, indicating that the reaction intermediate becomes free and is not handed directly from PHM to PAL in vertebrates. Wild-type mice fed a copper deficient diet and PAM(+/- mice exhibit similar behavioral deficits. While glycine-extended reaction intermediates accumulated in the PAM(+/- mice and reflected dietary copper availability, amidated products were far more prevalent under the conditions examined, suggesting that the behavioral deficits observed do not simply reflect a lack of amidated peptides.

  5. Probing the production of amidated peptides following genetic and dietary copper manipulations.

    Science.gov (United States)

    Yin, Ping; Bousquet-Moore, Danielle; Annangudi, Suresh P; Southey, Bruce R; Mains, Richard E; Eipper, Betty A; Sweedler, Jonathan V

    2011-01-01

    Amidated neuropeptides play essential roles throughout the nervous and endocrine systems. Mice lacking peptidylglycine α-amidating monooxygenase (PAM), the only enzyme capable of producing amidated peptides, are not viable. In the amidation reaction, the reactant (glycine-extended peptide) is converted into a reaction intermediate (hydroxyglycine-extended peptide) by the copper-dependent peptidylglycine-α-hydroxylating monooxygenase (PHM) domain of PAM. The hydroxyglycine-extended peptide is then converted into amidated product by the peptidyl-α-hydroxyglycine α-amidating lyase (PAL) domain of PAM. PHM and PAL are stitched together in vertebrates, but separated in some invertebrates such as Drosophila and Hydra. In addition to its luminal catalytic domains, PAM includes a cytosolic domain that can enter the nucleus following release from the membrane by γ-secretase. In this work, several glycine- and hydroxyglycine-extended peptides as well as amidated peptides were qualitatively and quantitatively assessed from pituitaries of wild-type mice and mice with a single copy of the Pam gene (PAM(+/-)) via liquid chromatography-mass spectrometry-based methods. We provide the first evidence for the presence of a peptidyl-α-hydroxyglycine in vivo, indicating that the reaction intermediate becomes free and is not handed directly from PHM to PAL in vertebrates. Wild-type mice fed a copper deficient diet and PAM(+/-) mice exhibit similar behavioral deficits. While glycine-extended reaction intermediates accumulated in the PAM(+/-) mice and reflected dietary copper availability, amidated products were far more prevalent under the conditions examined, suggesting that the behavioral deficits observed do not simply reflect a lack of amidated peptides.

  6. The Catalysis of NAD+, NADP+ and Nicotinic Amide for Methanol Electrooxidation at Platinum Electrode

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ping; SHI Yufang; ZHANG Qiaolian; TANG Zhiyong; ZHENG Hongtao; YUAN Runzhang

    2006-01-01

    A group of liquid catalysts composed of nicotinic amide functioning on the anode of DMFC were investigated at a Pt electrode, which were nicotinic amide, nicotinamide adenine dinucleotide (NAD+) and its phosphate (NAD(P)+). The kinetics of methanol anode oxidation in the three reaction systems was compared by measuring potentiodynamic current-potential curves and AC impedances. The experimental results show that the dynamic behavior of methanol oxidation at a Pt electrode has been changed with adding the three substances. The influence of temperature on the catalysis of these coenzymes and nicotinic amide was discussed by comparing the AC impedances spectra of methanol oxidation at different temperatures.

  7. Ruthenium(II)-Catalyzed Regioselective Ortho Amidation of Imidazo Heterocycles with Isocyanates.

    Science.gov (United States)

    Shakoor, S M Abdul; Kumari, Santosh; Khullar, Sadhika; Mandal, Sanjay K; Kumar, Anil; Sakhuja, Rajeev

    2016-12-16

    Direct ortho amidation at the phenyl ring of 2-phenylimidazo heterocycles with aryl isocyanates has been achieved via a chelation-assisted cationic ruthenium(II) complex catalyzed mechanism. The methodology provides a straightforward, high-yielding regioselective approach toward the synthesis of an array of ortho-amidated phenylimidazo heterocycles without prior activation of C(sp(2))-H. This also reports the first method for coupling of aryl isocyanates with the imidazo[1,2-a]pyridine system via a pentacyclometalated intermediate. The methodology is found to be easily scalable and could be applied toward the selective ortho amidation of 2-heteroarylimidazo[1,2-a]pyridine frameworks.

  8. 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...

  9. Studies and Applications of Metals for the Synthesis of Carbinols, Amides and Carbohydrates

    DEFF Research Database (Denmark)

    Osztrovszky, Gyorgyi

    the carbonyl addition was found to be faster or comparable to the protonation by the reagent. Project 2: Ruthenium catalyzed synthesis of amides from primary alcohols and amines The direct synthesis of amides from alcohols and amines with the simultaneous liberation of dihydrogen was previously discovered...... for the amidation. These two systems do not show any significant differences in reactivity indicating that the same catalytically active species is operating. Project 3: Synthesis of a trisaccharide probe as a putative dengue virus receptor At the Institute for Glycomics major research has been devoted to identify...

  10. Chelate effects in sulfate binding by amide/urea-based ligands.

    Science.gov (United States)

    Jia, Chuandong; Wang, Qi-Qiang; Begum, Rowshan Ara; Day, Victor W; Bowman-James, Kristin

    2015-07-01

    The influence of chelate and mini-chelate effects on sulfate binding was explored for six amide-, amide/amine-, urea-, and urea/amine-based ligands. Two of the urea-based hosts were selective for SO4(2-) in water-mixed DMSO-d6 systems. Results indicated that the mini-chelate effect provided by a single urea group with two NH binding sites appears to provide enhanced binding over two amide groups. Furthermore, additional urea binding sites incorporated into the host framework appeared to overcome to some extent competing hydration effects with increasing water content.

  11. 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.

  12. 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 ().

  13. Functional properties of Pfr(Tic)amide and BIBP3226 at human neuropeptide FF2 receptors.

    Science.gov (United States)

    Engström, Mia; Wurster, Siegfried; Savola, Juha-Matti; Panula, Pertti

    2003-12-01

    The functional characteristics of two putative neuropeptide FF (NPFF) antagonists, BIBP3226 and PFR(Tic)amide, on the human neuropeptide FF receptor subtype 2 (hNPFF2) were investigated. Surprisingly, PFR(Tic)amide was shown to exhibit agonist properties in the [35S]guanosine-5'-O-(3-thio)triphosphate ([35S]GTPgammaS) binding assay. The efficacy of PFR(Tic)amide was significantly greater than that of (1DMe)Y8Fa, a stable analog of NPFF, and PFR(Tic)amide can therefore be classified as a 'super-agonist'. BIBP3226 did act as a reversible competitive antagonist on the hNPFF2 receptor. However, high concentrations of BIBP3226 also non-specifically increased [35S]GTP-gammaS binding. The usefulness of BIBP3226 as an antagonist tool on the NPFF receptor is thus limited.

  14. 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.

  15. Comparison of pH-sensitive degradability of maleic acid amide derivatives.

    Science.gov (United States)

    Kang, Sunyoung; Kim, Youngeun; Song, Youngjun; Choi, Jin Uk; Park, Euddeum; Choi, Wonmin; Park, Jeongseon; Lee, Yan

    2014-05-15

    We synthesized five maleic acid amide derivatives (maleic, citraconic, cis-aconitic, 2-(2'-carboxyethyl) maleic, 1-methyl-2-(2'-carboxyethyl) maleic acid amide), and compared their degradability for the future development of pH-sensitive biomaterials with tailored kinetics of the release of drugs, the change of charge density, and the degradation of scaffolds. The degradation kinetics was highly dependent upon the substituents on the cis-double bond. Among the maleic acid amide derivatives, 2-(2'-carboxyethyl) maleic acid amide with one carboxyethyl and one hydrogen substituent showed appropriate degradability at weakly acidic pH, and the additional carboxyl group can be used as a pH-sensitive linker.

  16. Stereoelectronic effects dictate molecular conformation and biological function of heterocyclic amides.

    Science.gov (United States)

    Reid, Robert C; Yau, Mei-Kwan; Singh, Ranee; Lim, Junxian; Fairlie, David P

    2014-08-27

    Heterocycles adjacent to amides can have important influences on molecular conformation due to stereoelectronic effects exerted by the heteroatom. This was shown for imidazole- and thiazole-amides by comparing low energy conformations (ab initio MP2 and DFT calculations), charge distribution, dipole moments, and known crystal structures which support a general principle. Switching a heteroatom from nitrogen to sulfur altered the amide conformation, producing different three-dimensional electrostatic surfaces. Differences were attributed to different dipole and orbital alignments and spectacularly translated into opposing agonist vs antagonist functions in modulating a G-protein coupled receptor for inflammatory protein complement C3a on human macrophages. Influences of the heteroatom were confirmed by locking the amide conformation using fused bicyclic rings. These findings show that stereoelectronic effects of heterocycles modulate molecular conformation and can impart strikingly different biological properties.

  17. Crystal structure of the high-energy-density material guanylurea dipicryl-amide.

    Science.gov (United States)

    Deblitz, Raik; Hrib, Cristian G; Hilfert, Liane; Edelmann, Frank T

    2014-08-01

    The title compound, 1-carbamoylguanidinium bis-(2,4,6-tri-nitro-phen-yl)amide [H2NC(=O)NHC(NH2)2](+)[N{C6H2(NO2)3-2,4,6}2](-) (= guanylurea dipicryl-amide), was prepared as dark-red block-like crystals in 70% yield by salt-metathesis reaction between guanylurea sulfate and sodium dipicryl-amide. In the solid state, the new compound builds up an array of mutually linked guanylurea cations and dipicryl-amide anions. The crystal packing is dominated by an extensive network of N-H⋯O hydrogen bonds, resulting in a high density of 1.795 Mg m(-3), which makes the title compound a potential secondary explosive.

  18. 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

  19. Preparation and phytotoxicity of novel kaurane diterpene amides with potential use as herbicides.

    Science.gov (United States)

    Boaventura, Maria Amélia Diamantino; Pereira, Rondinelle Gomes; de Oliveira Freitas, Luiza B; Dos Reis, Leandro Alves; da Silva Vieira, Henriete

    2008-05-14

    Novel kaurane ditepene monoamides were synthesized in good yields directly from kaurenoic ( 1) and grandiflorenic ( 2) acids and unprotected symmetrical diamines, using a modified protocol for monoacylation. Amides from 1 and 2 and monoamines were also obtained and tested against seed germination and growth of radicle and shoot of Lactuca sativa (lettuce), at 10 (-3), 10 (-5), and 10 (-7) M. Amides from symmetrical diamines showed significant inhibitory activity at higher concentrations.

  20. The Synthesis and Characterisation of Novel Amide Initiators for the ATRP of OEGMA

    OpenAIRE

    Kliene, Aaron

    2015-01-01

    Whilst atom transfer radical polymerisation (ATRP) has been shown to be a robust and versatile technique for the creation of a wide range of polymers from many different initiators, there is relatively little previous research into the usage of initiators containing amide functionality. Low initiator efficiencies, often resulting in higher than predicted molecular weight parameters, and slow polymerisations with variable rates of reaction are generally reported when amide initiators have prev...

  1. Zirconyl chloride promoted highly efficient solid phase synthesis of amide derivatives

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    An efficient solid phase route for the synthesis of amide derivatives by the reaction of carboxylic acids with urea in the presence of catalytic amount of zirconyl chloride under microwave irradiation conditions was described. In this way, a range of interesting amide derivatives was obtained in good to excellent yields. The catalyst was recycled with fresh reactants and it gave almost similar results without significant loss of activity up to the third run.

  2. 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...

  3. Syntheses of Macrocyclic Amides from L-Amino Acid Esters by RCM

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A series of succinate-derived macrocyclic amides( 1 ) was synthesized via ring-closing metathesis (RCM) as the key step. The substrate included 12 to 15 members. The metathesis precursors were obtained from the amide coupling of tert-butyl 3-carboxyhex-5-enoate(2) with numerous side-chain alkenylated amino acid esters of general type(3)derived from L-lysine and L-ornithine.

  4. Polycarbonate modified with crystallisable bis-ester tetra-amide units in a reaction extrusion process

    NARCIS (Netherlands)

    Zuiderduin, W.C.J.; Gaymans, R.J.

    2008-01-01

    Dry blends of polycarbonate (PC) and a bis-ester tetra-amide were extruded at 305 °C with a mini twin screw extruder. The bis-ester tetra-amide diamide (T6T6T-dimethyl) was composed of two and a half repeat units of Nylon 6,T and had methyl ester endgroups. During the extrusion, a trans-esterificati

  5. 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.

  6. Hyperbranched Poly(amide-ester) Mildly Synthesized and Its Characterization

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    AB2-type-prepolymerized monomer was rapidly (2 h) prepared atIoom temperature (25℃) using commercially available maleic anhydride (MA) and diethanolamine (DEA) as raw materials.By employing toluene-p-sulfonic acid as a catalyzer, a series of hyperbranched poly(amide-ester) (HBPAE) were successfully synthesized from prepared AB2 monomer by solution condensation polymerization through "one-step process" or "pseudo one-step process" (using pen taerythritol as a center core).The processes were carried out at high temperature of 120 C for 6 h in air atmosphere (inert protection free) with reduced pressure distillation (0.08~0.096 MPa).The results of FT-IR, UV-Vis, TGA, and intrinsic viscosity testing by Ubbelodhe viscometer showed that the prepared HBPAEspossess three-dimensional configuration with unsaturated conjugate structure,large numbers of branches and numerous terminal hydroxyl groups.These result in their lowviscosity, high solubility and thermal stability.

  7. Synthesis, characterization and pharmacological evaluation of amide prodrugs of Flurbiprofen

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  8. NMR study of hydroxy and amide protons in hyaluronan polymers.

    Science.gov (United States)

    Nestor, Gustav; Sandström, Corine

    2017-02-10

    Hyaluronan (HA) is an important and well characterized glycosaminoglycan with high viscosity and water-retaining capacity. Nonetheless, it is not fully understood whether conformational properties of the easily characterized HA oligomers can be transferred to HA polymers. To investigate possible differences in hydration, hydrogen bonding and flexibility between HA polymers and oligomers, hydroxy and amide protons of HA polymers were studied by solution-state and high-resolution magic angle spinning (HR-MAS) NMR spectroscopy. Measurements of chemical shifts, temperature coefficients and NOEs in HA polymers revealed that the NMR data are very similar compared to the interior of a HA octasaccharide, supporting transient hydrogen bond interactions across the β(1→3) and β(1→4) glycosidic linkages. However, differences in NOEs suggested a cis-like orientation between NH and H2 in the HA polymer. The lack of concentration dependence of the hydroxy proton chemical shifts suggests that there are no direct inter-chain interactions involving hydroxy protons at the concentrations investigated.

  9. Effect of amide bonds on the self-assembly of gemini surfactants.

    Science.gov (United States)

    Hoque, Jiaul; Gonuguntla, Spandhana; Yarlagadda, Venkateswarlu; Aswal, Vinod K; Haldar, Jayanta

    2014-06-21

    This study provides an insight into the micellar aggregation properties in aqueous solutions of various gemini surfactants bearing one or more amide groups at the side chains and/or in the spacer by conductivity and small angle neutron scattering (SANS) studies. The amide functionality was found to enhance the surfactant aggregation properties as compared to the surfactants having no amide bond. Furthermore, the aggregation properties of the gemini surfactants bearing amide groups were found to strongly depend on the position and number of amide bonds. With the increase in the number of amide bonds, the aggregation number (N) and the size of the micelles increased. Additionally, the size and shape of the micelles were also found to depend both on the hydrocarbon chain length and the spacer chain length. It was also found that the aggregation number and the size of the micelles increased with an increase in concentration and decreased with an increase in temperature. The critical micellar concentration (CMC) values of the gemini surfactants obtained by a conductometric method were found to vary greatly with variation in the hydrocarbon chain.

  10. Smart synthesis of high performance thermosets based on ortho-(amide-co-imide functional benzoxazines

    Directory of Open Access Journals (Sweden)

    Hatsuo eIshida

    2015-02-01

    Full Text Available High performance thermosets via amide-imide functional benzoxazine resins as precursors have been synthesized. The structures of synthesized monomers have been confirmed by 1H NMR and FT-IR. Among these two benzoxazine monomers, the ortho-amide-imide functional benzoxazine resin shows powerful features both in the synthesis of benzoxazine monomers and the properties of the corresponding thermosets. For the cross-linked poly(amide-co-imide based on ortho-amide-imide functional benzoxazine, a smart route is adopted to develop a more thermally stable cross-linked poly(benzoxazole-co-imide. Besides, the poly(benzoxazole-co-imide can also undergo a further thermal treatment to form polybenzoxazole. Furthermore, a main-chain type ortho-functional polybenzoxazine with amide-co-imide and benzoxazine groups as repeating units has also been prepared. Both the ortho-amide-imide functional benzoxazine and main-chain type polybenzoxazine resins show the possibility to form high performance thermosets with low cost and easy processability .

  11. UV resonance Raman investigation of the aqueous solvation dependence of primary amide vibrations.

    Science.gov (United States)

    Punihaole, David; Jakubek, Ryan S; Dahlburg, Elizabeth M; Hong, Zhenmin; Myshakina, Nataliya S; Geib, Steven; Asher, Sanford A

    2015-03-12

    We investigated the normal mode composition and the aqueous solvation dependence of the primary amide vibrations of propanamide. Infrared, normal Raman, and UV resonance Raman (UVRR) spectroscopy were applied in conjunction with density functional theory (DFT) to assign the vibrations of crystalline propanamide. We examined the aqueous solvation dependence of the primary amide UVRR bands by measuring spectra in different acetonitrile/water mixtures. As previously observed in the UVRR spectra of N-methylacetamide, all of the resonance enhanced primary amide bands, except for the Amide I (AmI), show increased UVRR cross sections as the solvent becomes water-rich. These spectral trends are rationalized by a model wherein the hydrogen bonding and the high dielectric constant of water stabilizes the ground state dipolar (-)O-C═NH2(+) resonance structure over the neutral O═C-NH2 resonance structure. Thus, vibrations with large C-N stretching show increased UVRR cross sections because the C-N displacement between the electronic ground and excited state increases along the C-N bond. In contrast, vibrations dominated by C═O stretching, such as the AmI, show a decreased displacement between the electronic ground and excited state, which result in a decreased UVRR cross section upon aqueous solvation. The UVRR primary amide vibrations can be used as sensitive spectroscopic markers to study the local dielectric constant and hydrogen bonding environments of the primary amide side chains of glutamine (Gln) and asparagine (Asn).

  12. Retinoic acid amide inhibits JAK/STAT pathway in lung cancer which leads to apoptosis.

    Science.gov (United States)

    Li, Hong-Xing; Zhao, Wei; Shi, Yan; Li, Ya-Na; Zhang, Lian-Shuang; Zhang, Hong-Qin; Wang, Dong

    2015-11-01

    Small cell lung cancer (SCLC) accounts for 12 to 16% of lung neoplasms and has a high rate of metastasis. The present study demonstrates the antiproliferative effect of retinoic acid amide in vitro and in vivo against human lung cancer cells. The results from MTT assay showed a significant growth inhibition of six tested lung cancer cell lines and inhibition of clonogenic growth at 30 μM. Retinoic acid amide also leads to G2/M-phase cell cycle arrest and apoptosis of lung cancer cells. It caused inhibition of JAK2, STAT3, and STAT5, increased the level of p21WAF1, and decreased cyclin A, cyclin B1, and Bcl-XL expression. Retinoic acid amide exhibited a synergistic effect on antiproliferative effects of methotrexate in lung cancer cells. In lung tumor xenografts, the tumor volume was decreased by 82.4% compared to controls. The retinoic acid amide-treated tumors showed inhibition of JAK2/STAT3 activation and Bcl-XL expression. There was also increase in expression of caspase-3 and caspase-9 in tumors on treatment with retinoic acid amide. Thus, retinoic acid amide exhibits promising antiproliferative effects against human lung cancer cells in vitro and in vivo and enhances the antiproliferative effect of methotrexate.

  13. Computational Amide I Spectroscopy for Refinement of Disordered Peptide Ensembles: Maximum Entropy and Related Approaches

    Science.gov (United States)

    Reppert, Michael; Tokmakoff, Andrei

    The structural characterization of intrinsically disordered peptides (IDPs) presents a challenging biophysical problem. Extreme heterogeneity and rapid conformational interconversion make traditional methods difficult to interpret. Due to its ultrafast (ps) shutter speed, Amide I vibrational spectroscopy has received considerable interest as a novel technique to probe IDP structure and dynamics. Historically, Amide I spectroscopy has been limited to delivering global secondary structural information. More recently, however, the method has been adapted to study structure at the local level through incorporation of isotope labels into the protein backbone at specific amide bonds. Thanks to the acute sensitivity of Amide I frequencies to local electrostatic interactions-particularly hydrogen bonds-spectroscopic data on isotope labeled residues directly reports on local peptide conformation. Quantitative information can be extracted using electrostatic frequency maps which translate molecular dynamics trajectories into Amide I spectra for comparison with experiment. Here we present our recent efforts in the development of a rigorous approach to incorporating Amide I spectroscopic restraints into refined molecular dynamics structural ensembles using maximum entropy and related approaches. By combining force field predictions with experimental spectroscopic data, we construct refined structural ensembles for a family of short, strongly disordered, elastin-like peptides in aqueous solution.

  14. Pb(II)-promoted amide cleavage: mechanistic comparison to a Zn(II) analogue.

    Science.gov (United States)

    Elton, Eric S; Zhang, Tingting; Prabhakar, Rajeev; Arif, Atta M; Berreau, Lisa M

    2013-10-07

    Two new Pb(II) complexes of the amide-appended nitrogen/sulfur epppa (N-((2-ethylthio)ethyl)-N-((6-pivaloylamido-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine) chelate ligand, [(epppa)Pb(NO3)2] (4-NO3) and [(epppa)Pb(ClO4)2] (4-ClO4), were prepared and characterized. In the solid state, 4-NO3 exhibits κ(5)-epppa chelate ligand coordination as well as the coordination of two bidentate nitrate ions. In acetonitrile, 4-NO3 is a 1:1 electrolyte with a coordinated NO3(-), whereas 4-ClO4 is a 1:2 electrolyte. Treatment of 4-ClO4 with 1 equiv Me4NOH·5H2O in CH3CN:CH3OH (3:5) results in amide methanolysis in a reaction that is akin to that previously reported for the Zn(II) analogue [(epppa)Zn](ClO4)2 (3-ClO4). (1)H NMR kinetic studies of the amide methanolysis reactions of 4-ClO4 and 3-ClO4 as a function of temperature revealed free energies of activation of 21.3 and 24.5 kcal/mol, respectively. The amide methanolysis reactions of 4-ClO4 and 3-ClO4 differ in terms of the effect of the concentration of methanol (saturation kinetics for 4-ClO4; second-order behavior for 3-ClO4), the observation of a small solvent kinetic isotope effect (SKIE) only for the reaction of the Zn(II)-containing 3-ClO4, and the properties of an initial intermediate isolated from each reaction upon treatment with Me4NOH·5H2O. These experimental results, combined with computational studies of the amide methanolysis reaction pathways of 4-ClO4 and 3-ClO4, indicate that the Zn(II)-containing 3-ClO4 initially undergoes amide deprotonation upon treatment with Me4NOH·5H2O. Subsequent amide protonation from coordinated methanol yields a structure containing a coordinated neutral amide and methoxide anion from which amide cleavage can then proceed. The rate-determining step in this pathway is either amide protonation or protonation of the leaving group. The Pb(II)-containing 4-ClO4 instead directly forms a neutral amide-containing, epppa-ligated Pb(II)-OH/Pb(II)-OCH3 equilibrium mixture upon treatment

  15. Fatty acid amide hydrolase inhibition by neurotoxic organophosphorus pesticides.

    Science.gov (United States)

    Quistad, G B; Sparks, S E; Casida, J E

    2001-05-15

    Organophosphorus (OP) compound-induced inhibition of acetylcholinesterase (AChE) and neuropathy target esterase explains the rapid onset and delayed neurotoxic effects, respectively, for OP insecticides and related compounds but apparently not a third or intermediate syndrome with delayed onset and reduced limb mobility. This investigation tests the hypothesis that fatty acid amide hydrolase (FAAH), a modulator of endogenous signaling compounds affecting sleep (oleamide) and analgesia (anandamide), is a sensitive target for OP pesticides with possible secondary neurotoxicity. Chlorpyrifos oxon inhibits 50% of the FAAH activity (IC50 at 15 min, 25 degrees C, pH 9.0) in vitro at 40--56 nM for mouse brain and liver, whereas methyl arachidonyl phosphonofluoridate, ethyl octylphosphonofluoridate (EOPF), oleyl-4H-1,3,2-benzodioxaphosphorin 2-oxide (oleyl-BDPO), and dodecyl-BDPO give IC50s of 0.08--1.1 nM. These BDPOs and EOPF inhibit mouse brain FAAH in vitro with > or =200-fold higher potency than for AChE. Five OP pesticides inhibit 50% of the brain FAAH activity (ED50) at diazinon, and methamidophos occurs near acutely toxic levels, profenofos and tribufos are effective at asymptomatic doses. Two BDPOs (dodecyl and phenyl) and EOPF are potent inhibitors of FAAH in vivo (ED50 0.5--6 mg/kg). FAAH inhibition of > or =76% in brain depresses movement of mice administered anandamide at 30 mg/kg ip, often leading to limb recumbency. Thus, OP pesticides and related inhibitors of FAAH potentiate the cannabinoid activity of anandamide in mice. More generally, OP compound-induced FAAH inhibition and the associated anandamide accumulation may lead to reduced limb mobility as a secondary neurotoxic effect.

  16. N-acetylcysteine amide, a promising antidote for acetaminophen toxicity.

    Science.gov (United States)

    Khayyat, Ahdab; Tobwala, Shakila; Hart, Marcia; Ercal, Nuran

    2016-01-22

    Acetaminophen (N-acetyl-p-aminophenol, APAP) is one of the most widely used over the counter antipyretic and analgesic medications. It is safe at therapeutic doses, but its overdose can result in severe hepatotoxicity, a leading cause of drug-induced acute liver failure in the USA. Depletion of glutathione (GSH) is one of the initiating steps in APAP-induced hepatotoxicity; therefore, one strategy for restricting organ damage is to restore GSH levels by using GSH prodrugs. N-acetylcysteine (NAC), a GSH precursor, is the only currently approved antidote for an acetaminophen overdose. Unfortunately, fairly high doses and longer treatment times are required due to its poor bioavailability. In addition, oral and I.V. administration of NAC in a hospital setting are laborious and costly. Therefore, we studied the protective effects of N-acetylcysteine amide (NACA), a novel antioxidant with higher bioavailability, and compared it with NAC in APAP-induced hepatotoxicity in C57BL/6 mice. Our results showed that NACA is better than NAC at a low dose (106mg/kg) in preventing oxidative stress and protecting against APAP-induced damage. NACA significantly increased GSH levels and the GSH/GSSG ratio in the liver to 66.5% and 60.5% of the control, respectively; and it reduced the level of ALT by 30%. However, at the dose used, NAC was not effective in combating the oxidative stress induced by APAP. Thus, NACA appears to be better than NAC in reducing the oxidative stress induced by APAP. It would be of great value in the health care field to develop drugs like NACA as more effective and safer options for the prevention and therapeutic intervention in APAP-induced toxicity.

  17. Arg-Phe-amide-related peptides influence gonadotropin-releasing hormone neurons

    Institute of Scientific and Technical Information of China (English)

    Haluk Kelestimur; Emine Kacar; Aysegul Uzun; Mete Ozcan; Selim Kutlu

    2013-01-01

    The hypothalamic Arg-Phe-amide-related peptides, gonadotropin-inhibitory hormone and orthologous mammalian peptides of Arg-Phe-amide, may be important regulators of the hypothalamus-pituitary-gonadal reproductive axis. These peptides may modulate the effects of kisspeptins because they are presently recognized as the most potent activators of the hypothalamus-pituitary-gonadal axis. However, their effects on gonadotropin-releasing hormone neurons have not been investigated. In the current study, the GT1–7 cell line-expressing gonadotropin-releasing hormone was used as a model to explore the effects of Arg-Phe- amide-related peptides on kisspeptin activation. Intracellular calcium concentration was quantified using the calcium-sensitive dye, fura-2 acetoxymethyl ester. Gonadotropin-releasing hormone released into the medium was detected via enzyme-linked immunosorbent assay. Results showed that 100 nmol/L kisspeptin-10 significantly increased gonadotropin-releasing hormone levels (at 120 minutes of exposure) and intracellular calcium concentrations. Co-treatment of kisspeptin with 1 μmol/L gonadotropin-inhibitory hormone or 1 μmol/L Arg-Phe-amide-related peptide-1 significantly attenuated levels of kisspeptin-induced gonadotropin-releasing hormone but did not affect kisspeptin-induced elevations of intracellular calcium concentration. Overall, the results suggest that gonadotropin-inhibitory hormone and Arg-Phe-amide-related peptide-1 may have inhibitory effects on kisspeptin-activated gonadotropin-releasing hormone neurons independent of the calcium signaling pathway.

  18. Measurement of amide hydrogen exchange rates with the use of radiation damping.

    Science.gov (United States)

    Fan, Jing-Song; Lim, Jackwee; Yu, Binhan; Yang, Daiwen

    2011-09-01

    A simple method for measuring amide hydrogen exchange rates is presented, which is based on the selective inversion of water magnetization with the use of radiation damping. Simulations show that accurate exchange rates can be measured despite the complications of radiation damping and cross relaxation to the exchange process between amide and water protons. This method cannot eliminate the contributions of the exchange-relayed NOE and direct NOE to the measured exchange rates, but minimize the direct NOE contribution. In addition, the amides with a significant amount of such indirect contributions are possible to be identified from the shape of the exchange peak intensity profiles or/and from the apparent relaxation rates of amide protons which are extracted from fitting the intensity profiles to an equation established here for our experiment. The method was tested on ubiquitin and also applied to an acyl carrier protein. The amide exchange rates for the acyl carrier protein at two pHs indicate that the entire protein is highly dynamic on the second timescale. Low protection factors for the residues in the regular secondary structural elements also suggest the presence of invisible unfolded species. The highly dynamic nature of the acyl carrier protein may be crucial for its interactions with its substrate and enzymes.

  19. Enhancing ionic conductivity in lithium amide for improved energy storage materials

    Science.gov (United States)

    Davies, Rosalind A.; Hewett, David R.; Anderson, Paul A.

    2015-03-01

    Non-stoichiometry and bulk cation transport have been identified as key factors in the release and uptake of hydrogen in the Li-N-H system. Amide halide phases have been synthesized that have ionic conductivities several orders of magnitude greater than lithium amide, a faster rate of hydrogen release and elimination of the by-product, ammonia. Here we report the effect of both anion- and cation-doping on the hydrogen desorption properties of lithium amide, focusing in particular on how the presence of chloride anions and magnesium cations affects and controls the structure of the amide and imide compounds at the sub-nanometre level. Reducing the chloride content resulted in new low-chloride rhombohedral phases that contain around half of the chloride present in earlier amide chlorides, but maintained the enhancements seen in hydrogen desorption properties when compared to the halide-free system. These materials may also have potential in a range of other energy applications such as all solid state lithium ion batteries, supercapacitors, and CO2 capture and storage membranes. Invited talk at the 7th International Workshop on Advanced Materials Science and Nanotechnology IWAMSN2014, 2-6 November 2014, Ha Long, Vietnam.

  20. A comparative study of the complexation of uranium(VI) withoxydiacetic acid and its amide derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Rao, Linfeng; Tian, Guoxin

    2005-05-01

    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.

  1. The design, synthesis of amide KARI inhibitors and their biological activities

    Institute of Scientific and Technical Information of China (English)

    Baolei WANG; Yi MA; Yonghong LI; Suhua WANG; Zhengming LI

    2009-01-01

    Ketol-acid reductoisomerase(KARI) is a promising target for the design of herbicides yet there are only few reports on the molecular design of KARI inhibitors. In this paper, based on the reported 0.165 nm high resolution crystal structure of the spinach KARI complex, 279 molecules with low binding energy toward KARI were obtained from an MDL/ACD 3D database search using the program DOCK 4.0. According to the structural information of 279 molecules provided, some amide compounds have been designed and synthesized. The bioassay results show that most of these amides had inhibitory activity to rice KARI at a test concentration of 200 μg/mL. Among which eight amides, compounds 1 and 6 show 57.4% and 48.1% inhibitory activity to KARI. The herbicidal activities of these amides were further investigated on di-cotyledonous rape (Brassica campestris) and mono-cotyledonous bar-nyardgrass (Echinochloa crusgalli). Compounds 1 and 6 were more favorable than others and showed 52.0% and 72.6% inhibitory activity on rape root at 100 μg/mL concentration, respectively. These amides could be further optimized for finding more potent candidates.

  2. Lanthanide(III) complexation with an amide derived pyridinophane.

    Science.gov (United States)

    Castro, Goretti; Bastida, Rufina; Macías, Alejandro; Pérez-Lourido, Paulo; Platas-Iglesias, Carlos; Valencia, Laura

    2015-02-16

    Herein we report a detailed investigation of the solid state and solution structures of lanthanide(III) complexes with the 18-membered pyridinophane ligand containing acetamide pendant arms TPPTAM (TPPTAM = 2,2',2″-(3,7,11-triaza-1,5,9(2,6)-tripyridinacyclododecaphane-3,7,11-triyl)triacetamide). The ligand crystallizes in the form of a clathrated hydrate, where the clathrated water molecule establishes hydrogen-bonding interactions with the amide NH groups and two N atoms of the macrocycle. The X-ray structures of 13 different Ln(3+) complexes obtained as the nitrate salts (Ln(3+) = La(3+)-Yb(3+), except Pm(3+)) have been determined. Additionally, the X-ray structure of the La(3+) complex obtained as the triflate salt was also obtained. In all cases the ligand provides 9-fold coordination to the Ln(3+) ion, ten coordination being completed by an oxygen atom of a coordinated water molecule or a nitrate or triflate anion. The bond distances of the metal coordination environment show a quadratic change along the lanthanide series, as expected for isostructural series of Ln(3+) complexes. Luminescence lifetime measurements obtained from solutions of the Eu(3+) and Tb(3+) complexes in H2O and D2O point to the presence of a water molecule coordinated to the metal ion in aqueous solutions. The analysis of the Ln(3+)-induced paramagnetic shifts indicates that the complexes are ten-coordinated throughout the lanthanide series from Ce(3+) to Yb(3+), and that the solution structure is very similar to the structures observed in the solid state. The complexes of the light Ln(3+) ions are fluxional due to a fast Δ(λλλλλλ) ↔ Λ(δδδδδδ) interconversion that involves the inversion of the macrocyclic ligand and the rotation of the acetamide pendant arms. The complexes of the small Ln(3+) ions are considerably more rigid, the activation free energy determined from VT (1)H NMR for the Lu(3+) complex being ΔG(⧧)298 = 72.4 ± 5.1 kJ mol(-1).

  3. 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

  4. Synthesis, Anticancer and Antibacterial Activity of Salinomycin N-Benzyl Amides

    Directory of Open Access Journals (Sweden)

    Michał Antoszczak

    2014-11-01

    Full Text Available 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.

  5. 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.

  6. Amide Rotation Hindrance Predicts Proteolytic Resistance of Cystine-Knot Peptides.

    Science.gov (United States)

    Zhou, Yanzi; Xie, Daiqian; Zhang, Yingkai

    2016-04-07

    Cystine-knot peptides have remarkable stability against protease degradation and are attractive scaffolds for peptide-based therapeutic and diagnostic agents. In this work, by studying the hydrolysis reaction of a cystine-knot inhibitor MCTI-A and its variants with ab initio QM/MM molecular dynamics simulations, we have elucidated an amide rotation hindrance mechanism for proteolysis resistance: The proteolysis of MCTI-A is retarded due to the higher free energy cost during the rotation of NH group around scissile peptide bond at the tetrahedral intermediate of acylation, and covalent constraint provided by disulfide bonds is the key factor to hinder this rotation. A nearly linear correlation has been revealed between free energy barriers of the peptide hydrolysis reaction and the amide rotation free energy changes at the protease-peptide Michaelis complex state. This suggests that amide rotation hindrance could be one useful feature to estimate peptide proteolysis stability.

  7. 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...

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

    Science.gov (United States)

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

    2013-06-01

    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.

  9. 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...... of the 198 amino acid intein with an eight amino acid linker. The optimized intein construct was used to produce the PYY derivative under high cell density cultivation conditions, generating the peptide thioester precursor in good yields and subsequent amidation provided the target peptide......., 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...

  10. 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...... as their glycine-extended precursors, were characterized by sequence-specific radioimmunoassays, gel-chromatography, h.p.l.c. and amino acid sequencing. alpha MSH and gamma 1MSH constituted 0.27-1.32% and 0.10-5.10%, respectively, of the POMC-derived products [calculated as the sum of adrenocorticotropic hormone...... (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...

  11. 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.

  12. Synthesis and characterization of alternating poly(amide urea)s and poly(amide urethane urethane)s from ε-caprolactam, diamines, and diphenyl carbonate or ethylene carbonate

    NARCIS (Netherlands)

    Ubaghs, Luc; Sharma, Bhaskar; Keul, Helmut; Höcker, Hartwig; Loontjens, Ton; Benthem, Rolf van

    2003-01-01

    Alternating poly(amide urea)s from ε-caprolactam, diamines H2N-(CH2)x-NH2 (x = 2 - 4), and diphenyl carbonate were prepared in two steps. The microstructure of the poly(amide urea)s, as determined by means of 1H NMR spectroscopy, reveals a strictly alternating sequence of the building blocks. The mo

  13. Amide functionalized MWNT/SPEEK composite membrane for better electrochemical performance

    Science.gov (United States)

    Gahlot, Swati; Sharma, Prem P.; Kulshrestha, Vaibhav

    2016-05-01

    Nanocomposite membranes based on multiwalled carbon nanotube /SPEEK (sulfonated poly ether ether ketone) have been synthesized via simple solution casting. Prior to use CNT have been purified and grafted with carboxylic acid groups onto its walls by means of sulfuric and nitric acid. Afterwards, amidation of carboxylated CNTs (c-CNT) has been done. Amidated CNT (a-CNT) is then incorporated in SPEEK polymer matrix to synthesize nanocomposite membranes. Physicochemical, structural, thermal and mechanical characterizations are done through the respective techniques. Electric and ionic conductivities have also been evaluated. Composites membranes show the enhanced electrochemical performance with higher electric conductivity.

  14. 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...... QM results obtained for a small protein with an RMSD of 0.25 ppm (r = 0.94). ProCS is interfaced with the PHAISTOS protein simulation program and is used to infer statistical protein ensembles that reflect experimentally measured amide proton chemical shift values. Such chemical shift...

  15. 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)

  16. Naphthalene/quinoline amides and sulfonylureas as potent and selective antagonists of the EP4 receptor.

    Science.gov (United States)

    Burch, Jason D; Farand, Julie; Colucci, John; Sturino, Claudio; Ducharme, Yves; Friesen, Richard W; Lévesque, Jean-François; Gagné, Sébastien; Wrona, Mark; Therien, Alex G; Mathieu, Marie-Claude; Denis, Danielle; Vigneault, Erika; Xu, Daigen; Clark, Patsy; Rowland, Steve; Han, Yongxin

    2011-02-01

    Two new series of EP(4) antagonists based on naphthalene/quinoline scaffolds have been identified as part of our on-going efforts to develop treatments for inflammatory pain. One series contains an acidic sulfonylurea pharmacophore, whereas the other is a neutral amide. Both series show subnanomolar intrinsic binding potency towards the EP(4) receptor, and excellent selectivity towards other prostanoid receptors. While the amide series generally displays poor pharmacokinetic parameters, the sulfonylureas exhibit greatly improved profile. MF-592, the optimal compound from the sulfonylurea series, has a desirable overall preclinical profile that suggests it is suitable for further development.

  17. 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.

  18. 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...

  19. 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

    to calculate the dielectric from the mechanical response and vice versa. Using a single parameter for a given system, good agreement between model calculations and experimental data is achieved for the entire relaxation spectra, including secondary relaxations and the Debye-like dielectric peak......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...... in the secondary amides. In addition, the predictions of the shoving model are confirmed for the investigated liquids...

  20. Synthesis and characterization of alternating poly(amide urethane)s from ε-caprolactone, diamines and diphenyl carbonate

    NARCIS (Netherlands)

    Sharma, Bhaskar; Keul, Helmut; Höcker, Hartwig; Loontjens, Ton; Benthem, Rolf van

    2005-01-01

    The synthesis of alternating poly(amide urethane)s 5a–d was performed in three steps using ε-caprolactone, diamines, and diphenyl carbonate as starting materials. The microstructure and nature of the end groups of the poly(amide urethane)s were determined by means of 1H NMR spectroscopy, which revea

  1. Synthesis of new opioid derivatives with a propellane skeleton and their pharmacology. Part 2: Propellane derivatives with an amide side chain.

    Science.gov (United States)

    Nagase, Hiroshi; Akiyama, Junko; Nakajima, Ryo; Hirayama, Shigeto; Nemoto, Toru; Gouda, Hiroaki; Hirono, Shuichi; Fujii, Hideaki

    2012-04-15

    We designed and synthesized propellane derivatives with a 6- or 7-amide side chain on the basis of the active conformation of the κ selective agonist nalfurafine. The 6-amides showed high affinities for the κ receptor, and one of the 6β-amides showed higher κ selectivity than nalfurafine. On the other hand, although the affinities of the 7-amides decreased compared to the 6-amides, some 7α-amides showed the highest selectivities for the κ receptor among the tested compounds. The affinities of 7β-isomers were extremely low, which was postulated to result from the shielding effect of the 7β-amide side chain against the lone electron pair on the 17-nitrogen. This is the first conformational information about the 7-amide side chain in propellane derivatives.

  2. Studies of linear correlation factor of dielectric polarization and excess dipolar free energies of amides in apolar solvents

    Indian Academy of Sciences (India)

    M Malathi; R Sabesan; S Krishnan

    2005-09-01

    The Kirkwood–Frohlich correlation factor (), Eyring's parameters and * and the dipolar excess free energies of dilute solutions of formamide, acetamide, -methyl acetamide, , -dimethyl formamide and , -dimethyl acetamide in 1,4-dioxan/benzene were obtained from a measurement of their static dielectric permittivities at 308 K. The fluid structure of these amides is discussed. Both in formamide and acetamide a dimeric linear chain with the individual dipoles more or less parallely oriented is preferred. In -methyl acetamide, the antiparallel orientation of dipoles at lower concentrations turns into a parallel orientation with increase of concentration. In tertiary amides, with increase of concentration, parallel orientation of dipoles with global value of tending to unity is observed. The dipolar excess free energy of mixing in a given solvent is of the order primary amide > secondary amide > tertiary amide.

  3. Amide-Exchange-Rate-Edited NMR (AERE-NMR) Experiment:A Novel Method for Resolving Overlapping Resonances

    Institute of Scientific and Technical Information of China (English)

    LIU Xue-Hui; LIN Dong-Hai

    2007-01-01

    This paper describes an amide-exchange-rate-edited (AERE) NMR method that can effectively alleviate the problem of resonance overlap for proteins and peptides. This method exploits the diversity of amide proton exchange rates and consists of two complementary experiments: (1) SEA (solvent exposed amide)-type NMR experiments to map exchangeable surface residues whose amides are not involved in hydrogen bonding, and (2) presat-type NMR experiments to map solvent inaccessibly buried residues or nonexchangeable residues located in hydrogen-bonded secondary structures with properly controlled saturation transfer via amide proton exchanges with the solvent. This method separates overlapping resonances in a spectrum into two complementary spectra. The AERE-NMR method was demonstrated with a sample of 15N/13C/2H(70%) labeled ribosome-inactivating protein trichosanthin of 247 residues.

  4. 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.

  5. 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.

  6. 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- ethyl... Specific Chemical Substances § 721.9672 Amides, tall-oil fatty, N- ethyl], reaction products with sulfur... and significant new uses subject to reporting. (1) The chemical substance identified as amides,...

  7. 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 he...

  8. 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.

  9. 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...

  10. Effects of indole amides on lettuce and onion germination and growth.

    Science.gov (United States)

    Borgati, Thiago F; Boaventura, Maria Amelia D

    2011-01-01

    Auxins, such as indole-3-acetic acid (IAA), are important in plant germination and growth, while physiological polyamines, such as putrescine, are involved in cell proliferation and differentiation, and their concentrations increase during germination. In this work, novel indole amides were synthesized in good yields by monoacylation of morpholine and unprotected symmetrical diamines with indole-3-carboxylic acid, a putative metabolite of IAA, possessing no auxin-like activity. These amides were tested for their effects on seed germination and growth of the radicles and shoots of Lactuca sativa (lettuce) and Allium cepa (onion) seedlings, at 100.0, 1.0, and 0.01 microM concentrations. Germination was generally stimulated, with the exception of amide 3, derived from morpholine, at 100 microM. On radicle and shoot growth, the effect of these compounds was predominantly inhibitory. Compound 3 was the best inhibitor of growth of lettuce and onion, at the highest concentration. Amides, such as propanil, among others, are described as having herbicidal activity.

  11. Synthesis and characterization of some N-substituted amides of salicylic acid

    OpenAIRE

    Lupea Xenia Alfa; Padure Mirabela

    2003-01-01

    The synthesis of some N-substituted aromatic amides in the salicylic acid series was achieved, by direct reaction between primary amines and salicylic acid in inert organic solvent, in the presence of PCl3. The compounds that were obtained, partially not described in literature, were characterized by chemical-physical methods.

  12. Synthesis and characterization of some N-substituted amides of salicylic acid

    Directory of Open Access Journals (Sweden)

    Lupea Xenia Alfa

    2003-01-01

    Full Text Available The synthesis of some N-substituted aromatic amides in the salicylic acid series was achieved, by direct reaction between primary amines and salicylic acid in inert organic solvent, in the presence of PCl3. The compounds that were obtained, partially not described in literature, were characterized by chemical-physical methods.

  13. Amides from Piper capense with CNS activity

    DEFF Research Database (Denmark)

    Pedersen, Mikael Egebjerg; Metzler, Bjørn; Stafford, Gary Ivan;

    2009-01-01

    (A) receptor (IC(50) values of 1.2 mM and 1.0 mM, respectively). The present study suggests that strict structural properties of the amides are essential for affinity. Taken together, these observations suggest that the carbon chain must contain not less than four carbons, and that a conjugated double bond...

  14. Amide, urea and thiourea-containing triphenylene derivatives: influence of H-bonding on mesomorphic properties

    NARCIS (Netherlands)

    Paraschiv, I.; Tomkinson, A.; Giesbers, M.; Sudhölter, E.J.R.; Zuilhof, H.; Marcelis, A.T.M.

    2007-01-01

    The synthesis and thermotropic properties are reported for a series of hexaalkoxytriphenylenes that contain an amide, urea or thiourea group in one of their alkoxy tails. The intermolecular hydrogen bonding abilities of these molecules have a disturbing influence on the formation and stability of th

  15. 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,…

  16. 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, ...

  17. 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...

  18. 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....

  19. 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.

  20. 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

    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...

  1. Biocatalytic Synthesis of Highly Enantiopure 1,4-Benzodioxane-2-carboxylic Acid and Amide

    Institute of Scientific and Technical Information of China (English)

    LIU Jun; WANG De-Xian; ZHENG Qi-Yu; WANG Mei-Xiang

    2006-01-01

    Catalyzed by Rhodococcus erythropolis A J270, a nitrile hydratase and amidase containing microbial whole-cell catalyst, at 10 ℃ and with the use of methanol as a co-solvent, nitrile and amide biotransformations produce 2S-1,4-benzodioxane-2-carboxamide and 2R-1,4-benzodioxane-2-carboxylic acid in high yields with excellent enantioselectivity.

  2. Computational Amide I 2D IR Spectroscopy as a Probe of Protein Structure and Dynamics

    Science.gov (United States)

    Reppert, Mike; Tokmakoff, Andrei

    2016-05-01

    Two-dimensional infrared spectroscopy of amide I vibrations is increasingly being used to study the structure and dynamics of proteins and peptides. Amide I, a primarily carbonyl stretching vibration of the protein backbone, provides information on secondary structures as a result of vibrational couplings and on hydrogen-bonding contacts when isotope labeling is used to isolate specific sites. In parallel with experiments, computational models of amide I spectra that use atomistic structures from molecular dynamics simulations have evolved to calculate experimental spectra. Mixed quantum-classical models use spectroscopic maps to translate the structural information into a quantum-mechanical Hamiltonian for the spectroscopically observed vibrations. This allows one to model the spectroscopy of large proteins, disordered states, and protein conformational dynamics. With improvements in amide I models, quantitative modeling of time-dependent structural ensembles and of direct feedback between experiments and simulations is possible. We review the advances in developing these models, their theoretical basis, and current and future applications.

  3. Synthesis and Quantitation of Six Phenolic Amides in Amaranthus spp

    DEFF Research Database (Denmark)

    Pedersen, Hans A; Steffensen, Stine Krogh; 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, we...

  4. Microstructure and Kinetic Rheological Behavior of Amidated and Nonamidated LM Pectin Gels

    NARCIS (Netherlands)

    Lofgren, C.; Guillotin, S.E.; Hermansson, A.M.

    2006-01-01

    The microstructure, kinetics of gelation, and rheological properties have been investigated for gels of nonamidated pectin (C30), amidated pectin (G), and saponified pectin (sG) at different pH values, both with and without sucrose. The low-methoxyl (LM) pectin gels were characterized in the presenc

  5. Synthesis of polypiperazine-amide thin-film membrane on PPESK hollow fiber UF membrane

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A new interfacial polymerization (IP) procedure is developed in order to synthesize polypiperazine-amide thin-film membrane on the inner surface of poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber ultrafiltration (UF) membrane. A hollow fiber composite membrane with good performance was prepared and studied by FT-IR and scanning electron microscopy.

  6. Formation of amide bonds without a condensation agent and implications for origin of life.

    Science.gov (United States)

    Keller, M; Blöchl, E; Wächtershäuser, G; Stetter, K O

    1994-04-28

    Amide bonds are of central importance for biochemistry; in the guise of peptide bonds, they form the backbone of proteins. The formation of amide bonds without the assistance of enzymes poses a major challenge for theories of the origin of life. Enzyme-free formation of amide bonds between amino acids has been demonstrated in the presence of condensing agents such as cyanamide. Here we report the formation of amide bonds in aqueous solution in the absence of any condensing agent. We find that the formation of pyrite (FeS2) from FeS and H2S can provide the driving force for reductive acetylation of amino acids with mercaptoacetic acid (HSCH2COOH). The redox energy of pyrite formation permits the activation of the carboxylic acid group, which is converted to a species that reacts readily with amines. This process provides support for the chemo-autotrophic theory for the origin of life, in which pyrite formation supplies the energy source for the first autocatalytic reproduction cycle.

  7. 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.

  8. Segmented copolymers of uniform tetra-amide units and poly(phenylene oxide) by direct coupling

    NARCIS (Netherlands)

    Krijgsman, J.; Biemond, G.J.E.; Gaymans, R.J.

    2007-01-01

    Segmented copolymers with telechelic poly(2,6-dimethyl-1,4-phenylene ether) (PPE) segments and crystallizable bisester tetra-amide units (two-and-a-half repeating unit of nylon-6,T) were studied. The copolymers were synthesized by reacting bifunctional PPE with hydroxylic end groups with an average

  9. Synthesis and intrinsic blue fluorescence study of hyperbranched poly(ester-amide-ether)

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A series of hyperbranched poly(ester-amide-ether)s (H-PEAEs) were synthesized via the A2+CB3 approach by the self-transesterification of ethyl ester-amide-ethers end-capped with three hydroxyl groups and ethyl ester group at two terminals.The molecular structures were characterized with 1H NMR and FT-IR spectroscopy.The number average molecular weights were estimated by GPC analysis to possess bimodal wide distribution from 1.57 to 2.09.The strong inherent blue fluorescence was observed at 330 nm for excitation and 390 nm for emission.Moreover,the emission intensity and fluorescence quantum yield increased along with the incorporated ether chain length,as well as almost linearly with the H-PEAE concentration in an aqueous solution.For comparing the fluorescence performance,the linear poly(ester-amide-ether) (L-PEAE) and hyperbranched poly(ester-amide) (H-PEA) were synthesized.The results showed that the coexistence of ether bond and carboxyl group in the molecular chain was essential for generating the strong fluorescence.However,the compact backbone of H-PEAE would be propitious to the enhancement of fluorescence properties.

  10. Development of chiral metal amides as highly reactive catalysts for asymmetric [3 + 2] cycloadditions

    Science.gov (United States)

    Yamashita, Yasuhiro; Yoshimoto, Susumu; Dutton, Mark J

    2016-01-01

    Summary Highly efficient catalytic asymmetric [3 + 2] cycloadditions using a chiral copper amide are reported. Compared with the chiral CuOTf/Et3N system, the CuHMDS system showed higher reactivity, and the desired reactions proceeded in high yields and high selectivities with catalyst loadings as low as 0.01 mol %. PMID:27559396

  11. One pot direct synthesis of amides or oxazolines from carboxylic acids using Deoxo-Fluor reagent.

    Science.gov (United States)

    Kangani, Cyrous O; Kelley, David E

    2005-12-19

    A mild and highly efficient one pot-one step condensation and/or condensation-cyclization of various acids to amides and/or oxazolines using Deoxo-Fluor reagents is described. Parallel syntheses of various free fatty acids with 2-amino-2, 2-dimethyl-1-propanol resulted with excellent yields.

  12. Learner Identity Amid Figured Worlds: Constructing (In)competence at an Urban High School

    Science.gov (United States)

    Rubin, Beth C.

    2007-01-01

    This article explores the figured world of learning at urban Oakcity High School, describing the learner identities that were available to students amid the practices, categories, discourses and interactions of this world. My aims are 2-fold and interconnected: (1) to reframe a taken-for-granted phenomenon--that students tend to do poorly at urban…

  13. 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...

  14. Gas-phase acidities of aspartic acid, glutamic acid, and their amino acid amides

    Science.gov (United States)

    Li, Zhong; Matus, Myrna H.; Velazquez, Hector Adam; Dixon, David A.; Cassady, Carolyn J.

    2007-09-01

    Gas-phase acidities (GA or [Delta]Gacid) for the two most acidic common amino acids, aspartic acid and glutamic acid, have been determined for the first time. Because of the amide linkage's importance in peptides and as an aid in studying side chain versus main chain deprotonation, aspartic acid amide and glutamic acid amide were also studied. Experimental GA values were measured by proton transfer reactions in an electrospray ionization/Fourier transform ion cyclotron resonance mass spectrometer. Calculated GAs were obtained by density functional and molecular orbital theory approaches. The best agreement with experiment was found at the G3MP2 level; the MP2/CBS and B3LYP/aug-cc-pVDZ results are 3-4 kcal/mol more acidic than the G3MP2 results. Experiment shows that aspartic acid is more acidic than glutamic acid by ca. 3 kcal/mol whereas the G3MP2 results show a smaller acidity difference of 0.2 kcal/mol. Similarly, aspartic acid amide is experimentally observed to be ca. 2 kcal/mol more acidic than glutamic acid amide whereas the G3MP2 results show a correspondingly smaller energy difference of 0.7 kcal/mol. The computational results clearly show that the anions are all ring-like structures with strong hydrogen bonds between the OH or NH2 groups and the CO2- group from which the proton is removed. The two amino acids are main-chain deprotonated. In addition, use of the COSMO model for the prediction of the free energy differences in aqueous solution gave values in excellent agreement with the most recent experimental values for pKa. Glutamic acid is predicted to be more acidic than aspartic acid in aqueous solution due to differential solvation effects.

  15. Gas-phase Acidities of Aspartic Acid, Glutamic Acid, and their Amino Acid Amides.

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhong; Matus, Myrna H; Velazquez, Hector A; Dixon, David A; Cassady, Carolyn J

    2007-02-14

    Gas-phase acidities (GA or ΔGacid) for the two most acidic common amino acids, aspartic acid and glutamic acid, have been determined for the first time. Because of the amide linkage’s importance in peptides and as an aid in studying side chain versus main chain deprotonation, aspartic acid amide and glutamic acid amide were also studied. Experimental GA values were measured by proton transfer reactions in an electrospray ionization/Fourier transform ion cyclotron resonance mass spectrometer. Calculated GAs were obtained by density functional and molecular orbital theory approaches. The best agreement with experiment was found at the G3MP2 level; the MP2/CBS and B3LYP/aug-cc-pVDZ results are 3–4 kcal/mol more acidic than the G3MP2 results. Experiment shows that aspartic acid is more acidic than glutamic acid by ca. 3 kcal/mol whereas the G3MP2 results show a smaller acidity difference of 0.2 kcal/mol. Similarly, aspartic acid amide is experimentally observed to be ca. 2 kcal/mol more acidic than glutamic acid amide whereas the G3MP2 results show a correspondingly smaller energy difference of 0.7 kcal/mol. The computational results clearly show that the anions are all ring-like structures with strong hydrogen bonds between the OH or NH2 groups and the CO2- group from which the proton is removed. The two amino acids are main-chain deprotonated. In addition, use of the COSMO model for the prediction of the free energy differences in aqueous solution gave values in excellent agreement with the most recent experimental values for pKa. Glutamic acid is predicted to be more acidic than aspartic acid in aqueous solution due to differential solvation effects.

  16. 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.

  17. 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

    2015-03-01

    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.

  18. Uncovering the Sensitivity of Amide-II Vibration to Peptide-Ion Interactions.

    Science.gov (United States)

    Zhao, Juan; Wang, Jianping

    2016-09-15

    In this work, linear infrared spectroscopy was used to examine the effect of salt on the amide-II mode in a model β-peptide (N-ethylpropionamide, NEPA) in its deuterated form, to reveal the sensitivity of this mode in reporting peptide-ion interactions. In comparison to the case of NEPA in water, the amide-II spectra mainly showed a red-shifted component in four typical saline solutions (NaCl, CaCl2, MgCl2, and AlCl3) examined in this work. Our results suggest that highly populated hydrated ion complexes under high salt concentration conditions destroy the hydration layer of the model peptide and result in mostly a salting-out state of the peptide. Molecular dynamics simulations suggest that the hydrated cation mainly interacts with the peptide backbone on the amide C═O side, whereas the hydrated anion interacts on the amide N-H side. As the amide-II mode is mainly a combination of the C-N stretching and N-H in-plane-bending vibrations, this mode is advantageous in being responsive to ionic interaction from both the C═O and N-H sides. Such a dual sensitivity should be very useful in probing the breaking and/or formation of the interamide hydrogen bond between the C═O and N-H groups, which is a very important interaction involved in the solvation and stabilization, as well as folding/unfolding of proteins.

  19. 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

    2015-06-16

    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'-(13)C-2-(15)N-labeled and 2'-(13)C-2-(15)N-labeled SMs were prepared, and the rotational-axis direction and order parameters of the SM amide in bilayers were determined based on (13)C and (15)N chemical-shift anisotropies and intramolecular (13)C-(15)N 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.

  20. Structural insights into the specific recognition of N-heterocycle biodenitrogenation-derived substrates by microbial amide hydrolases.

    Science.gov (United States)

    Wu, Geng; Chen, Duoduo; Tang, Hongzhi; Ren, Yiling; Chen, Qihua; Lv, Yang; Zhang, Zhenyi; Zhao, Yi-Lei; Yao, Yuxiang; Xu, Ping

    2014-03-01

    N-heterocyclic compounds from industrial wastes, including nicotine, are environmental pollutants or toxicants responsible for a variety of health problems. Microbial biodegradation is an attractive strategy for the removal of N-heterocyclic pollutants, during which carbon-nitrogen bonds in N-heterocycles are converted to amide bonds and subsequently severed by amide hydrolases. Previous studies have failed to clarify the molecular mechanism through which amide hydrolases selectively recognize diverse amide substrates and complete the biodenitrogenation process. In this study, structural, computational and enzymatic analyses showed how the N-formylmaleamate deformylase Nfo and the maleamate amidase Ami, two pivotal amide hydrolases in the nicotine catabolic pathway of Pseudomonas putida S16, specifically recognize their respective substrates. In addition, comparison of the α-β-α groups of amidases, which include Ami, pinpointed several subgroup-characteristic residues differentiating the two classes of amide substrates as containing either carboxylate groups or aromatic rings. Furthermore, this study reveals the molecular mechanism through which the specially tailored active sites of deformylases and amidases selectively recognize their unique substrates. Our work thus provides a thorough elucidation of the molecular mechanism through which amide hydrolases accomplish substrate-specific recognition in the microbial N-heterocycles biodenitrogenation pathway.

  1. Self-assembly and antimicrobial activity of long-chain amide-functionalized ionic liquids in aqueous solution.

    Science.gov (United States)

    Garcia, M Teresa; Ribosa, Isabel; Perez, Lourdes; Manresa, Angeles; Comelles, Francesc

    2014-11-01

    Surface active amide-functionalized ionic liquids (ILs) consisting of a long alkyl chain (C6C14) connected to a polar head group (methylimidazolium or pyridinium cation) via an amide functional group were synthesized and their thermal stability, micellar properties and antimicrobial activity in aqueous solution investigated. The incorporation of an amide group increased the thermal stability of the functionalized ionic liquids compared to simple alkyl chain substituted ionic liquids. The surface activity and aggregation behaviour in aqueous solution of amide-functionalized ionic liquids were examined by tensiometry, conductivity and spectrofluorimetry. Amide-functionalized ILs displayed surface activity and their critical micelle concentration (cmc) in aqueous media decreased with the elongation of the alkyl side chain as occurs for typical surfactants. Compared to non-functionalized ILs bearing the same alkyl chain, ionic liquids with an amide moiety possess higher surface activity (pC20) and lower cmc values. The introduction of an amide group in the hydrophobic chain close to the polar head enhances adsorption at the air/water interface and micellization which could be attributed to the H-bonding in the headgroup region. The antimicrobial activity was evaluated against a panel of representative Gram-negative and Gram-positive bacteria and fungi. Amide-functionalized ILs with more than eight carbon atoms in the side chain showed broad antimicrobial activity. Antibacterial activities were found to increase with the alkyl chain length being the C12 homologous the most effective antimicrobial agents. The introduction of an amide group enhanced significantly the antifungal activity as compared to non-functionalized ILs.

  2. Structure-based interpretation of biotransformation pathways of amide-containing compounds in sludge-seeded bioreactors.

    Science.gov (United States)

    Helbling, Damian E; Hollender, Juliane; Kohler, Hans-Peter E; Fenner, Kathrin

    2010-09-01

    Partial microbial degradation of xenobiotic compounds in wastewater treatment plants (WWTPs) results in the formation of transformation products, which have been shown to be released and detectable in surface waters. Rule-based systems to predict the structures of microbial transformation products often fail to discriminate between alternate transformation pathways because structural influences on enzyme-catalyzed reactions in complex environmental systems are not well understood. The amide functional group is one such common substructure of xenobiotic compounds that may be transformed through alternate transformation pathways. The objective of this work was to generate a self-consistent set of biotransformation data for amide-containing compounds and to develop a metabolic logic that describes the preferred biotransformation pathways of these compounds as a function of structural and electronic descriptors. We generated transformation products of 30 amide-containing compounds in sludge-seeded bioreactors and identified them by means of HPLC-linear ion trap-orbitrap mass spectrometry. Observed biotransformation reactions included amide hydrolysis and N-dealkylation, hydroxylation, oxidation, ester hydrolysis, dehalogenation, nitro reduction, and glutathione conjugation. Structure-based interpretation of the results allowed for identification of preferences in biotransformation pathways of amides: primary amides hydrolyzed rapidly; secondary amides hydrolyzed at rates influenced by steric effects; tertiary amides were N-dealkylated unless specific structural moieties were present that supported other more readily enzyme-catalyzed reactions. The results allowed for the derivation of a metabolic logic that could be used to refine rule-based biotransformation pathway prediction systems to more specifically predict biotransformations of amide-containing compounds.

  3. 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.

  4. 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.

  5. 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

    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......M. Thus, both amidated and glycine-extended GLP-I molecules are produced in the small intestine and in the pancreas in humans. Both amidated and glycine-extended GLP-I are measurable in fasting plasma.(ABSTRACT TRUNCATED AT 250 WORDS)...

  6. 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

    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...

  7. Novel endogenous N-acyl amides activate TRPV1-4 receptors, BV-2 microglia, and are regulated in brain in an acute model of inflammation

    Directory of Open Access Journals (Sweden)

    Siham eRaboune

    2014-08-01

    Full Text Available 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.

  8. 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.

  9. Antifungal agents. 4. Chemical modification of antibiotics from Polyangium cellulosum var. fulvum. Ester and amide analogues of ambruticin.

    Science.gov (United States)

    Connor, D T; von Strandtmann, M

    1979-09-01

    A series of ester and amide analogues of ambruticin (1) was prepared. The analogues were tested against Histoplasma capsulatum, Microsporum fulvum, Candida albicans and Streptococcus pyogenes. Structure-activity relationships are described.

  10. 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.

  11. High sensitivity of amide V bands in uracil and its derivatives to the strengths of hydrogen bonding

    Science.gov (United States)

    Bandekar, Jagdeesh; Zundel, Georg

    Bands due to CO, CH and NH out-of-plane bending modes have been identified and studied as a function of temperature in the cis-amide uracil and its derivatives. Only the bands due to NH out-of-plane bending modes, the so-called amide V bands, are found to be sensitive to the strengths of hydrogen bonds. This sensitivity is found to be as great as that of NH stretching bands. It is shown that the amide V bands could be used, among other things, to detect the possibility and/or extent of hydrogen bonding in Hoogsteen-type base-pairs. This provides a very simple way to detect the presence of undesirable uncomplexed bases in the study of base-paired complexes. These results point to the need to understand better the origin of amide V bands.

  12. Is there any difference in Amide and NOE CEST effects between white and gray matter at 7 T?

    Science.gov (United States)

    Khlebnikov, Vitaliy; Siero, Jeroen C. W.; Wijnen, Jannie; Visser, Fredy; Luijten, Peter R.; Klomp, Dennis W. J.; Hoogduin, Hans

    2016-11-01

    Measurement of Chemical Exchange Saturation Transfer (CEST) is providing tissue physiology dependent contrast, e.g. by looking at Amide and NOE (Nuclear Overhauser Enhancement) effects. CEST is unique in providing quantitative metabolite information at high imaging resolution. However, direct comparison of Amide and NOE effects between different tissues may result in wrong conclusions on the metabolite concentration due to the additional contributors to the observed CEST contrast, such as water content (WC) and water T1 relaxation (T1w). For instance, there are multiple contradictory reports in the literature on Amide and NOE effects in white matter (WM) and gray matter (GM) at 7 T. This study shows that at 7 T, tissue water T1 relaxation is a stronger contributor to CEST contrasts than WC. After water T1 correction, there was no difference in Amide effects between WM and GM, whereas WM/GM contrast was enhanced for NOE effects.

  13. 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.

  14. β-Amino functionalization of cinnamic Weinreb amides in ionic liquid

    Directory of Open Access Journals (Sweden)

    Yi-Ning Wang

    2016-11-01

    Full Text Available 2-Ns-Protected β-amino Weinreb amides were synthesized by aminochlorination of α,β-unsaturated Weinreb amides in an ionic liquid, 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonylimide ([BMIM][NTf2]. Processed without the use of metal catalysts or the need of an inert gas atmosphere, the presented process can be readily performed as a one-pot synthesis at room temperature. Moreover, the preparation has the distinct advantages of the use of 2-NsNCl2 as an inexpensive and stable nitrogen/halogen source and the ionic liquid as a recyclable reaction media. Nine examples were examined, and modest to good isolated chemical yields (40–83% were obtained.

  15. 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.

  16. 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...... 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...... not show any significant differences in reactivity, which indicates that the same catalytically active species is operating. The reaction is believed to proceed by initial dehydrogenation of the primary alcohol to the aldehyde that stays coordinated to ruthenium and is not released into the reaction...

  17. Mechanism of arylboronic acid-catalyzed amidation reaction between carboxylic acids and amines.

    Science.gov (United States)

    Wang, Chen; Yu, Hai-Zhu; Fu, Yao; Guo, Qing-Xiang

    2013-04-07

    Arylboronic acids were found to be efficient catalysts for the amidation reactions between carboxylic acids and amines. Theoretical calculations have been carried out to investigate the mechanism of this catalytic process. It is found that the formation of the acyloxyboronic acid intermediates from the carboxylic acid and the arylboronic acid is kinetically facile but thermodynamically unfavorable. Removal of water (as experimentally accomplished by using molecular sieves) is therefore essential for overall transformation. Subsequently C-N bond formation between the acyloxyboronic acid intermediates and the amine occurs readily to generate the desired amide product. The cleavage of the C-O bond of the tetracoordinate acyl boronate intermediates is the rate-determining step in this process. Our analysis indicates that the mono(acyloxy)boronic acid is the key intermediate. The high catalytic activity of ortho-iodophenylboronic acid is attributed to the steric effect as well as the orbital interaction between the iodine atom and the boron atom.

  18. Preparation and characterization of amidated pectin based hydrogels for drug delivery system.

    Science.gov (United States)

    Mishra, R K; Datt, M; Pal, K; Banthia, A K

    2008-06-01

    In the current studies attempts were made to prepare hydrogels by chemical modification of pectin with ethanolamine (EA) in different proportions. Chemically modified pectin products were crosslinked with glutaraldehyde reagent for preparing hydrogels. The hydrogels were characterized by Fourier transform infrared spectroscopy (FTIR), organic elemental analysis, X-ray diffraction studies (XRD), swelling studies, biocompatibility and hemocompatibility studies. Mechanical properties of the prepared hydrogels were evaluated by tensile test. The hydrogels were loaded with salicylic acid (used as a model drug) and drug release studies were done in a modified Franz's diffusion cell. FTIR spectroscopy indicated the presence of primary and secondary amide absorption bands. XRD studies indicated increase in crystallinity in the hydrogels as compared to unmodified pectin. The degree of amidation (DA) and molar and mass reaction yields (YM and YN) was calculated based on the results of organic elemental analysis. The hydrogels showed good water holding properties and were found to be compatible with B-16 melanoma cells & human blood.

  19. Synthesis, Characterization and Properties of Amide Anions Based Ionic Liquids Containing Nitrile Group

    Institute of Scientific and Technical Information of China (English)

    ZOU Ting; LU Liang; LIU Xiuli; ZHANG Zhan; XUE Yunrong; YANG Yu; Li Caimeng; FU Xianlei; GAO Guohua

    2009-01-01

    A series of novel amide anion based ionic liquids containing nitrile groups have been synthesized using the method of ion-exchange between potassium amide and various quaternary halide salts such as trimethylamine,triethylamine,tributylamine,N-methylpyrrolidine,and N-methylimidazole.All of the functionalised ionic liquids were characterized by IR,1H and 13C NMR,and MS.The synthesized ionic liquids exhibited advantageously high thermal stability.The decomposition temperature of ionic liquids measured via TGA ranged from 224 to 289 ℃.The functionalised ionic liquid,l-ethyl-3-methylimidazolium propionyl cyanamide ([EMIm][N(CN)COC2H5]),was used as a ligand in the palladium catalyzed Suzuki coupling reaction.The yields of the coupling reaction increased by 10%-20% by the addition of [EMIm]IN(CN)COC2H5].

  20. Benzoxazole and benzothiazole amides as novel pharmacokinetic enhancers of HIV protease inhibitors.

    Science.gov (United States)

    Jonckers, Tim H M; Rouan, Marie-Claude; Haché, Geerwin; Schepens, Wim; Hallenberger, Sabine; Baumeister, Judith; Sasaki, Jennifer C

    2012-08-01

    A new class of benzoxazole and benzothiazole amide derivatives exhibiting potent CYP3A4 inhibiting properties was identified. Extensive lead optimization was aimed at improving the CYP3A4 inhibitory properties as well as overall ADME profile of these amide derivatives. This led to the identification of thiazol-5-ylmethyl (2S,3R)-4-(2-(ethyl(methyl)amino)-N-isobutylbenzo[d]oxazole-6-carboxamido)-3-hydroxy-1-phenylbutan-2-ylcarbamate (C1) as a lead candidate for this class. This compound together with structurally similar analogues demonstrated excellent 'boosting' properties when tested in dogs. These findings warrant further evaluation of their properties in an effort to identify valuable alternatives to Ritonavir as pharmacokinetic enhancers.

  1. 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.

  2. Diverging Novobiocin Anti-Cancer Activity from Neuroprotective Activity through Modification of the Amide Tail.

    Science.gov (United States)

    Ghosh, Suman; Liu, Yang; Garg, Gaurav; Anyika, Mercy; McPherson, Nolan T; Ma, Jiacheng; Dobrowsky, Rick T; Blagg, Brian S J

    2016-08-11

    Novobiocin is a natural product that binds the Hsp90 C-terminus and manifests Hsp90 inhibitory activity. Structural investigations on novobiocin led to the development of both anti-cancer and neuroprotective agents. The varied pharmacological activity manifested by these novobiocin analogs prompted the investigation of structure-function studies to identify these contradictory effects, which revealed that modifications to the amide side chain produce either anti-cancer or neuroprotective activity. Compounds that exhibit neuroprotective activity contain a short alkyl or cycloalkyl amide side chain. In contrast, anti-cancer agents contain five or more carbons, disrupt interactions between Hsp90α and Aha1, and induce the degradation of Hsp90-dependent client proteins.

  3. Temperature-Dependence of the Amide-I Frequency Map for Peptides and Proteins

    Institute of Scientific and Technical Information of China (English)

    Chen Han; Jian-ping Wang

    2011-01-01

    In our recent work [Phys.Chem.Chem.Phys.11,9149 (2009)],a molecular-mechanics force field-based amide-I vibration frequency map (MM-map) for peptides and proteins was constructed.In this work,the temperature dependence of the MM-map is examined based on high-temperature molecular dynamics simulations and infrared (IR) experiments.It is shown that the 298-K map works for up to 500-K molecular dynamics trajectories,which reasonably reproduces the 88 ℃ experimental IR results.Linear IR spectra are also simulated for two tripeptides containing natural and unnatural amino acid residues,and the results are in reasonable agreement with experiment.The results suggest the MM-map can be used to obtain the temperature-dependent amide-I local mode frequencies and their distributions for peptide oligomers,which is useful in particular for understanding the IR signatures of the thermally unfolded species.

  4. Synthesis of Poly(aryl amide imide)s Derived from o-diphenyltrimellitic Anhydride

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The synthesis and characterization of a series of novel poly(aryl amide imide)s based on o-diphenyltrimellitic anhydride are described.The poly(aryl amide-imide)s having inherent viscosities of 0.39-1.43dL/g in N-methyl-2-pyrrolidinone at 30℃,were prepared by polymerization with aromatic diamines in N,N-dimethylacetamide and subsequent chemical imidization.All the polymers were amorphous,readily soluble in aprotic polar solvents such as DMAC,NMP,DMF,DMSO,and m-cresol,and could be cast to form flexible and tough films.The glass trsanition temperatures were in the range of 284-336℃,and the temperatures for 5% weight loss in nitrogen were above 468℃.

  5. 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.

  6. 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)

  7. Amides from Piper capense with CNS Activity – A Preliminary SAR Analysis

    Directory of Open Access Journals (Sweden)

    Hasse B. Rasmussen

    2009-09-01

    Full Text Available Piper capense L.f. (Piperaceae is used traditionally in South Africa as a sleep inducing remedy. Bioassay-guided fractionation of the roots of P. capense led to the isolation of piperine (1 and 4,5-dihydropiperine (2, which showed moderate affinity for the benzodiazepine site on the GABAA receptor (IC50 values of 1.2 mM and 1.0 mM, respectively. The present study suggests that strict structural properties of the amides are essential for affinity. Taken together, these observations suggest that the carbon chain must contain not less than four carbons, and that a conjugated double bond, adjacent to the amide group, is necessary for binding to the receptor and that the amine part should be bulky.

  8. 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.

  9. Microwave assisted synthesis and solid-state characterization of lithocholyl amides of isomeric aminopyridines.

    Science.gov (United States)

    Ahonen, Kari V; Lahtinen, Manu K; Valkonen, Arto M; Dracínský, Martin; Kolehmainen, Erkki T

    2011-02-01

    Microwave (MW) assisted synthesis and solid state structural characterizations of novel lithocholyl amides of 2-, 3-, and 4-aminopyridine are reported. It is shown that the MW technique is a proper method in the preparation of N-lithocholyl amides of isomeric aminopyridines. It offers many advantages compared to conventional heating. The molecular and crystal structures as well as the polymorphic and hydrated forms of prepared conjugates with their thermodynamic stabilities have been characterized by means of high resolution liquid- and solid-state NMR spectroscopy, single crystal and powder X-ray diffraction, and thermogravimetric analysis. Owing to the many biological functions of bile acids and amino substituted nitrogen heterocycles, knowledge of the crystal packing of these novel conjugates may have relevance for potential pharmaceutical applications.

  10. Novel hydrazone derivatives containing pyridine amide moiety: Design, synthesis, and insecticidal activity.

    Science.gov (United States)

    Yang, Zai-Bo; Hu, De-Yu; Zeng, Song; Song, Bao-An

    2016-02-15

    A series of novel hydrazone derivatives containing pyridine amide moiety were designed, synthesized, and evaluated for their insecticidal activity. Bioassays indicated that some of the target compounds exhibited good insecticidal activities against Nilaparvata lugens (N. lugens), Plutella xylostella (P. xylostella), Mythimna separata (M. separata), Helicoverpa armigera (H. armigera), Pyrausta nubilalis (P. nubilalis), and Culex pipiens pallens (C. pipiens pallens). In particular, compound 5j revealed excellent insecticidal activity against C. pipiens pallens, with the 50% lethal concentration (LC50) and the 95% lethal concentration (LC95) values of 2.44 and 5.76 mg/L, respectively, which were similar to those of chlorpyrifos (3.26 and 6.98 mg/L, respectively), tebufenozide (1.22 and 2.49 mg/L, respectively), and RH-5849 (2.61 and 6.37 mg/L, respectively). These results indicated that hydrazone derivatives containing pyridine amide moiety could be developed as novel and promising insecticides.

  11. Iron(II) cage complexes of N-heterocyclic amide and bis(trimethylsilyl)amide ligands: synthesis, structure, and magnetic properties.

    Science.gov (United States)

    Sulway, Scott A; Collison, David; McDouall, Joseph J W; Tuna, Floriana; Layfield, Richard A

    2011-03-21

    Metallation of hexahydropyrimidopyrimidine (hppH) by [Fe{N(SiMe(3))(2)}(2)] (1) produces the trimetallic iron(II) amide cage complex [{(Me(3)Si)(2)NFe}(2)(hpp)(4)Fe] (2), which contains three iron(II) centers, each of which resides in a distorted tetrahedral environment. An alternative, one-pot route that avoids use of the highly air-sensitive complex 1 is described for the synthesis of the iron(II)-lithium complex [{(Me(3)Si)(2)N}(2)Fe{Li(bta)}](2) (3) (where btaH = benzotriazole), in which both iron(II) centers reside in 3-coordinated pyramidal environments. The structure of 3 is also interpreted in terms of the ring laddering principle developed for alkali metal amides. Magnetic susceptibility measurements reveal that both compounds display very weak antiferromagnetic exchange between the iron(II) centers, and that the iron(II) centers in 2 and 3 possess large negative axial zero-field splittings.

  12. A mechanistic study on the amidation of esters mediated by sodium formamide.

    Science.gov (United States)

    Ramirez, Antonio; Mudryk, Boguslaw; Rossano, Lucius; Tummala, Srinivas

    2012-01-06

    Kinetic and computational studies on the amidation of esters with mixtures of formamide and sodium methoxide are described. Rate studies are consistent with a fast deprotonation of formamide followed by two reversible acyl transfers affected by solvent participation. MP2 calculations suggest that the first acyl transfer between the ester and sodium formamide is rate-determining. The transition structures leading to the formation and collapse of the first tetrahedral intermediate are calculated to be isoenergetic.

  13. End-Crosslinking Gelation of Poly(amide acid) Gels studied with Scanning Microscopic Light Scattering

    OpenAIRE

    Furukawa, Hidemitsu; Kobayashi, Mizuha; Miyashita, Yoshiharu; HORIE, Kazuyuki

    2006-01-01

    Network formation in the gelation process of end-crosslinked poly(amide acid) gels, which are the precursor of end-crosslinked polyimide gels, was studied by scanning dynamic light scattering. The gelation process is essentially non-reversible due to the formation of covalent bonds. The molecular structure formed in the gelation process is controlled by varying the equivalence ratio of end-crosslinker to oligomer during the preparation. It was found that a couple of relaxation modes are obser...

  14. Synthesis and Absorption Properties of Calix[6]amides-based Polymers

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Reacting calix[6]arene hexaesters with poly(ethyleneimine), a series of calix [6]amides- based polymers were obtained for the first time.It is found that they show high absorption capacities towards soft cations comparing to hard cations, and the absorption abilities enhanced with the increasing of calixarene content, which may indicates the cavity of calixarene plays crucial role in absorption.Polymer 2c shows good selective absorption capability towards Ag+ among the tested cations.

  15. Selective Colorimetric Fluoride Sensor: A Heteroditopic Re-ceptor Combining Pyrrolic Amide with Urea

    Institute of Scientific and Technical Information of China (English)

    YIN Zhenming; LIU Shangyuan

    2009-01-01

    A heteroditopic anion receptor, beating one pyrrolic amide site and a urea site, has been synthesized. UV-Vis spectrum studies in CH3CN solution revealed that the receptor had higher anion binding ability than the homoditopic one. A naked-eye detectable color change, from colorless to yellow, of the receptor solution took place when fluoride was added, which indicates that the receptor has potential application to selective colorimetric fluo-ride sensing.

  16. Settlement of Internal Cutthroat Competition Amid IT Group Companies: Away from "Prisoners' Dilemma" of Price Wars

    Institute of Scientific and Technical Information of China (English)

    CHEN Chao-long

    2006-01-01

    Cutthroat competition amid subsidiary companies of IT Group Company due to immanent characteristics of IT industry and grouping management mechanism infringes upon the collective profits. Two ways to avoid cutthroat competition of group company with game theory are studied: the assessment objective made by IT group company for subsidiary companies focuses on profits not revenue;the supervisory department of group company shall intensify law enforcement strength and give severe punishment against illegal depreciation of the subsidiary company.

  17. Chiral amide from (1, 2)-(+)-norephedrine and furoic acid: An efficient catalyst for asymmetric Reformatsky reaction

    Indian Academy of Sciences (India)

    Nallamuthu Ananthi; Sivan Velmathi

    2014-01-01

    Chiral amide derived from (1, 2)-(+)-norephedrine and 2-furoic acid was found to catalyse the asymmetric Reformatsky reaction between prochiral aldehydes and α-bromo ethylacetate with diethylzinc as zinc source. The corresponding chiral -hydroxy esters were formed in 99% yield with over 80% enantiomeric excess. The presence of air was found to be essential for the effective C-C bond formation. The mechanism for the catalytic reaction was proposed.

  18. Anti-proliferative activity of Monensin and its tertiary amide derivatives.

    Science.gov (United States)

    Huczyński, Adam; Klejborowska, Greta; Antoszczak, Michał; Maj, Ewa; Wietrzyk, Joanna

    2015-10-15

    New tertiary amide derivatives of polyether ionophore Monensin A (MON) were synthesised and their anti-proliferative activity against cancer cell lines was studied. Very high activity (IC50=0.09 μM) and selectivity (SI=232) of MON against human biphenotypic myelomonocytic leukemia cell line (MV4-11) was demonstrated. The MON derivatives obtained exhibit interesting anti-proliferative activity, high selectivity index and also are able to break the drug-resistance of cancer cell line.

  19. New improved thermosets obtained from DGEBA and a hyperbranched poly(ester-amide)

    OpenAIRE

    Morell, Mireia; Ramis Juan, Xavier; Ferrando Piera, Francesc; Yu, Yingfeng; Serra Albet, Àngels

    2009-01-01

    The influence on the curing process of a commercial hydroxy-functionalized hyperbranched poly(ester-amide) (HBP) Hybrane® S1200 on diglycidylether of bisphenol A (DGEBA) was studied. By Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR) the curing reaction was studied and the covalent incorporation of the modifier in the matrix was proved. By Thermomechanical Analysis (TMA) the reduction of the contraction after gelation on changing the S1200 proportio...

  20. Synthesis and Properties of Lactic Acid-based Cross-linked Poly(ester-amide)

    Institute of Scientific and Technical Information of China (English)

    Yue Ying HE; Cong Ming XIAO

    2006-01-01

    A novel lactic acid-based cross-linked poly(ester-amide) (LCPEA) was synthesized. The gel fraction of the LCPEA could be modulated by the reaction conditions and it affected the mechanical and thermal properties of the LCPEA. The tensile strength, elastic modulus and bend strength of the LCPEA of 65% gel fraction were 4.65, 136.55 and 39.63 MPa, respectively. The thermal decomposition temperature (50 wt%) of the LCPEA was around 410 ℃.

  1. 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.

  2. A new route to indazolone via amidation reaction of o-carboxyazobenzene.

    Science.gov (United States)

    Li, Chengjie; Zhang, Tianyi; Zeng, Zhe; Liu, Xiujun; Zhao, Yunfeng; Zhang, Bao; Feng, Yaqing

    2012-01-20

    One new route for the synthesis of amino-substituted indazol-3,5-dione via the amidation reaction of o-carboxyazobenzenes is reported. Optimization which includes effects of the solvents, molar ratio of starting materials, and dehydrating agents on this reaction has been studied. A possible reaction mechanism has been proposed on the basis of the product's structure, and the steric hindrance could be the main reason for low yield.

  3. Synthesis, structural and conformational study of some amides derived from N-methylpiperazine

    Science.gov (United States)

    Iriepa, I.; Madrid, A. I.; Gálvez, E.; Bellanato, J.

    2006-04-01

    Some amides ( 1- 6) derived from N-methylpiperazine were synthesized and studied by IR, 1H and 13C NMR spectroscopy. In CDCl 3 solution, at room temperature, a fast interconversion of the piperazine ring with the N-CH 3 group in equatorial position can be proposed. α,β-unsaturated compounds 4 and 5 adopt in liquid state and in solution (CCl 4, CCl 2dbnd6 CCl 2, CDCl 3) both s- cis and s- trans conformations.

  4. 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.

  5. Inferential protein structure determination and refinement using fast, electronic structure based backbone amide chemical shift predictions

    CERN Document Server

    Christensen, Anders S

    2015-01-01

    This report covers the development of a new, fast method for calculating the backbone amide proton chemical shifts in proteins. Through quantum chemical calculations, structure-based forudsiglese the chemical shift for amidprotonen in protein has been parameterized. The parameters are then implemented in a computer program called Padawan. The program has since been implemented in protein folding program Phaistos, wherein the method andvendes to de novo folding of the protein structures and to refine the existing protein structures.

  6. Arg-Phe-amide-like peptides in the primitive nervous systems of coelenterates

    DEFF Research Database (Denmark)

    Grimmelikhuijzen, C J; Ebbesen, Ditte Graff

    1985-01-01

    By using immunocytochemistry and radioimmunoassays, several substances resembling vertebrate or invertebrate neuropeptides have been found in the nervous systems of coelenterates. The most abundant neuropeptides were those related to the molluscan neuropeptide Phe-Met-Arg-Phe-amide (FMRFamide......). Of antisera against different fragments of FMRFamide, those against RFamide were superior in recognizing the coelenterate peptide. Incubation of whole mounts with these RFamide antisera visualized the coelenterate nervous system in such a detail as has previously not been possible. By using a radioimmunoassay...

  7. Synthesis of 2, 6-(substituded) pyridine Derivatives Using Amide and Imine Groups

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A new ‘two-armed' acyclic diamide Ⅰa 2, 6-bis(1-ethanecarbozamido-2-amino)pyridine,and a new series of aromatic aldehyde schiff bases containing pyridine ring and amide bridge, Ⅱa-f,were prepared. The compounds were characterized by elemental analysis, IR, 1HNMR and MS.The bioactivity half inhibitory concentration C1/2 is given.

  8. Oxazoline-Promoted Rh-Catalyzed C-H Amidation of Benzene Derivatives with Sulfonamides and Trifluoroacetamide. A Comparative Study.

    Science.gov (United States)

    Maiden, Tracy M M; Swanson, Stephen; Procopiou, Panayiotis A; Harrity, Joseph P A

    2016-11-18

    A Rh-catalyzed ortho-amidation of 2-aryloxazolines offers an efficient and direct route to a range of sulfonamides. The scope of the reaction is very broad with respect to sulfonamide substrate, but the position and electronic nature of the substituents on the aryl moiety of the oxazoline lead to a surprising modulation of reactivity. The reactivity of sulfonamides in comparison to trifluoroacetamide is compared, the latter undergoing Rh-catalyzed amidation more rapidly.

  9. Conformational isomerization of N-(naphthalen-1-yl)-N-(phenyl(quinolin-3-yl)methyl)amide derivatives

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A series of N-(naphthalen-1-yl)-N-(phenyl(quinolin-3-yl)methyl)amide derivatives were designed and synthesized as anti-Mycobacterium tuberculosis drugs. NMR spectra showed that two conformational isomers of these compounds exist in solution,which is not due to cis-trans isomerization of amide bond. We proposed that the spatial interactions between three large aromatic groups caused the conformational isomerization,which was supported by molecular modeling and X-ray diffraction.

  10. 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

  11. Structure and property of self-assemble valinyl bolaform amides having different chirality.

    Science.gov (United States)

    Doi, M; Asano, A; Yoshida, H; Inouguchi, M; Iwanaga, K; Sasaki, M; Katsuya, Y; Taniguchi, T; Yamamoto, D

    2005-10-01

    Bolaform amides were designed from N,N'-bis(carboethoxy-L-valinyl)-diaminoethane (1) by linking t-butyloxycarbonyl-valine through ethylenediamine (EDA) to enable spectroscopic and X-ray diffraction analyses. N,N'-Bis(Boc-L-valinyl)-diaminoethane (2) and N,N'-bis(Boc-D-valinyl)-diaminoethane (3) were composed of L-Val and D-Val, respectively. N-(Boc-L-valinyl)-N'-(Boc-D-valinyl)-diaminoethane (4) was composed of both L-Val and D-Val, and was achiral (meso-peptide). Peptide 5 was a 1:1 mixture of 2 and 3, and was also achiral (racemate). These peptides mediated gelation of corn oil at a concentration of approximately 1%. Within crystals, the peptides formed beta-sheet ribbons, but differences were observed in hydrogen-bonding patterns and side-chain arrangements. These differences were also deduced from temperature dependence of amide protons. Force-field calculations based on the crystal structures indicated that association of beta-sheet ribbons had energy benefits, and it was assumed that molecular aggregation progressed spontaneously. These structural studies indicated the chirality of amino acids affected for the properties of bolaform amides.

  12. Amides from Piper nigrum L. with dissimilar effects on melanocyte proliferation in-vitro.

    Science.gov (United States)

    Lin, Zhixiu; Liao, Yonghong; Venkatasamy, Radhakrishnan; Hider, Robert C; Soumyanath, Amala

    2007-04-01

    Melanocyte proliferation stimulants are of interest as potential treatments for the depigmentary skin disorder, vitiligo. Piper nigrum L. (Piperaceae) fruit (black pepper) water extract and its main alkaloid, piperine (1), promote melanocyte proliferation in-vitro. A crude chloroform extract of P. nigrum containing piperine was more stimulatory than an equivalent concentration of the pure compound, suggesting the presence of other active components. Piperine (1), guineensine (2), pipericide (3), N-feruloyltyramine (4) and N-isobutyl-2E, 4E-dodecadienamide (5) were isolated from the chloroform extract. Their activity was compared with piperine and with commercial piperlongumine (6) and safrole (7), and synthetically prepared piperettine (8), piperlonguminine (9) and 1-(3, 4-methylenedioxyphenyl)-decane (10). Compounds 6-10 either occur in P. nigrum or are structurally related. Compounds 1, 2, 3, 8 and 9 stimulated melanocyte proliferation, whereas 4, 5, 6, 7 and 10 did not. Comparison of structures suggests that the methylenedioxyphenyl function is essential for melanocyte stimulatory activity. Only those compounds also possessing an amide group were active, although the amino component of the amide group and chain linking it to the methylenedioxyphenyl group can vary. P. nigrum, therefore, contains several amides with the ability to stimulate melanocyte proliferation. This finding supports the traditional use of P. nigrum extracts in vitiligo and provides new lead compounds for drug development for this disease.

  13. Menkes protein contributes to the function of peptidylglycine alpha-amidating monooxygenase.

    Science.gov (United States)

    Steveson, Tami C; Ciccotosto, Giuseppe D; Ma, Xin-Ming; Mueller, Gregory P; Mains, Richard E; Eipper, Betty A

    2003-01-01

    Menkes protein (ATP7A) is a P-type ATPase involved in copper uptake and homeostasis. Disturbed copper homeostasis occurs in patients with Menkes disease, an X-linked disorder characterized by mental retardation, neurodegeneration, connective tissue disorders, and early childhood death. Mutations in ATP7A result in malfunction of copper-requiring enzymes, such as tyrosinase and copper/zinc superoxide dismutase. The first step of the two-step amidation reaction carried out by peptidylglycine alpha-amidating monooxygenase (PAM) also requires copper. We used tissue from wild-type rats and mice and an ATP7A-specific antibody to determine that ATP7A is expressed at high levels in tissues expressing high levels of PAM. ATP7A is largely localized to the trans Golgi network in pituitary endocrine cells. The Atp7a mouse, bearing a mutation in the Atp7a gene, is an excellent model system for examining the consequences of ATP7A malfunction. Despite normal levels of PAM protein, levels of several amidated peptides were reduced in pituitary and brain extracts of Atp7a mice, demonstrating that PAM function is compromised when ATP7A is inactive. Based on these results, we conclude that a reduction in the ability of PAM to produce bioactive end-products involved in neuronal growth and development could contribute to many of the biological effects associated with Menkes disease.

  14. 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.

  15. Synthesis and thermal degradation characterization of novel poly(phosphazene-aryl amides

    Directory of Open Access Journals (Sweden)

    Z. P. Zhao

    2012-04-01

    Full Text Available New fully aromatic poly(phosphazene-aryl amides were prepared by polycondensation reaction of our synthesized aromatic diamine: 1,1,3,5-tetraphenoxy-4,6-bis(4-aminophenoxyoligocyclotriphosphazene (monomer 1 with terephthaloyl dichloride. Their chemical structure and composition were characterized by elemental analysis, 1H and 31P NMR (Nuclear Magnetic Resonance, and FT-IR (Fourier transform infrared spectroscopy, whereas their thermal degradation properties were determined by DSC (Differential Scanning Calorimetry and TGA (Thermal Gravimertic Analysis techniques. The solid residues of all samples were analysed by FT-IR and SEM (Scanning Electron Microscopy. Compared to conventional PPTA (poly(p-phenylene terephthamide, PPAA (poly(phosphazene-aryl amide shows excellent thermal stability and solubility in polar protic solvents. All poly(phosphazene-aryl amides show two thermal degradation in the temperature range 150–600°C. The monomer 1, due to its structure, shows the first maximum rate of thermal decomposition temperature around 150–350°C, which may be due to the decomposition of the P–O–C bone. Morphology of the solid residues by Scanning Electron Microscope exhibit that the granular of the solid residues gradual disappearance with the increase of monomer 1 content. The surface layer of PPAA solid residues has been grumous, for the syneresis of P–O–P took place.

  16. Temperature dependence of amino acid side chain IR absorptions in the amide I' region.

    Science.gov (United States)

    Anderson, Benjamin A; Literati, Alex; Ball, Borden; Kubelka, Jan

    2014-05-01

    Amide I' IR spectra are widely used for studies of structural changes in peptides and proteins as a function of temperature. Temperature dependent absorptions of amino acid side-chains that overlap the amide I' may significantly complicate the structural analyses. While the side-chain IR spectra have been investigated previously, thus far their dependence on temperature has not been reported. Here we present the study of the changes in the IR spectra with temperature for side-chain groups of aspartate, glutamate, asparagine, glutamine, arginine, and tyrosine in the amide I' region (in D2O). Band fitting analysis was employed to extract the temperature dependence of the individual spectral parameters, such as peak frequency, integrated intensity, band width, and shape. As expected, the side-chain IR bands exhibit significant changes with temperature. The majority of the spectral parameters, particularly the frequency and intensity, show linear dependence on temperature, but the direction and magnitude vary depending on the particular side-chain group. The exception is arginine, which exhibits a distinctly nonlinear frequency shift with temperature for its asymmetric CN3H5(+) bending signal, although a linear fit can account for this change to within ~1/3 cm(-1). The applicability of the determined spectral parameters for estimations of temperature-dependent side-chain absorptions in peptides and proteins are discussed.

  17. 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.

  18. Role of an amide bond for self-assembly of surfactants.

    Science.gov (United States)

    Bordes, Romain; Tropsch, Juergen; Holmberg, Krister

    2010-03-01

    Self-assembly in solution and adsorption at the air-water interface and at solid surfaces were investigated for two amino-acid-based surfactants with conductimetry, NMR, tensiometry, quartz crystal microbalance with monitoring of the dissipation (QCM-D), and surface plasmon resonance (SPR). The surfactants studied were sodium N-lauroylglycinate and sodium N-lauroylsarcosinate, differing only in a methyl group on the amide nitrogen for the sarcosinate. Thus, the glycinate but not the sarcosinate surfactant is capable of forming intermolecular hydrogen bonds via the amide group. It was found that the amide bond, N-methylated or not, gave a substantial contribution to the hydrophilicity of the amphiphile. The ability to form intermolecular hydrogen bonds led to tighter packing at the air-water interface and at a hydrophobic surface. It also increased the tendency for precipitation as an acid-soap pair on addition of acid. Adsorption of the surfactants at a gold surface was also investigated and gave unexpected results. The sarcosine-based surfactant seemed to give bilayer adsorption, while the glycine derivative adsorbed as a monolayer.

  19. First synthesis and structural determination of a monomeric, unsolvated lithium amide, LiNH(2).

    Science.gov (United States)

    Grotjahn, D B; Sheridan, P M; Al Jihad, I; Ziurys, L M

    2001-06-13

    Alkali metal amides typically aggregate in solution and the solid phase, and even in the gas phase. In addition, even in the few known monomeric structures, the coordination number of the alkali metal is raised by binding of Lewis-basic solvent molecules, with concomitant changes in structure. In contrast, the simplest lithium amide LiNH(2) has never been made in a monomeric form, even though its structure has been theoretically predicted several times. Here, the first experimental structural data for a monomeric, unsolvated lithium amide are determined using a combination of gas-phase synthesis and millimeter/submillimeter-wave spectroscopy. All data point to a planar structure for LiNH(2). The r(o) structure of LiNH(2) has a Li-N distance of 1.736(3) A, an N-H distance of 1.022(3) A, and a H-N-H angle of 106.9(1) degrees. These results are compared with theoretical predictions for LiNH(2), and experimental data for oligomeric, solid-phase samples, which could not resolve the question of whether LiNH(2) is planar or not. In addition, comparisons are made with revised gas-phase and solid-phase data and calculated structures of NaNH(2).

  20. A revised mechanism for the α-ketoacid hydroxylamine amide forming ligations.

    Science.gov (United States)

    Patil, Mahendra

    2017-01-04

    Computational investigations of the α-ketoacid-hydroxylamine amide-forming (KAHA) ligation of O-unsubstituted (type-I) and O-benzoyl substituted (type-II) hydroxylamine have revealed a distinct mechanistic pathway for the KAHA ligation reactions. Instead of a pathway involving lactone and oxiridine intermediates for the reaction of O-unsubstituted hydroxylamine and ketoacids (type-I KAHA), as had been proposed in the experimental studies, the computational results favor the pathway which involves migration of the hydroxy group (-OH) to the adjacent carbon in one of the key steps. The new pathway for the type I KAHA reaction explains the distribution of the (18)O label in the final product (amide) that is observed in (18)O labeling experiments of type-I ligation reaction. A coherent mechanistic course is also identified for the reaction of O-benzoyl substituted hydroxylamine and ketoacid (type II KAHA) reactions. The proposed pathway for the type-II KAHA ligation reaction proceeds with the retention of an oxygen atom of the keto group of ketoacids rather than hydroxylamine in the final product (amide). These findings are consistent with the results of (18)O labeling experiments performed by Bode and coworkers on the KAHA reactions.

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

    CERN Document Server

    Christensen, Anders S; Borg, Mikael; Boomsma, Wouter; Lindorff-Larsen, Kresten; Hamelryck, Thomas; Jensen, Jan H

    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 QM results obtained for a small protein with an RMSD of 0.25 ppm (r = 0.94). ProCS is interfaced with the PHAISTOS protein simulation program and is used to infer statistical protein ensembles that reflect experimentally measured amide proton chemical shift values. Such chemical shift-based structural refinements, starting from high-resolution X-ray structures of Protein G, ubiquitin, and SMN Tudor Domain, result in average chemical shifts, hydrogen bond geometries, and trans-hydrogen bond (h3JNC') spin-spin coupling constants that are in excellent agreement with experiment. We show that the structural sensitivity of the QM-based amide proton chemical shift predictions is needed to refine protein structures to this...

  2. Structural origins of chiral second-order optical nonlinearity in collagen: amide I band.

    Science.gov (United States)

    Reiser, Karen M; McCourt, Alexander B; Yankelevich, Diego R; Knoesen, André

    2012-11-21

    The molecular basis of nonlinear optical (NLO) chiral effects in the amide I region of type I collagen was investigated using sum-frequency generation vibrational spectroscopy; chiral and achiral tensor elements were separated using different input/output beam polarization conditions. Spectra were obtained from native rat tail tendon (RTT) collagen and from cholesteric liquid crystal-like (LC) type I collagen films. Although RTT and LC collagen both possess long-range order, LC collagen lacks the complex hierarchical organization of RTT collagen. Their spectra were compared to assess the role of such organization in NLO chirality. No significant differences were observed between RTT and LC with respect to chiral or achiral spectra. These findings suggest that amide I NLO chiral effects in type I collagen assemblies arise predominantly from the chiral organization of amide chromophores within individual collagen molecules, rather than from supramolecular structures. The study suggests that sum-frequency generation vibrational spectroscopy may be uniquely valuable in exploring fundamental aspects of chiral nonlinearity in complex macromolecular structures.

  3. Chlorination of N-methylacetamide and amide-containing pharmaceuticals. Quantum-chemical study of the reaction mechanism.

    Science.gov (United States)

    Šakić, Davor; Šonjić, Pavica; Tandarić, Tana; Vrček, Valerije

    2014-03-27

    Chlorination of amides is of utmost importance in biochemistry and environmental chemistry. Despite the huge body of data, the mechanism of reaction between amides and hypochlorous acid in aqueous environment remains unclear. In this work, the three different reaction pathways for chlorination of N-methylacetamide by HOCl have been considered: the one-step N-chlorination of the amide, the chlorination via O-chlorinated intermediate, and the N-chlorination of the iminol intermediate. The high-level quantum chemical G3B3 composite procedure, double-hybrid B2-PLYPD, B2K-PLYP methods, and global hybrid M06-2X and BMK methods have been employed. The calculated energy barriers have been compared to the experimental value of ΔG(#)298 ≈ 87 kJ/mol, which corresponds to reaction rate constant k(r) ≈ 0.0036 M(-1) s(-1). Only the mechanism in which the iminol form of N-methylacetamide reacts with HOCl is consistent (ΔG(#)298 = 87.3 kJ/mol at G3B3 level) with experimental results. The analogous reaction mechanism has been calculated as the most favorable pathway in the chlorination of small-sized amides and amide-containing pharmaceuticals: carbamazepine, acetaminophen, and phenytoin. We conclude that the formation of the iminol intermediate followed by its reaction with HOCl is the general mechanism of N-chlorination for a vast array of amides.

  4. 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.

  5. [Bis(2-methoxyethyl)amino]sulfur trifluoride, the Deoxo-Fluor reagent: application toward one-flask transformations of carboxylic acids to amides.

    Science.gov (United States)

    White, Jonathan M; Tunoori, Ashok Rao; Turunen, Brandon J; Georg, Gunda I

    2004-04-02

    The use of the Deoxo-Fluor reagent is a versatile method for acyl fluoride generation and subsequent one-flask amide coupling. It provides mild conditions and facile purification of the desired products in good to excellent yields. We have explored the utility of this reagent for the one-flask conversion of acids to amides and Weinreb amides and as a peptide-coupling reagent.

  6. Synthesis of new fatty acids amides from aminolysis of fatty acid methyl esters (FAMEs); Sintese de novas amidas graxas a partir da aminolise de esteres metilicos

    Energy Technology Data Exchange (ETDEWEB)

    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., E-mail: dqmdoca@furg.b [Universidade Federal do Rio Grande, RS (Brazil). Escola de Quimica e Alimentos

    2010-07-01

    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)

  7. Far-infrared amide IV-VI spectroscopy of isolated 2- and 4-Methylacetanilide

    Science.gov (United States)

    Yatsyna, Vasyl; Bakker, Daniël J.; Feifel, Raimund; Rijs, Anouk M.; Zhaunerchyk, Vitali

    2016-09-01

    Delocalized molecular vibrations in the far-infrared and THz ranges are highly sensitive to the molecular structure, as well as to intra- and inter-molecular interactions. Thus, spectroscopic studies of biomolecular structures can greatly benefit from an extension of the conventional mid-infrared to the far-infrared wavelength range. In this work, the conformer-specific gas-phase far-infrared spectra of two aromatic molecules containing the peptide -CO-NH- link, namely, 2- and 4-Methylacetanilide, are investigated. The planar conformations with trans configuration of the peptide link have only been observed in the supersonic-jet expansion. The corresponding far-infrared signatures associated with the vibrations of the peptide -CO-NH- moiety, the so-called amide IV-VI bands, have been assigned and compared with the results of density functional theory frequency calculations based on the anharmonic vibrational second-order perturbation theory approach. The analysis of the experimental and theoretical data shows that the amide IV-VI bands are highly diagnostic for the geometry of the peptide moiety and the molecular backbone. They are also strongly blue-shifted upon formation of the NH⋯O-C hydrogen bonding, which is, for example, responsible for the formation of secondary protein structures. Furthermore, the amide IV-VI bands are also diagnostic for the cis configuration of the peptide link, which can be present in cyclic peptides. The experimental gas-phase data presented in this work can assist the vibrational assignment of similar biologically important systems, either isolated or in natural environments.

  8. Far-infrared amide IV-VI spectroscopy of isolated 2- and 4-Methylacetanilide.

    Science.gov (United States)

    Yatsyna, Vasyl; Bakker, Daniël J; Feifel, Raimund; Rijs, Anouk M; Zhaunerchyk, Vitali

    2016-09-14

    Delocalized molecular vibrations in the far-infrared and THz ranges are highly sensitive to the molecular structure, as well as to intra- and inter-molecular interactions. Thus, spectroscopic studies of biomolecular structures can greatly benefit from an extension of the conventional mid-infrared to the far-infrared wavelength range. In this work, the conformer-specific gas-phase far-infrared spectra of two aromatic molecules containing the peptide -CO-NH- link, namely, 2- and 4-Methylacetanilide, are investigated. The planar conformations with trans configuration of the peptide link have only been observed in the supersonic-jet expansion. The corresponding far-infrared signatures associated with the vibrations of the peptide -CO-NH- moiety, the so-called amide IV-VI bands, have been assigned and compared with the results of density functional theory frequency calculations based on the anharmonic vibrational second-order perturbation theory approach. The analysis of the experimental and theoretical data shows that the amide IV-VI bands are highly diagnostic for the geometry of the peptide moiety and the molecular backbone. They are also strongly blue-shifted upon formation of the NH⋯O-C hydrogen bonding, which is, for example, responsible for the formation of secondary protein structures. Furthermore, the amide IV-VI bands are also diagnostic for the cis configuration of the peptide link, which can be present in cyclic peptides. The experimental gas-phase data presented in this work can assist the vibrational assignment of similar biologically important systems, either isolated or in natural environments.

  9. Proximate and qualitative analysis of different parts of Piper sarmentosum, and quantification of total amides in various extracts

    Directory of Open Access Journals (Sweden)

    K Hussain

    2009-01-01

    Full Text Available Present study aimed to analyze crude powders and extracts of different parts of Piper sarmentosum for proximate, qualitative and quantitative studies to prepare standardized botanical drugs from the plant. Unlike synthetic drugs, standardization of botanical drugs is always challenging for natural product researchers due to inadequacy and unavailability of standards and methods. Standardization of botanical drugs is not just an analytical process which ends with the detection of few constituents rather it embodies a set of analytical, biochemical and biological protocols. Keeping analytical protocols in view, crude powders were analyzed for the content of moisture, total ash, acid insoluble ash, sulphated ash and soluble extractives in water and methanol. These physicochemical properties were found within specified limits. Comparison of Fourier Transform Infrared (FTIR fingerprints of crude powders of different parts indicated the difference of constituents. Similarly, comparison of ultra violet (UV profiles of extracts of all the parts exhibited discrimination. Qualitative analysis of aqueous and ethanol extracts by high performance thin layer chromatography (HPTLC indicated the presence of amides in ethanol extracts of all parts of the plant. Quantitative analysis of extracts indicated that total amide content was significantly higher by colorimetry as compared to UV spectrophotometry. The distribution of amides in different parts was in the order fruit > root > leaf > stem (P=0.000. It is concluded from the study that amide content varies in different parts of the plant and ethanol is a better solvent for their extraction. Additionally, colorimetric method exhibits high content of amides.

  10. Distribution of serotonin and FMRF-amide in the brain of Lymnaea stagnalis with respect to the visual system

    Institute of Scientific and Technical Information of China (English)

    Oksana P.TUCHINA; Valery V.ZHUKOV; Victor B.MEYER-ROCHOW

    2012-01-01

    Despite serotonin's and FMRF-amide's wide distribution in the nervous system of invertebrates and their importance as neurotransmitters,the exact roles they play in neuronal networks leaves many questions.We mapped the presence of serotonin and FMRF-amide-immunoreactivity in the central nervous system and eyes of the pond snail Lymnaea stagnalis and interpreted the results in connection with our earlier findings on the central projections of different peripheral nerves.Since the chemical nature of the intercellular connections in the retina of L.stagnalis is still largely unknown,we paid special attention to clarifying the role of serotonin and FMRF-amide in the visual system of this snail and compared our findings with those reported from other species.At least one serotonin- and one FMRF-amidergic fibre were labeled in each optic nerve,and since no cell bodies in the eye showed immunoreactivity to these neurotransmitters,we believe that efferent fibres with somata located in the central ganglia branch at the base of the eye and probably release 5HT and FMRF-amide as neuro-hormones.Double labelling revealed retrograde transport of neurobiotin through the optic nerve,allowing us to conclude that the central pathways and serotonin- and FMRF-amide-immunoreactive cells and fibres have different locations in the CNS in L.stagnalis.The chemical nature of the fibres,which connect the two eyes in L.stagnalis,is neither serotoninergic nor FMRF-amidergic.

  11. Involvement of mammalian RF-amide peptides and their receptors in the modulation of nociception in rodents

    Directory of Open Access Journals (Sweden)

    Safia eAyachi

    2014-10-01

    Full Text Available Mammalian RF-amide peptides, which all share a conserved carboxyl-terminal Arg-Phe-NH2 sequence, constitute a family of five groups of neuropeptides that are encoded by five different genes. They act through five G protein-coupled receptors and each group of peptide binds to and activates mostly one receptor: RF-amide related peptide (RFRP group binds to NPFFR1, neuropeptide FF (NPFF group to NPFFR2, pyroglutamylated RF-amide peptide (QRFP group to QRFPR, prolactin releasing peptide (PrRP group to PrRPR, and kisspeptin group to Kiss1R. These peptides and their receptors have been involved in the modulation of several functions including reproduction, feeding and cardiovascular regulation. Data from the literature now provide emerging evidence that all RF-amide peptides and their receptors are also involved in the modulation of nociception. This review will present the current knowledge on the involvement in rodents of the different mammalian RF-amide peptides and their receptors in the modulation of nociception in basal and chronic pain conditions as well as their modulatory effects on the analgesic effects of opiates.

  12. 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.

  13. 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

    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...... was the key to obtain good potency. This approach yielded compounds such as (E)-N-[6-(hydroxyamino)-6-oxohexyl]-3-(7-quinolinyl)-2-propenamide (27) (HDAC IC(50) 8 nM) which showed potent in vivo activity in the P388 mouse leukemia syngeneic model (an increased lifespan (ILS) of 111% was obtained...

  14. Discovery of MK-3168: A PET Tracer for Imaging Brain Fatty Acid Amide Hydrolase.

    Science.gov (United States)

    Liu, Ping; Hamill, Terence G; Chioda, Marc; Chobanian, Harry; Fung, Selena; Guo, Yan; Chang, Linda; Bakshi, Raman; Hong, Qingmei; Dellureficio, James; Lin, Linus S; Abbadie, Catherine; Alexander, Jessica; Jin, Hong; Mandala, Suzanne; Shiao, Lin-Lin; Li, Wenping; Sanabria, Sandra; Williams, David; Zeng, Zhizhen; Hajdu, Richard; Jochnowitz, Nina; Rosenbach, Mark; Karanam, Bindhu; Madeira, Maria; Salituro, Gino; Powell, Joyce; Xu, Ling; Terebetski, Jenna L; Leone, Joseph F; Miller, Patricia; Cook, Jacquelynn; Holahan, Marie; Joshi, Aniket; O'Malley, Stacey; Purcell, Mona; Posavec, Diane; Chen, Tsing-Bau; Riffel, Kerry; Williams, Mangay; Hargreaves, Richard; Sullivan, Kathleen A; Nargund, Ravi P; DeVita, Robert J

    2013-06-13

    We report herein the discovery of a fatty acid amide hydrolase (FAAH) positron emission tomography (PET) tracer. Starting from a pyrazole lead, medicinal chemistry efforts directed toward reducing lipophilicity led to the synthesis of a series of imidazole analogues. Compound 6 was chosen for further profiling due to its appropriate physical chemical properties and excellent FAAH inhibition potency across species. [(11)C]-6 (MK-3168) exhibited good brain uptake and FAAH-specific signal in rhesus monkeys and is a suitable PET tracer for imaging FAAH in the brain.

  15. Using ovality to predict nonmutagenic, orally efficacious pyridazine amides as cell specific spleen tyrosine kinase inhibitors.

    Science.gov (United States)

    Lucas, Matthew C; Bhagirath, Niala; Chiao, Eric; Goldstein, David M; Hermann, Johannes C; Hsu, Pei-Yuan; Kirchner, Stephan; Kennedy-Smith, Joshua J; Kuglstatter, Andreas; Lukacs, Christine; Menke, John; Niu, Linghao; Padilla, Fernando; Peng, Ying; Polonchuk, Liudmila; Railkar, Aruna; Slade, Michelle; Soth, Michael; Xu, Daigen; Yadava, Preeti; Yee, Calvin; Zhou, Mingyan; Liao, Cheng

    2014-03-27

    Inhibition of spleen tyrosine kinase has attracted much attention as a mechanism for the treatment of cancers and autoimmune diseases such as asthma, rheumatoid arthritis, and systemic lupus erythematous. We report the structure-guided optimization of pyridazine amide spleen tyrosine kinase inhibitors. Early representatives of this scaffold were highly potent and selective but mutagenic in an Ames assay. An approach that led to the successful identification of nonmutagenic examples, as well as further optimization to compounds with reduced cardiovascular liabilities is described. Select pharmacokinetic and in vivo efficacy data are presented.

  16. Clean SEA-TROSY Experiments to Map Solvent Exposed Amides in Large Proteins

    Institute of Scientific and Technical Information of China (English)

    林东海

    2004-01-01

    It is well known that the SEA-TROSY experiment could alleviate some of the problems of resonance overlap in 15N/2H labeled proteins as it was designed to selectively map solvent exposed amide protons. However, SEATROSY spectra may be contaminated with exchange-relayed NOE contributions from fast exchanged hydroxyl or amine protons and contributions from longitudinal relaxation. Also, perdeuteration of the protein sample is a prerequisite for this experiment. In this communication, a modified version, clean SEA-TROSY, was proposed to eliminate these artifacts and to allow the experiment to be applied to protonated or partially deuterated proteins and protein complexes.

  17. Oxidative burst inhibitory and cytotoxic amides and lignans from the stem bark of Fagara heitzii (Rutaceae).

    Science.gov (United States)

    Mbaze, Luc Meva'a; Lado, Jean Alexandre; Wansi, Jean Duplex; Shiao, Tze Chieh; Chiozem, David Dako; Mesaik, Muhammad Ahmed; Choudhary, Muhammad Iqbal; Lacaille-Dubois, Marie-Aleth; Wandji, Jean; Roy, René; Sewald, Norbert

    2009-01-01

    Two amides, heitziamide A and heitziamide B and two phenylethanoids, heitziethanoid A and heitziethanoid B together with thirteen known compounds were isolated from F. heitzii (Letouzey). The structures of all compounds were established by spectroscopic analysis. Nine compounds were evaluated for oxidative burst inhibitory activity in a chemoluminescence assay and for cytotoxicity against PC-3 prostate cancer cells. All compounds exhibited a clear suppressive effect on phagocytosis response upon activation with serum opsonized zymosan at the range of IC(50)=2.0-6.5 microM, but no cytotoxic effect was observed (IC(50)>100 microM).

  18. A Three-Dimensional View of Turbulence Amid Complex Structure in the HD 163296 Protoplanetary Disk

    Science.gov (United States)

    Flaherty, Kevin M.; Hughes, A. Meredith; Rose, Sanaea; Andrews, Sean M.; Wilner, David J.; Chiang, Eugene; Simon, Jacob B.

    2017-01-01

    Gas kinematics are an important part of planet formation, influencing processes ranging from the growth of sub-micron sized grains to the migration of gas giant planets. Dynamical behavior can be traced with both synoptic observations of the mid-infrared excess, sensitive to the inner disk, and spatially resolved radio observations of gas emission, sensitive to the outer disk. I report new constraints on the vertical structure of turbulence in the disk around HD 163296, based on ALMA observations of DCO+ and CO isotoplogues that are sensitive to different layers of the disk. These data place upper limits on the turbulence (ALMA constraints on turbulence amid differing ionization environments.

  19. The Role of Arginine-Phenylalanine-Amide-Related Peptides in Mammalian Reproduction

    Directory of Open Access Journals (Sweden)

    Mohammad Saied Salehi

    2015-10-01

    Full Text Available Until 2000 it was believed that gonadotropin-releasing hormone (GnRH was the sole regulator of hypophyseal gonadotropes. In 2000, the discovery of a gonadotropin inhibitory hormone (GnIH initiated a revolution in the field of reproductive physiology. Identification of GnIH homologues in mammals, the arginine-phenylalanine- amide (RFamide-related peptides (RFRPs, indicated a similar function. Subsequently, further works conducted in various laboratories worldwide have shown that these neuropeptides inhibit the hypothalamic-hypophyseal axis. This review discusses the role of RFRPs in mammalian reproductive processes.

  20. Methods for attaching polymerizable ceragenins to water treatment membranes using amine and amide linkages

    Science.gov (United States)

    Hibbs, Michael; Altman, Susan J.; Jones, Howland D.T.; Savage, Paul B.

    2013-10-15

    This invention relates to methods for chemically grafting and attaching ceragenin molecules to polymer substrates; methods for synthesizing ceragenin-containing copolymers; methods for making ceragenin-modified water treatment membranes and spacers; and methods of treating contaminated water using ceragenin-modified treatment membranes and spacers. Ceragenins are synthetically produced antimicrobial peptide mimics that display broad-spectrum bactericidal activity. Alkene-functionalized ceragenins (e.g., acrylamide-functionalized ceragenins) can be attached to polyamide reverse osmosis membranes using amine-linking, amide-linking, UV-grafting, or silane-coating methods. In addition, silane-functionalized ceragenins can be directly attached to polymer surfaces that have free hydroxyls.

  1. New Neutral Receptors for Fluoride Based on Calix[4]arene Bearing Thiourea and Amide

    Institute of Scientific and Technical Information of China (English)

    刘顺英; 徐括喜; 何永炳; 秦海娟; 孟令芝

    2005-01-01

    Two-armed neutral anion receptors (4,5), calix[4]arenes beating thiourea and amide binding sites, were prepared and examined their anion-binding ability by the UV-vis spectra. The results of non-linear curve fitting and Job plot indicate that 4 or 5 forms 1:1 stoichiometry complex with fluoride by hydrogen bonding interactions. Receptors 4 and 5 have an excellent selectivity for fluoride but have no binding ability with acetate, dihydrogen phosphate and the halogen anions (Cl-,Br-,I-).

  2. Pyrazole phenylcyclohexylcarbamates as inhibitors of human fatty acid amide hydrolases (FAAH).

    Science.gov (United States)

    Aghazadeh Tabrizi, Mojgan; Baraldi, Pier Giovanni; Ruggiero, Emanuela; Saponaro, Giulia; Baraldi, Stefania; Romagnoli, Romeo; Martinelli, Adriano; Tuccinardi, Tiziano

    2015-06-05

    Fatty acid amide hydrolase (FAAH) inhibitors have gained attention as potential therapeutic targets in the management of neuropathic pain. Here, we report a series of pyrazole phenylcyclohexylcarbamate derivatives standing on the known carbamoyl FAAH inhibitor URB597. Structural modifications led to the recognition of compound 22 that inhibited human recombinant FAAH (hrFAAH) in the low nanomolar range (IC50 = 11 nM). The most active compounds of this series showed significant selectivity toward monoacylglycerol lipase (MAGL) enzyme. In addition, molecular modeling and reversibility behavior of the new class of FAAH inhibitors are presented in this article.

  3. The cardiovascular effects of PFRFamide and PFR(Tic)amide, a possible agonist and antagonist of neuropeptide FF (NPFF).

    Science.gov (United States)

    Huang, E Y; Li, J Y; Tan, P P; Wong, C H; Chen, J C

    2000-02-01

    Neuropeptide FF (NPFF), an endogenous opioid-related neuromodulater, has been reported to show significant effects on the cardiovascular system, namely elevation of arterial blood pressure (BP) and heart rate (HR) in rats. In the present study, we synthesized two novel NPFF analogs, PFRFamide (putative NPFF agonist) and PFR(Tic)amide (putative NPFF antagonist), and examined their cardiovascular effect on BP and HR in anesthetized rats. The arterial mean BP and HR were measured by way of direct femoral artery catheterization. The data showed that PFRFamide increased BP in a dose-dependent manner, while PFR(Tic)amide decreased BP dose-dependently. These results revealed the possibility of PFRFamide and PFR(Tic)amide to be NPFF agonist and antagonist (or inverse agonist), respectively. These two NPFF analogs may possess potential in new drug design, and the NPFF system could be very important in mammalian cardiovascular function.

  4. 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.

  5. SYNTHESIS AND CHARACTERIZATION OF THERMOTROPIC COPOLYESTERS AND COPOLY (ESTER-AMIDE)S CONTAINING OXYETHYLENE-ETHER AS THE SPACER

    Institute of Scientific and Technical Information of China (English)

    WANG Shanger; MO Zhishen; ZHANG Hongfang; FENG Zhiliu

    1995-01-01

    Flexible oxyethylene-ether was introduced into the aromatic copolyesters and copoly (ester-amide)s to reduce the melting point of resulting polymers. The melting point was greatly reduced to 200℃ or even lower in some cases, and the molecular weight was satisfactorily high as reflected by inherent viscosity. The polymers exhibited high thermal stability and good mechanical properties as determined by TGA and mechanical tests. The copolyester showed better crystallinity and liquid crystallinity than corresponding copoly(ester-amide)s with similar monomer composition as reflected by POM observation and WAXD study. The melting points for both copolyesters and copoly (ester-amide)s showed great dependence on the pacetoxybenzoic acid (PAB) content in monomer composition and reached the lowest value when PAB was 29 mol%.

  6. Detailed insights into the retention mechanism of caffeine metabolites on the amide stationary phase in hydrophilic interaction chromatography.

    Science.gov (United States)

    Guo, Yong; Shah, Rajan

    2016-09-09

    The amide phase was investigated using a wide range of acetonitrile content in the mobile phase in both the HILIC and RPLC modes. Using caffeine metabolites as the model compounds, the retention, thermodynamic and kinetic data was obtained under various mobile phase conditions and supported the previous postulation that there might be a transition of the predominant retention mechanism in relation to the acetonitrile content in HILIC. On the amide phase, hydrophilic partitioning seemed to be the predominant retention mechanism below 85% acetonitrile; and a different retention mechanism (presumably surface adsorption) made more and more significant contributions to the overall retention when the acetonitrile content reached above 85%. This study also provided more direct evidences to explain the effect of salt concentration on the retention of non-charged solutes in HILIC. In addition, the retention, thermodynamic and kinetic data suggest that the amide phase behaved very differently from the conventional C18 phase in the RPLC mode.

  7. Unravelling exceptional acetylene and carbon dioxide adsorption within a tetra-amide functionalized metal-organic framework

    Science.gov (United States)

    Moreau, Florian; da Silva, Ivan; Al Smail, Nada H.; Easun, Timothy L.; Savage, Mathew; Godfrey, Harry G. W.; Parker, Stewart F.; Manuel, Pascal; Yang, Sihai; Schröder, Martin

    2017-02-01

    Understanding the mechanism of gas-sorbent interactions is of fundamental importance for the design of improved gas storage materials. Here we report the binding domains of carbon dioxide and acetylene in a tetra-amide functionalized metal-organic framework, MFM-188, at crystallographic resolution. Although exhibiting moderate porosity, desolvated MFM-188a exhibits exceptionally high carbon dioxide and acetylene adsorption uptakes with the latter (232 cm3 g-1 at 295 K and 1 bar) being the highest value observed for porous solids under these conditions to the best of our knowledge. Neutron diffraction and inelastic neutron scattering studies enable the direct observation of the role of amide groups in substrate binding, representing an example of probing gas-amide binding interactions by such experiments. This study reveals that the combination of polyamide groups, open metal sites, appropriate pore geometry and cooperative binding between guest molecules is responsible for the high uptakes of acetylene and carbon dioxide in MFM-188a.

  8. 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...

  9. Bioactive surface modification on amide-photografted poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

    Energy Technology Data Exchange (ETDEWEB)

    Ke Yu; Xue Wei [Institute of Life and Health Engineering, Jinan University, Guangzhou (China); Wang Yingjun; Ren Li; Wu Gang, E-mail: lisa6863@163.com [Biomaterial Research Institute, College of Material Science and Engineering, South China University of Technology, Guangzhou (China)

    2011-04-15

    Collagen was chemically immobilized on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) films via hydrophilic polyacrylamide spacers, aiming to establish the bioactive surface and the inner surface models. The inner surface modified films presented higher wettability than the surface modified films. Wide-angle x-ray diffraction results showed that the d-spacing values of the inner surface model increased compared with those of the surface model, but there was no significant difference between the amide- and collagen-modified PHBV films. The peak melting temperatures of PHBV and the special endotherm around 70 {sup 0}C were following the order: PHBV > amide-modified PHBV > collagen-modified PHBV. The weight loss of the collagen-modified PHBV (inner surface model) might involve hydrolyzation and mineralization during 360 days of incubation, with a maximum value of 18.24%, while PHBV films did not show significant weight loss. The pH value of the degradation fluids fluctuated in the range of 6.86-7.22, as the initial pH was recorded at 7.20. Based on the surface model, collagen-modified PHBV scaffolds were prepared, which enhanced chondrocyte adhesion and spread on the biomimetic surface. Two surface modification models might develop a protocol with a view to generating a biocompatible and biomechanical scaffold for use in meniscus regeneration.

  10. Mapping the amide I absorption in single bacteria and mammalian cells with resonant infrared nanospectroscopy

    Science.gov (United States)

    Baldassarre, L.; Giliberti, V.; Rosa, A.; Ortolani, M.; Bonamore, A.; Baiocco, P.; Kjoller, K.; Calvani, P.; Nucara, A.

    2016-02-01

    Infrared (IR) nanospectroscopy performed in conjunction with atomic force microscopy (AFM) is a novel, label-free spectroscopic technique that meets the increasing request for nano-imaging tools with chemical specificity in the field of life sciences. In the novel resonant version of AFM-IR, a mid-IR wavelength-tunable quantum cascade laser illuminates the sample below an AFM tip working in contact mode, and the repetition rate of the mid-IR pulses matches the cantilever mechanical resonance frequency. The AFM-IR signal is the amplitude of the cantilever oscillations driven by the thermal expansion of the sample after absorption of mid-IR radiation. Using purposely nanofabricated polymer samples, here we demonstrate that the AFM-IR signal increases linearly with the sample thickness t for t \\gt 50 nm, as expected from the thermal expansion model of the sample volume below the AFM tip. We then show the capability of the apparatus to derive information on the protein distribution in single cells through mapping of the AFM-IR signal related to the amide-I mid-IR absorption band at 1660 cm-1. In Escherichia Coli bacteria we see how the topography changes, observed when the cell hosts a protein over-expression plasmid, are correlated with the amide I signal intensity. In human HeLa cells we obtain evidence that the protein distribution in the cytoplasm and in the nucleus is uneven, with a lateral resolution better than 100 nm.

  11. Benzothiazole derivatives bearing amide moiety: potential cytotoxic and apoptosis-inducing agents against cervical cancer.

    Science.gov (United States)

    Singh, Meenakshi; Modi, Arusha; Narayan, Gopeshwar; Singh, Sushil K

    2016-07-01

    Cervical cancer is a major cause of morbidity and mortality in women worldwide. In recent years, benzothiazole analogues have attracted considerable attention in anticancer research. Therefore, in this study, the earlier reported amide series of benzothiazole derivatives were investigated for their antiproliferative activity. The activity of amide derivatives was evaluated using the 3-(4, 5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, flow cytometric analysis, apoptosis assay, and DNA fragmentation on two human cervical cancer cell lines: SiHa and C33-A. The data reported from this investigation indicated that benzothiazole derivatives show pronounced cytotoxicity in the HPV16-positive SiHa cells compared with HPV-negative C-33A cells. The in-vitro cytotoxicity of the compounds on the HEK-293 noncancer cell line was evaluated to establish selectivity. Cells treated with benzothiazole derivatives showed prominent morphological features as evidenced by cell shrinkage, membrane blebbing, apoptotic nuclei, and DNA fragmentation. The benzothiazole derivatives show accumulation of cells in the sub-G1 and S-phase of the cell cycle in SiHa and C33-A, respectively. In addition, these derivatives exert their beneficial effect by inducing apoptosis, in the chemoprevention of cervical cancer cells, and were further ascertained using a DNA fragmentation assay. The compounds studied showed potent cytotoxic and apoptotic properties against SiHa and C33-A cancer cell lines and thus represent an excellent starting point for further optimization of therapeutically effective anticancer drugs.

  12. Enhanced Cellular Uptake and Pharmacokinetic Characteristics of Doxorubicin-Valine Amide Prodrug.

    Science.gov (United States)

    Park, Yohan; Park, Ju-Hwan; Park, Suryeon; Lee, Song Yi; Cho, Kwan Hyung; Kim, Dae-Duk; Shim, Won-Sik; Yoon, In-Soo; Cho, Hyun-Jong; Maeng, Han-Joo

    2016-09-22

    In this study, we synthesized the valine (Val)-conjugated amide prodrug of doxorubicin (DOX) by the formation of amide bonds between DOX and Val. The synthesis of the DOX-Val prodrug was identified by a proton nuclear magnetic resonance (¹H-NMR) assay. In the MCF-7 cells (human breast adenocarcinoma cell; amino acid transporter-positive cell), the cellular accumulation efficiency of DOX-Val was higher than that of DOX according to the flow cytometry analysis data. Using confocal laser scanning microscopy (CLSM) imaging, it was confirmed that DOX-Val as well as DOX was mainly distributed in the nucleus of cancer cells. DOX-Val was intravenously administered to rats at a dose of 4 mg/kg, and the plasma concentrations of DOX-Val (prodrug) and DOX (formed metabolite) were quantitatively determined. Based on the systemic exposure (represented as area under the curve (AUC) values) of DOX-Val (prodrug) and DOX (formed metabolite), approximately half of DOX-Val seemed to be metabolized into DOX. However, it is expected that the remaining DOX-Val may exert improved cellular uptake efficiency in cancer cells after its delivery to the cancer region.

  13. An Investigation of Solid-State Amidization and Imidization Reactions in Vapor Deposited Poly (amic acid)

    Energy Technology Data Exchange (ETDEWEB)

    Anthamatten, M; Letts, S A; Day, K; Cook, R C; Gies, A P; Hamilton, T P; Nonidez, W K

    2004-06-28

    The condensation polymerization reaction of 4,4'-oxydianiline (ODA) with pyromellitic dianhydride (PMDA) to form poly(amic acid) and the subsequent imidization reaction to form polyimide were investigated for films prepared using vapor deposition polymerization techniques. Fourier-transform infrared spectroscopy (FT-IR), thermal analysis, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) of films at different temperatures indicate that additional solid-state polymerization occurs prior to imidization reactions. Experiments reveal that, upon vapor deposition, poly(amic acid) oligomers form that have a number-average molecular weight of about 1500 Daltons. Between 100 - 130 C these chains undergo additional condensation reaction to form slightly higher molecular weight oligomers. Calorimetry measurements show that this reaction is exothermic ({Delta}H {approx} -30 J/g) with an activation energy of about 120 kJ/mol. Experimental reaction enthalpies are compared to results from ab initio molecular modeling calculations to estimate the number of amide groups formed. At higher temperatures (150 - 300 C) imidization of amide linkages occurs as an endothermic reaction ({Delta}H {approx} +120 J/g) with an activation energy of about 130 kJ/mol. Solid-state kinetics were found to depend on reaction conversion as well as the processing conditions used to deposit films.

  14. Amide bond cleavage initiated by coordination with transition metal ions and tuned by an auxiliary ligand.

    Science.gov (United States)

    Yang, Yongpo; Lu, Chunxin; Wang, Hailong; Liu, Xiaoming

    2016-06-21

    The reaction of ligand , N,N-bis(pyridin-2-ylmethyl)acetamide, with five transition metal salts, FeCl3·6H2O, CuCl2·2H2O, Cu(ClO4)2·6H2O, ZnCl2 and K2PtCl4/KI, produced five metal complexes, [(μ-O)(FeClL')(FeCl3)] (), [CuLCl2] (), [CuBPA(ClO4)(CHCN)] ClO4 (), [ZnLCl2] () and [PtLI2] (), where = 1-(2,4,5-tri(pyridin-2-yl)-3-(pyridin-2-ylmethyl)imidazolidin-1-yl)ethanone which formed in situ, and BPA = bis(pyridin-2-ylmethyl)amine. The ligand and complexes were characterized by a variety of spectroscopic techniques including X-ray single crystal diffraction where applicable. Depending on the metal ion and auxiliary ligand of the complex, the acetyl group of the ligand could be either intact or cleaved. When ferric chloride hexahydrate was used, the deacetylation proceeded even further and a novel heterocyclic compound () was formed in situ. A possible mechanism was proposed for the formation of the heterocyclic compound found in complex . Our results indicate that to cleave effectively an amide bond, it is essential for a metal centre to bind to the amide bond and the metal centre is of sufficient Lewis acidity.

  15. Synthesis and Evaluation of Coumaroyl Dipeptide Amide as Potential Whitening Agents

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jaeil; Lee, Jaeho [Gwangju Institute of Science and Technology, Gwangju (Korea, Republic of); Lee, Hyesuk; Shin, Kyonghoon; Ryu, Geunseog; Cho, Inshik; Kim, Hanyoung [Central Research Laboratories, Daejeon (Korea, Republic of)

    2013-10-15

    Coumaroyl dipeptide amide, Coumaric acid-LG-NH{sub 2}, was prepared successfully using the solid-phase method, and its efficacy as a skin whitening agent was studied. Coumaric acid-LG-NH{sub 2} was prepared with Rink-amide resin, and 96.354% of purity was obtained. Using MTT assay and LDH release assay, we found that it exhibited very low cytotoxicity. And, we found that Coumaric acid-LG-NH{sub 2} inhibited tyrosinase activity dose-dependently and showed superior tyrosinase inhibitory activity to well-known whitening agent, arbutin. IC{sub 50} value of Coumaric acid-LG-NH{sub 2} was 182.4 μM, and IC{sub 50} value of arbutin was 384.6 μM. Also, in measurement of melanin contents using B16F1 melanoma cell lines, Coumaric acid-LG-NH{sub 2} reduced melanin production induced by α-MSH statistically significant, and showed superior melanin inhibitory activity to p-coumaric acid or arbutin. In addition, Coumaric acid-LG-NH{sub 2} reduced MC1R mRNA expression level. Thus, we concluded that MC1R pathway is the significant pathway of Coumaric acid-LG-NH{sub 2}, and Coumaric acid-LG-NH{sub 2} has great potential to be used as novel whitening agents.

  16. Development of CXCR4 modulators by virtual HTS of a novel amide-sulfamide compound library.

    Science.gov (United States)

    Bai, Renren; Shi, Qi; Liang, Zhongxing; Yoon, Younghyoun; Han, Yiran; Feng, Amber; Liu, Shuangping; Oum, Yoonhyeun; Yun, C Chris; Shim, Hyunsuk

    2017-01-27

    CXCR4 plays a crucial role in recruitment of inflammatory cells to inflammation sites at the beginning of the disease process. Modulating CXCR4 functions presents a new avenue for anti-inflammatory strategies. However, using CXCR4 antagonists for a long term usage presents potential serious side effect due to their stem cell mobilizing property. We have been developing partial CXCR4 antagonists without such property. A new computer-aided drug design program, the FRESH workflow, was used for anti-CXCR4 lead compound discovery and optimization, which coupled both compound library building and CXCR4 docking screens in one campaign. Based on the designed parent framework, 30 prioritized amide-sulfamide structures were obtained after systemic filtering and docking screening. Twelve compounds were prepared from the top-30 list. Most synthesized compounds exhibited good to excellent binding affinity to CXCR4. Compounds Ig and Im demonstrated notable in vivo suppressive activity against xylene-induced mouse ear inflammation (with 56% and 54% inhibition). Western blot analyses revealed that Ig significantly blocked CXCR4/CXCL12-mediated phosphorylation of Akt. Moreover, Ig attenuated the amount of TNF-α secreted by pathogenic E. coli-infected macrophages. More importantly, Ig had no observable cytotoxicity. Our results demonstrated that FRESH virtual high throughput screening program of targeted chemical class could successfully find potent lead compounds, and the amide-sulfamide pharmacophore was a novel and effective framework blocking CXCR4 function.

  17. Amidation reaction of eugenyl oxyacetate ethyl ester with 1,3 diaminopropane

    Science.gov (United States)

    Suryanti, V.; Wibowo, F. R.; Kusumaningsih, T.; Wibowo, A. H.; Khumaidah, S. A.; Wijayanti, L. A.

    2016-04-01

    Eugenol having various substituents on the aromatic ring (hydroxy, methoxy and allyl) are useful for starting material in synthesizing of its derivatives. Eugenol derivatives have shown wide future potential applications in many areas, especially as future drugs against many diseases. The aim of this work was to synthesize an amide of eugenol derivative. The starting material used was eugenol from clove oil and the reaction was conducted in 3 step reactions to give the final product. Firstly, eugenol was converted into eugenyl oxyacetate [2-(4-allyl-2-methoxyphenoxy) acetic acid] as a white crystal with 70.5% yield, which was then esterified with ethanol to have eugenyl oxyacetate ethyl ester [ethyl 2-(4-allyl-2-methoxyphenoxy) acetate] as brown liquid in 75.7%. The last step was the reaction between eugenyl oxyacetate ethyl ester and 1,3 diaminopropane to give 2-(4-allyl-2-methoxyphenoxy)-N-(3-aminopropyl) acetamide as a brown powder with 71.6% yield, where the amidation reaction was occurred.

  18. Dethreading of Tetraalkylsuccinamide-Based [2]Rotaxanes for Preparing Benzylic Amide Macrocycles.

    Science.gov (United States)

    Martinez-Cuezva, Alberto; Rodrigues, Leticia V; Navarro, Cristian; Carro-Guillen, Fernando; Buriol, Lilian; Frizzo, Clarissa P; Martins, Marcos A P; Alajarin, Mateo; Berna, Jose

    2015-10-16

    The dethreading of a series of succinamide-based [2]rotaxanes bearing benzylic amide macrocycles is reported herein. These transformations proceeded quantitatively either under flash vacuum pyrolysis, conventional heating, or microwave irradiation. Studying the size complementarity of the stoppers at the ends of the thread and the cavity of the macrocycle allowed us to set up the best substituents for implementing the extrusion of the thread from the interlocked precursors. A variety of (1)H NMR kinetic experiments were carried out in order to evaluate the rate constants of the dethreading process, the half-life times of the rotaxanes, and the influence of temperature and solvents on these processes. The use of dibutylamino groups as stoppers yielded the rotaxane precursor in a reasonable yield and allowed the quantitative deslipping of the rotaxane. The overall process, including the rotaxane formation and its further dethreading, has been exploited for preparing benzylic amide macrocycles enhancing, in most cases, the results of the classical (2 + 2) condensation and other reported stepwise syntheses. The kinetics of the dethreading process is fairly sensitive to the electronic effects of the substituents on the isophthalamide unit or to the electronic nature of the pyridine rings through a conformational equilibrium expanding or contracting the cavity of the interlocked precursor.

  19. 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).

  20. 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.

  1. Enhanced Cellular Uptake and Pharmacokinetic Characteristics of Doxorubicin-Valine Amide Prodrug

    Directory of Open Access Journals (Sweden)

    Yohan Park

    2016-09-01

    Full Text Available In this study, we synthesized the valine (Val-conjugated amide prodrug of doxorubicin (DOX by the formation of amide bonds between DOX and Val. The synthesis of the DOX-Val prodrug was identified by a proton nuclear magnetic resonance (1H-NMR assay. In the MCF-7 cells (human breast adenocarcinoma cell; amino acid transporter–positive cell, the cellular accumulation efficiency of DOX-Val was higher than that of DOX according to the flow cytometry analysis data. Using confocal laser scanning microscopy (CLSM imaging, it was confirmed that DOX-Val as well as DOX was mainly distributed in the nucleus of cancer cells. DOX-Val was intravenously administered to rats at a dose of 4 mg/kg, and the plasma concentrations of DOX-Val (prodrug and DOX (formed metabolite were quantitatively determined. Based on the systemic exposure (represented as area under the curve (AUC values of DOX-Val (prodrug and DOX (formed metabolite, approximately half of DOX-Val seemed to be metabolized into DOX. However, it is expected that the remaining DOX-Val may exert improved cellular uptake efficiency in cancer cells after its delivery to the cancer region.

  2. 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 .

  3. Photodynamic activity of the boronated chlorin e6 amide in artificial and cellular membranes.

    Science.gov (United States)

    Antonenko, Yuri N; Kotova, Elena A; Omarova, Elena O; Rokitskaya, Tatyana I; Ol'shevskaya, Valentina A; Kalinin, Valery N; Nikitina, Roza G; Osipchuk, Julia S; Kaplan, Mikhail A; Ramonova, Alla A; Moisenovich, Mikhail M; Agapov, Igor I; Kirpichnikov, Mikhail P

    2014-03-01

    Photodynamic tumor-destroying activity of the boronated chlorin e6 derivative BACE (chlorin e6 13(1)-N-{2-[N-(1-carba-closo-dodecaboran-1-yl)methyl]aminoethyl}amide-15(2), 17(3)-dimethyl ester), previously described in Moisenovich et al. (2010) PLoS ONE 5(9) e12717, was shown here to be enormously higher than that of unsubstituted chlorin e6, being supported by the data on much higher photocytotoxicity of BACE in M-1 sarcoma cell culture. To validate membrane damaging effect as the basis of the enhanced tumoricidal activity, BACE was compared with unsubstituted chlorin e6 in the potency to photosensitize dye leakage from liposomes, transbilayer lipid flip-flop, inactivation of gramicidin A ionic channels in planar lipid membranes and erythrocyte hemolysis. In all the models comprising artificial and cellular membranes, the photodynamic effect of BACE exceeded that of chlorin e6. BACE substantially differed from chlorin e6 in the affinity to liposomes and erythrocytes, as monitored by fluorescence spectroscopy, flow cytometry and centrifugation. The results support the key role of membrane binding in the photodynamic effect of the boronated chlorin e6 amide.

  4. Chelating tris(amidate) ligands: versatile scaffolds for nickel(II).

    Science.gov (United States)

    Jones, Matthew B; Newell, Brian S; Hoffert, Wesley A; Hardcastle, Kenneth I; Shores, Matthew P; MacBeth, Cora E

    2010-01-14

    The synthesis and characterization of nickel complexes supported by a family of open-chain, tetradentate, tris(amidate) ligands, [N(o-PhNC(O)R)(3)](3-) ([L(R)](3-) where R = (i)Pr, (t)Bu, and Ph) is described. The complexes [Ni(L(iPr))](-), [Ni(L(tBu))](-), and [Ni(L(Ph))(CH(3)CN)](-) have been characterized by solution-state spectroscopic methods and single crystal X-ray diffraction. Each ligand gives rise to a different primary coordination sphere about the nickel centre. These studies indicate that the ligands' acyl substituents can be used to regulate the coordination mode of the amidate donors to nickel and the coordination number of the nickel centres. In addition, the ability of these complexes to bind cyanide has been explored. These experiments demonstrate that only one of these complexes, [Ni(L(iPr))](-), is able to irreversibly bind cyanide and can be used to assemble [Et(4)N](3)[Ni(L(iPr))(mu(2)-CN)Co(L(iPr))], a cyanide bridged, heterobimetallic complex. The synthesis and characterization of the cyanide containing complexes, including magnetic susceptibility studies, are described.

  5. Microwave assisted synthesis, spectral, magnetic and bioevolution of few Mn (II)-amide complexes

    Science.gov (United States)

    Joshi, Gaurav; Verma, K. K.; Gudesaria, D. D.; Bhojak, N.

    2016-05-01

    The importance and versatility of amide group containing ligands have promoted the selection of this class of ligands and their complexes for the study. The present work describes the synthesis, spectral and biological investigations on the complexes of amides derived from heterocyclic amines with Mn (II) ions. Four ligands derived 2-aminopyridine and their complexes with Mn (II) have been synthesized. A method for the synthesis of complexes has been developed by the use of microwave irradiation which is in agreement to Green chemistry approach. The complexes have been characterized on the basis of elemental analysis, infrared, electronic, ESR spectra and magnetic susceptibility studies. The diffuse reflectance spectrum of the complexes show bands in the region 20,000 cm-1 to 26,000 cm-1 assignable to 6A1g → 4T2g and 6A1g → 4E1g transitions. These are also typical of tetrahedral environment around the manganese. The magnetic moment (5.80 BM) of the complex indicates high spin tetrahedral environment. The microwave method of synthesis of complexes have been found easier, convenient and ecofriendly. Antimicrobial activities of compounds were also carried out against bacteria and fungi. Further minimal inhibitory concentration (MIC) was also determined for each compound.

  6. Refining Disordered Peptide Ensembles with Computational Amide I Spectroscopy: Application to Elastin-Like Peptides

    Science.gov (United States)

    Reppert, Mike; Roy, Anish R.; Tempkin, Jeremy O. B.; Dinner, Aaron R.; Tokmakoff, Andrei

    2017-01-01

    The characterization of intrinsically disordered protein (IDP) ensembles is complicated both by inherent heterogeneity and by the fact that many common experimental techniques function poorly when applied to IDPs. For this reason, the development of alternative structural tools for probing IDP ensembles has attracted considerable attention. Here we describe our recent work in developing experimental and computational tools for characterizing IDP ensembles using Amide I (backbone carbonyl stretch) vibrational spectroscopy. In this approach, the infrared (IR) absorption frequencies of isotope-labeled amide bonds probe their local electrostatic environments and structures. Empirical frequency maps allow us to use this spectroscopic data as a direct experimental test of atomistic structural models. We apply these methods to a family of short elastin-like peptides (ELPs), fragments of the elastin protein based around the Pro-Gly turn motif characteristic of the elastomeric segments of the full protein. Using a maximum entropy analysis of experimental spectra on the basis of predicted spectra from molecular dynamics (MD) ensembles, we find that peptides with Ala or Val sidechains preceding the Pro-Gly turn unit exhibit a stronger tendency toward extended structures than do Gly-Pro-Gly motifs, suggesting an important role for steric interactions in tuning the molecular properties of elastin. PMID:27736076

  7. 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)

  8. Biodistribution of Amine-Amide Chlorin e6 Derivative Conjugate with a Boron Nanoparticle for Boron Neutron-Capture Therapy

    OpenAIRE

    А.B. Volovetsky; N.Y. Shilyagina; V.V. Dudenkova; S.О. Pasynkova; М.А. Grin; А.F. Mironov; А.V. Feofanov; I.V. Balalaeva; А.V. Maslennikova

    2016-01-01

    The aim of the investigation was to study the biodistribution of amino-amide chlorin e6 derivative conjugate with cobalt bis-dicarbollide as a potential boron transporter for the tasks of boron neutron-capture therapy. Materials and Methods. The experiments were carried out on Balb/c mice with induced murine colon carcinoma CT-26. Amino-amide chlorin e6 derivative conjugate with cobalt bis-dicarbollide was administered intravenously, the dose being 5 and 10 mg/kg body mass. The sampling for m...

  9. Amide as an efficient ligand in the palladium-catalyzed Suzuki coupling reaction in water/ethanol under aerobic conditions

    Institute of Scientific and Technical Information of China (English)

    Hai Yang Liu; Kun Wang; Hai Yan Fu; Mao Lin Yuan; Hua Chen; Rui Xiang Li

    2011-01-01

    Amide, which is derived from proline and is inexpensive and air-stable, has been synthesized and characterized by 1H NMR,13C NMR, and MS. It was found to be an efficient ligand in the palladium-catalyzed Suzuki cross-coupling reaction. In the Pd/amide catalytic system, aryl bromides can be coupled with phenylboronic acid in ethanol/water (1:2;v/v) in excellent yields even with a low Pd loading of 0.01 mol%. Moreover, the scope of the reaction is broad, and a wide variety of functional groups are tolerant.

  10. 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.

  11. Syntheses and metal ions recognition of dendritic calix[n]arenes(n=6,8)amide derivative

    Institute of Scientific and Technical Information of China (English)

    WANG Yunyan; CAI Yahua; YAN Chaoguo

    2007-01-01

    Dendritic p-t'butylcalix[n]arene amide derivatives with terminal amino groups of the first and second generations were synthesized by using divergent methods from ammonolysis of ethyl calixarylacetate with 1,6-diaminohexane and Michael addition of methyl acrylate.Their structures were confirmed by IR,1H NMR.The recognition properties of these amide derivatives for several kinds of metal ions were studied with UV-Vis spectroscopy.The results showed a great affinity for soft Ag+ and UO22+ ions and formed 1:2 or 1:3 stoichiometric complexes.

  12. Processing of pro-opiomelanocortin-derived amidated joining peptide and glycine-extended precursor in monkey pituitary

    DEFF Research Database (Denmark)

    Fenger, M

    1991-01-01

    The molecular forms of proopiomelanocortin (POMC) derived amidated and C-terminal glycine-extended joining peptide from monkey (Macaca mulatta) pituitary were determined. The predominant forms of joining peptide found were the low molecular peptides POMC(76-105) and POMC(76-106), respectively....... Significant amounts of N-terminally truncated POMC(78-105) and POMC(78-106) were also detected in the posterior-intermediate lobe. No N-terminal extended forms were detected. The relative amount of amidated joining peptide to total joining peptide was 6-35%. It is concluded that not only is the primary...

  13. 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...

  14. 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)

    Rochon, Kristina; Proteau-Gagné, Arnaud; Bourassa, Philippe; Nadon, Jean-François; Côté, Jérome; Bournival, Véronique; Gobeil, Fernand; Guérin, Brigitte; Dory, Yves L; Gendron, Louis

    2013-08-21

    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.

  15. Influence of alkali and alkaline earth ions on the -alkylation of the lower rim phenolic-OH groups of -tert-butyl-calix[4]arene to result in amide-pendants: Template action of K+ and the structure of K+ bound tetra-amide derivative crystallized with a -tert-butylcalix[4]arene anion

    Indian Academy of Sciences (India)

    Amjad Ali; Chebrolu P Rao; Philippe Guionneau

    2008-03-01

    Role of alkali and alkaline earth ions on the formation of calix[4]arene-amide derivatives through -alkylation of the lower rim phenolic-OH groups in general and template action of K+ in particular have been explored. Na+ and K+ ions among alkali, and Ca2+ and Sr2+ ions among alkaline earth have shown tetra-amide derivatives bound to metal ion species. Among all these, potassium salts act as template and yields a K+ bound tetra-amide derivative where the charge is counter balanced by a calix[4] arene-monoanion and the product is crystallographically characterized. Change in the amide precursor used in these -alkylation reactions has no effect on the type of the amide derivative formed. Also demonstrated is a direct one-step reaction for the preparation of 1,3-di-amide derivative in high yield and low reaction period using CsHCO3.

  16. GLP-1 amidation efficiency along the length of the intestine in mice, rats and pigs and in GLP-1 secreting cell lines.

    Science.gov (United States)

    Kuhre, Rune Ehrenreich; Albrechtsen, Nicolai Wewer; Windeløv, Johanne Agerlin; Svendsen, Berit; Hartmann, Bolette; Holst, Jens Juul

    2014-05-01

    XXX: Measurements of plasma concentrations of the incretin hormone GLP-1 are complex because of extensive molecular heterogeneity. This is partly due to a varying and incompletely known degree of C-terminal amidation. Given that virtually all GLP-1 assays rely on a C-terminal antibody, it is essential to know whether or not the molecule one wants to measure is amidated. We performed a detailed analysis of extractable GLP-1 from duodenum, proximal jejunum, distal ileum, caecum, proximal colon and distal colon of mice (n=9), rats (n=9) and pigs (n=8) and determined the degree of amidation 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 continuously along the intestine all the way to the rectum, but were highest in the distal ileum and proximal colon of the rat. In the pig, very little or no GLP-1 was present before the distal ileum with similar levels from ileum to distal colon. In the mouse, GLP-1 was extensively amidated at all sampling 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-amidated GLP-1.

  17. 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.

  18. 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

    2016-03-01

    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.

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

    Directory of Open Access Journals (Sweden)

    Duan S

    2012-07-01

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

  20. C-terminal amide to alcohol conversion changes the cardiovascular effects of endomorphins in anesthetized rats.

    Science.gov (United States)

    Yu, Ye; Wang, Chang-lin; Cui, Yun; Fan, Ying-zhe; Liu, Jing; Shao, Xuan; Liu, Hong-mei; Wang, Rui

    2006-01-01

    Endomorphin1-ol (Tyr-Pro-Trp-Phe-ol, EM1-ol) and endomorphin2-ol (Tyr-Pro-Phe-Phe-ol, EM2-ol), with C-terminal alcohol (-ol) containing, have been shown to exhibit higher affinity and lower intrinsic efficacy in vitro than endomorphins. In the present study, in order to investigate the alterations of systemic hemodynamic effects induced by C-terminal amide to alcohol conversion, responses to intravenous (i.v.) or intracerebroventricular (i.c.v.) injection of EM1-ol, EM2-ol and their parents were compared in the system arterial pressure (SAP) and heart rate (HR) of anesthetized rats. Both EM1-ol and EM2-ol induced dose-related decrease in SAP and HR when injected in doses of 3-100 nmol/kg, i.v. In terms of relative vasodepressor activity, it is interesting to note that EM2-ol was more potent than endomorphin2 [the dose of 25% decrease in SAP (DD25) = 6.01+/-3.19 and 13.99+/-1.56 nmol/kg, i.v., respectively] at a time when responses to EM1-ol were less potent than endomorphin1. Moreover, decreases in SAP in response to EM1-ol and EM2-ol were reduced by naloxone, atropine sulfate, L-NAME and bilateral vagotomy. It indicated that the vasodepressor responses were possibly mediated by a naloxone-sensitive, nitric oxide release, vagus-activated mechanism. It is noteworthy that i.c.v. injections of -ol derivatives produced dose-related decreases in SAP and HR, which were significantly less potent than endomorphins and were attenuated by naloxone and atropine sulfate. In summary, the results of the present study indicated that the C-terminal amide to alcohol conversion produced different effects on the vasodepressor activity of endomorphin1 and endomorphin2 and endowed EM2-ol distinctive hypotension characters in peripheral (i.v.) and central (i.c.v.) tissues. Moreover, these results provided indirect evidence that amidated C-terminus might play an important role in the regulation of the cardiovascular system.

  1. Backbone amide linker strategy for the synthesis of 1,4-triazole-containing cyclic tetra- and pentapeptides

    NARCIS (Netherlands)

    Springer, J.; de Cuba, K.R.; Calvet-Vitale, S.; Geenevasen, J.A.J.; Hermkens, P.H.H.; Hiemstra, H.; van Maarseveen, J.H.

    2008-01-01

    A backbone amide linker strategy was chosen for the solid-phase synthesis of triazole-containing Cyclic tetra- and pentapeptides. An alkyne-substituted linker derived from 4-hydroxy-2-methoxybenzaldehyde was elongated by using standard "Fmoc-based" solid phase chemistry and terminated by coupling of

  2. An insight into the photophysical properties of amide hydrogen bonded N-(benzo[d]thiazol-2-yl) acetamide crystals

    Science.gov (United States)

    Balijapalli, Umamahesh; Udayadasan, Sathiskumar; Panyam Muralidharan, Vivek; Sukumarapillai, Dileep Kumar; Shanmugam, Easwaramoorthi; Paduthapillai Gopal, Aravindan; S. Rathore, Ravindranath; Kulathu Iyer, Sathiyanarayanan

    2017-02-01

    Three distinct, hydrogen bond associated N-(benzo[d]thiazol-2-yl) acetamides were synthesized by refluxing benzothiazoles with acetic acid. The nature of the assemblies was characteristic to the substituent in the benzothiazole moiety. In N-(benzo[d]thiazol-2-yl)acetamide, water acts as a bridge for forming three hydrogen bonds, as an acceptor to amide Nsbnd H, and donors to carbonyl of amide and thiazole nitrogen assembles of three different N-(benzo[d]thiazol-2-yl)acetamide molecules. The N-(6-methylbenzo[d]thiazol-2-yl)acetamide formed a (amide) N-H…N (thiazole) bonded R22(8) molecular dimers by two homo-intermolecular hydrogen bonding interactions. N-(6-methoxybenzo[d]thiazol-2-yl)acetamide formed (amide)N-H…O (acid) & (acid)O-H…N (thiazole) interactions with the acetic acid, forming a R22(8) hydrogen-bonded ring by two hetero-intermolecular hydrogen bonding interactions.

  3. Rapid and efficient synthesis of new chiral aromatic amide molecular tweezers under solvent-free conditions using microwave

    Institute of Scientific and Technical Information of China (English)

    Xiao Xiang Zhao; Zhi Gang Zhao; Xing Li Liu; Xiu Ming Wu

    2009-01-01

    An efficient and simple method for the synthesis of new chiral aromatic amide molecular tweezers by irradiation with microwave under solvent-free conditions has been developed.Its main advantages are short reaction times.good conversions and the environmentally friendly nature of the process.

  4. Amidate prodrugs of 9-[2-(phosphonomethoxy)ethyl]adenine as inhibitors of adenylate cyclase toxin from Bordetella pertussis.

    Science.gov (United States)

    Šmídková, Markéta; Dvoráková, Alexandra; Tloust'ová, Eva; Česnek, Michal; Janeba, Zlatko; Mertlíková-Kaiserová, Helena

    2014-01-01

    Adenylate cyclase toxin (ACT) is the key virulence factor of Bordetella pertussis that facilitates its invasion into the mammalian body. 9-[2-(Phosphonomethoxy)ethyl]adenine diphosphate (PMEApp), the active metabolite of the antiviral drug bis(POM)PMEA (adefovir dipivoxil), has been shown to inhibit ACT. The objective of this study was to evaluate six novel amidate prodrugs of PMEA, both phenyloxy phosphonamidates and phosphonodiamidates, for their ability to inhibit ACT activity in the J774A.1 macrophage cell line. The two phenyloxy phosphonamidate prodrugs exhibited greater inhibitory activity (50% inhibitory concentration [IC50] = 22 and 46 nM) than the phosphonodiamidates (IC50 = 84 to 3,960 nM). The inhibitory activity of the prodrugs correlated with their lipophilicity and the degree of their hydrolysis into free PMEA in J774A.1 cells. Although the prodrugs did not inhibit ACT as effectively as bis(POM)PMEA (IC50 = 6 nM), they were significantly less cytotoxic. Moreover, they all reduced apoptotic effects of ACT and prevented an ACT-induced elevation of intracellular [Ca(2+)]i. The amidate prodrugs were less susceptible to degradation in Caco-2 cells compared to bis(POM)PMEA, while they exerted good transepithelial permeability in this assay. As a consequence, a large amount of intact amidate prodrug is expected to be available to target macrophages in vivo. This feature makes nontoxic amidate prodrugs attractive candidates for further investigation as novel antimicrobial agents.

  5. Is there any difference in Amide and NOE CEST effects between white and gray matter at 7T?

    NARCIS (Netherlands)

    Khlebnikov, Vitaly; Siero, JCW; Wijnen, Jannie; Visser, F; Luijten, Peter R; Klomp, DWJ; Hoogduin, Hans

    2016-01-01

    Measurement of Chemical Exchange Saturation Transfer (CEST) is providing tissue physiology dependent contrast, e.g. by looking at Amide and NOE (Nuclear Overhauser Enhancement) effects. CEST is unique in providing quantitative metabolite information at high imaging resolution. However, direct compar

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

    Science.gov (United States)

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

    2009-01-01

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

  7. 40 CFR 721.6183 - Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow alkyl amines...

    Science.gov (United States)

    2010-07-01

    ... - maleic anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine... Substances § 721.6183 Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow... anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine (PMN...

  8. Quantification of primary fatty acid amides in commercial tallow and tallow fatty acid methyl esters by HPLC-APCI-MS.

    Science.gov (United States)

    Madl, Tobias; Mittelbach, Martin

    2005-04-01

    Primary fatty acid amides are a group of biologically highly active compounds which were already identified in nature. Here, these substances were determined in tallow and tallow fatty acid methyl esters for the first time. As tallow is growing in importance as an oleochemical feedstock for the soap manufacturing, the surfactant as well as the biodiesel industry, the amounts of primary fatty acid amides have to be considered. As these compounds are insoluble in tallow as well as in the corresponding product e.g. tallow fatty acid methyl esters, filter plugging can occur. For the quantification in these matrices a purification step and a LC-APCI-MS method were developed. Although quantification of these compounds can be performed by GC-MS, the presented approach omitted any derivatization and increased the sensitivity by two orders of magnitude. Internal standard calibration using heptadecanoic acid amide and validation of the method yielded a limit of detection of 18.5 fmol and recoveries for the tallow and fatty acid methyl ester matrices of 93% and 95%, respectively. A group of commercially available samples were investigated for their content of fatty acid amides resulting in an amount of up to 0.54%m/m (g per 100 g) in tallow and up to 0.16%m/m (g per 100 g) in fatty acid methyl esters.

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

    Science.gov (United States)

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

  10. Sol–gel immobilization of Alcalase from Bacillus licheniformis for application in the synthesis of C-terminal peptide amides

    NARCIS (Netherlands)

    Corici, L.N.; Frissen, A.E.; Zoelen, van D.J.; Eggen, I.F.; Peter, F.; Davidescu, C.M.; Boeriu, C.G.

    2011-01-01

    Alcalase 2.4L FG, a commercial preparation of Subtilisin A, was physically entrapped in glass sol–gel matrices using alkoxysilanes of different types mixed with tetramethoxysilane (TMOS). The materials were used for catalyzing C-terminal amidation of Z-Ala-Phe-OMe in a mixture of tert-butanol/DMF. F

  11. Copper-Catalyzed N-Arylation of Amides Using (S-N-Methylpyrrolidine-2-carboxylate as the Ligand

    Directory of Open Access Journals (Sweden)

    Dong-Sheng Ma

    2010-03-01

    Full Text Available (S-N-methylpyrrolidine-2-carboxylate, a derivative of natural L-proline, was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides with aryl halides under mild conditions. A variety of N-arylamides were synthesized in good to high yields.

  12. Selective and reactive hydration of nitriles to amides in water using silver nanoparticles stabilized by organic ligands

    Energy Technology Data Exchange (ETDEWEB)

    Kawai, Koji [Hokkaido University, Division of Materials Science and Engineering, Faculty of Engineering (Japan); Kawakami, Hayato [Miyoshi Oil & Fat Co., Ltd. (Japan); Narushima, Takashi; Yonezawa, Tetsu, E-mail: tetsu@eng.hokudai.ac.jp [Hokkaido University, Division of Materials Science and Engineering, Faculty of Engineering (Japan)

    2015-02-15

    Water-dispersible silver nanoparticles stabilized by silver–carbon covalent bonds were prepared. They exhibited high catalytic activities for the selective hydration of nitriles to amides in water. The activation of a nitrile group by the functional groups of the substrates and the hydrophobic layer on the nanoparticles influenced the catalyzed reaction were confirmed. Alkyl nitriles could also be selectively hydrated.

  13. Application of two-dimensional infrared spectroscopy to benchmark models for the amide I band of proteins

    NARCIS (Netherlands)

    Bondarenko, Anna S.; Jansen, Thomas L. C.

    2015-01-01

    In this paper, we present a novel benchmarking method for validating the modelling of vibrational spectra for the amide I region of proteins. We use the linear absorption spectra and two-dimensional infrared spectra of four experimentally well-studied proteins as a reference and test nine combinatio

  14. 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...

  15. Proton-driven amide bond-cleavage pathways of gas-phase peptide ions lacking mobile protons.

    Science.gov (United States)

    Bythell, Benjamin J; Suhai, Sándor; Somogyi, Arpád; Paizs, Béla

    2009-10-07

    The mobile proton model (Dongre, A. R., Jones, J. L., Somogyi, A. and Wysocki, V. H. J. Am. Chem. Soc. 1996, 118 , 8365-8374) of peptide fragmentation states that the ionizing protons play a critical role in the gas-phase fragmentation of protonated peptides upon collision-induced dissociation (CID). The model distinguishes two classes of peptide ions, those with or without easily mobilizable protons. For the former class mild excitation leads to proton transfer reactions which populate amide nitrogen protonation sites. This enables facile amide bond cleavage and thus the formation of b and y sequence ions. In contrast, the latter class of peptide ions contains strongly basic functionalities which sequester the ionizing protons, thereby often hindering formation of sequence ions. Here we describe the proton-driven amide bond cleavages necessary to produce b and y ions from peptide ions lacking easily mobilizable protons. We show that this important class of peptide ions fragments by different means from those with easily mobilizable protons. We present three new amide bond cleavage mechanisms which involve salt-bridge, anhydride, and imine enol intermediates, respectively. All three new mechanisms are less energetically demanding than the classical oxazolone b(n)-y(m) pathway. These mechanisms offer an explanation for the formation of b and y ions from peptide ions with sequestered ionizing protons which are routinely fragmented in large-scale proteomics experiments.

  16. Rat NPFF(1) receptor-mediated signaling: functional comparison of neuropeptide FF (NPFF), FMRFamide and PFR(Tic)amide.

    Science.gov (United States)

    Chen, Jin-Chung; Lee, Wei-Hsin; Chen, Pei-Chun; Tseng, Ching-Ping; Huang, Eagle Yi-Kung

    2006-05-01

    Neuropeptide FF (NPFF) participates in many physiological functions associated with opioids in the mammalian CNS. We established a pheochromocytoma PC-12 cell line clone stably expressing rat NPFF1 receptors. Both NPFF and FMRFamide activated NPFF1 receptors to couple with Gi/o protein and inhibited adenylyl cyclase activity in PC-12/rNPFF1 cells, but there were no effects on MAPKs (ERK1/2 and p38 MAPK) or PI3K/Akt pathway. FMRFamide also inhibited DARPP-32/Thr34 phosphorylation in the presence of forskolin. Similarly, PFR(Tic)amide, a 'super-agonist' of NPFF receptors, inhibited the production of cAMP and slightly decreased DARPP-32/Thr34 phosphorylation in PC-12/rNPFF1 cells. Intracerebroventricular injections of PFR(Tic)amide blocked behavioral sensitization of locomotor activity to amphetamine, and intrathecal injection of PFR(Tic)amide caused a dose-dependent antinociception in vivo in rats. Thus, "over-activation" of NPFF receptors by PFR(Tic)amide induced different bio-effects from those induced by NPFF in vivo.

  17. Amidated joining peptide in the human pituitary, gut, adrenal gland and bronchial carcinoids. Immunocytochemical and immunochemical evidence

    DEFF Research Database (Denmark)

    Bjartell, A; Fenger, M; Ekman, R;

    1990-01-01

    The distribution of the proopiomelanocortin-derivated amidated joining peptide (JP-N) was examined in the human pituitary gland, adrenal gland, gut and in three bronchial carcinoids. Double immunostaining showed coexistence of immunoreactive JP-N and other proopiomelanocortin derivatives, e...

  18. Aminolysis reaction of calix [ 4 ] arene esters and crystal structures and conformational behaviors of calix[4]arene amides

    Institute of Scientific and Technical Information of China (English)

    WU, Yong; LIU, Hui-Biao; HU, Jun; DUAN, Chun-Ying; XU, Zheng

    2000-01-01

    We first make use of aminolysis of calix[4]arene esters to synthesize calix[4]arene amides. When the two ethyl esters of the calix[4]arene esters are aminolysized, the 1, 3-amide derivative is formed selectively. The crystal structures of the calix[4]arene with two butyl amide (3b) and four butyl amide moieties (4b) were determined. The intermolecular hydrogen bonds make 4b form two-dimensional net work insolid state.The 1H NMR spectra prove that 3b is of a pinched cone conformation, while 4b and tetraheptylamide-calix[4]arene (6b)take fast interconversion between two C2v isomers in solution and appear an apparent cone conformation at room temperature. As decreasing temperature, the interconversion rate decreases gradually and, finally, the interconversion process is frozen at Tc= - 10℃, which makes both conformations of 4b and 6b the pinched cone structures. The hydrogen bond improves the interconversion barrier, and the large different values of the potential barrier between 6b and 4b (or 6b) may be of forming different hydrogen bonds.

  19. Structure-activity relationships of fatty acid amide ligands in activating and desensitizing G protein-coupled receptor 119.

    Science.gov (United States)

    Kumar, Pritesh; Kumar, Akhilesh; Song, Zhao-Hui

    2014-01-15

    The purpose of the current study was to apply a high throughput assay to investigate the structure-activity relationships of fatty acid amides for activating and desensitizing G protein-coupled receptor 119, a promising therapeutic target for both type 2 diabetes and obesity. A cell-based, homogenous time resolved fluorescence (HTRF) method for measuring G protein-coupled receptor 119-mediated increase of cyclic adenosine monophosphate (cAMP) levels was validated and applied in this study. Using novel fatty acid amides and detailed potency and efficacy analyses, we have demonstrated that degree of saturation in acyl chain and charged head groups of fatty acid amides have profound effects on the ability of these compounds to activate G protein-coupled receptor 119. In addition, we have demonstrated for the first time that pretreatments with G protein-coupled receptor 119 agonists desensitize the receptor and the degrees of desensitization caused by fatty acid amides correlate well with their structure-activity relationships in activating the receptor.

  20. Evaluation of physicochemical properties, skin permeation and accumulation profiles of salicylic acid amide prodrugs as sunscreen agent.

    Science.gov (United States)

    Yan, Yi-Dong; Sung, Jun Ho; Lee, Dong Won; Kim, Jung Sun; Jeon, Eun-Mi; Kim, Dae-Duk; Kim, Dong Wuk; Kim, Jong Oh; Piao, Ming Guan; Li, Dong Xun; Yong, Chul Soon; Choi, Han Gon

    2011-10-31

    Various amide prodrugs of salicylic acid were synthesised, and their physicochemical properties including lipophilicity, chemical stability and enzymatic hydrolysis were investigated. In vivo skin permeation and accumulation profiles were also evaluated using a combination of common permeation enhancing techniques such as the use of a supersaturated solution of permeants in an enhancer vehicle, a lipophilic receptor solution, removal of the stratum corneum and delipidisation of skin. Their capacity factor values were proportional to the degree of carbon-carbon saturation in the side chain. All these amides were highly stable in acetonitrile and glycerine. Amide prodrugs were converted to salicylic acid both in hairless mouse liver and skin homogenates. N-dodecyl salicylamide (C12SM) showed the lowest permeation of salicylic acid in skin compared to the other prodrugs, probably due to its low aqueous solubility. It had a high affinity for the stratum corneum and its accumulation was restricted to only the uppermost layer of skin. Thus, this amide prodrug could be a safer topical sunscreen agent with minimum potential for systemic absorption.

  1. 2D IR spectroscopy of histidine: probing side-chain structure and dynamics via backbone amide vibrations.

    Science.gov (United States)

    Ghosh, Ayanjeet; Tucker, Matthew J; Gai, Feng

    2014-07-17

    It is well known that histidine is involved in many biological functions due to the structural versatility of its side chain. However, probing the conformational transitions of histidine in proteins, especially those occurring on an ultrafast time scale, is difficult. Herein we show, using a histidine dipeptide as a model, that it is possible to probe the tautomer and protonation status of a histidine residue by measuring the two-dimensional infrared (2D IR) spectrum of its amide I vibrational transition. Specifically, for the histidine dipeptide studied, the amide unit of the histidine gives rise to three spectrally resolvable amide I features at approximately 1630, 1644, and 1656 cm(-1), respectively, which, based on measurements at different pH values and frequency calculations, are assigned to a τ tautomer (1630 cm(-1) component) and a π tautomer with a hydrated (1644 cm(-1) component) or dehydrated (1656 cm(-1) component) amide. Because of the intrinsic ultrafast time resolution of 2D IR spectroscopy, we believe that the current approach, when combined with the isotope editing techniques, will be useful in revealing the structural dynamics of key histidine residues in proteins that are important for function.

  2. 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.

  3. pH and urea dependence of amide hydrogen-deuterium exchange rates in the beta-trefoil protein hisactophilin.

    Science.gov (United States)

    Houliston, R Scott; Liu, Chengsong; Singh, Laila M R; Meiering, Elizabeth M

    2002-01-29

    Amide hydrogen/deuterium exchange rates were measured as a function of pH and urea for 37 slowly exchanging amides in the beta-trefoil protein hisactophilin. The rank order of exchange rates is generally maintained under different solution conditions, and trends in the pH and urea dependence of exchange rates are correlated with the rank order of exchange rates. The observed trends are consistent with the expected behavior for exchange of different amides via global and/or local unfolding. Analysis of the pH dependence of exchange in terms of rate constants for structural opening and closing reveals a wide range of rates in different parts of the hisactophilin structure. The slowest exchanging amides have the slowest opening and closing rates. Many of the slowest exchanging amides are located in trefoil 2, but there are also some slow exchanging amides in trefoils 1 and 3. Slow exchangers tend to be near the interface between the beta-barrel and the beta-hairpin triplet portions of this single-domain structure. The pattern of exchange behaviour in hisactophilin is similar to that observed previously in interleukin-1 beta, indicating that exchange properties may be conserved among beta-trefoil proteins. Comparisons of opening and closing rates in hisactophilin with rates obtained for other proteins reveal clear trends for opening rates; however, trends in closing rates are less apparent, perhaps due to inaccuracies in the values used for intrinsic exchange rates in the data fitting. On the basis of the pH and urea dependence of exchange rates and optical measurements of stability and folding, EX2 is the main exchange mechanism in hisactophilin, but there is also evidence for varying levels of EX1 exchange at low and high pH and high urea concentrations. Equilibrium intermediates in which subglobal portions of structure are cooperatively disrupted are not apparent from analysis of the urea dependence of exchange rates. There is, however, a strong correlation between

  4. MEDV-13 for QSAR Studies on the COX-2 Inhibition by In domethacin Amides and Esters

    Institute of Scientific and Technical Information of China (English)

    LIU,Shu-Shen (刘树深); YIN,Chun-Sheng(印春生); SHI,Yun-Yu(施蕴渝); CAI,Shao-Xi(蔡绍皙); LI,Zhi-Liang(李志良)

    2001-01-01

    A molecular electronegativity distance vector based on 13 atomic types (MEDV-13), is a descriptor for predicting the biological activities of molecules based on the quantitative structure-activity relationship (QSAR). The MEDV-13 with 91 descriptors is employed to describe the structures of a series of selective cydooxygenase-2 (COX-2) inhibitors inchuding 16 indomethacin and its amide and ester derivatives (ImAE). A principal component regression (PCR) is used to derive a QSAR model relating the biological activities expressed by pIC50 values to the MEDV-13. With the number of principal components of 6, the correlation coeffcient (R) and the root mean square error (RMS) are 0.9245 and 0.1682 in modeling stage, and 0.8417 and 0.2389 in leave-one-out prediction step, respectively.

  5. 2D-QSAR Studies on Triazolone Compounds Containing Benzenesulfonic Amide

    Institute of Scientific and Technical Information of China (English)

    WEI Qing-Li; GAO Jun; SUN Dao-Xing; ZHANG Shu-Sheng

    2007-01-01

    The geometry structures of 6 triazolone compounds containing benzenesulfonic amide were fully optimized with DFT (Density Functional Theory) method at the B3LYP/6-31G level, and the structural and electronic parameters of the compounds were calculated. The hydrophobic and topological parameters of the title compounds were calculated by HyperChem software. The mono- and bi-parametric models between the parameters and biological activity of the compounds were analyzed by Multiple Linear Regression method based on Hansch-Fujita model. The results show that the activities of the title compounds were increased with higher hydrophobic property logP and molecular volume V, lower molecular energy ETOTAL and electronegative of benzene ring Qph.

  6. Synthesis, characterization and luminescence studies of gold(I–NHC amide complexes

    Directory of Open Access Journals (Sweden)

    Adrián Gómez-Suárez

    2013-10-01

    Full Text Available A flexible, efficient and straightforward methodology for the synthesis of N-heterocyclic carbene gold(I–amide complexes is reported. Reaction of the versatile building block [Au(OH(IPr] (1 (IPr = 1,3-bis(2,6-diisopropylphenylimidazol-2-ylidene with a series of commercially available (heteroaromatic amines leads to the synthesis of several [Au(NRR’(IPr] complexes in good yields and with water as the sole byproduct. Interestingly, these complexes present luminescence properties. UV–vis and fluorescence measurements have allowed the identification of their excitation and emission wavelengths (λmax. These studies revealed that by selecting the appropriate amine ligand the emission can be easily tuned to achieve a variety of colors, from violet to green.

  7. Efficient Synthesis of Single-Chain Polymer Nanoparticles via Amide Formation

    Directory of Open Access Journals (Sweden)

    Ana Sanchez-Sanchez

    2015-01-01

    Full Text Available Single-chain technology (SCT allows the transformation of individual polymer chains to folded/collapsed unimolecular soft nanoparticles. In this work we contribute to the enlargement of the SCT toolbox by demonstrating the efficient synthesis of single-chain polymer nanoparticles (SCNPs via intrachain amide formation. In particular, we exploit cross-linking between active methylene groups and isocyanate moieties as powerful “click” chemistry driving force for SCNP construction. By employing poly(methyl methacrylate- (PMMA- based copolymers bearing β-ketoester units distributed randomly along the copolymer chains and bifunctional isocyanate cross-linkers, SCNPs were successfully synthesized at r.t. under appropriate reaction conditions. Characterization of the resulting SCNPs was carried out by means of a combination of techniques including size exclusion chromatography (SEC, infrared (IR spectroscopy, proton nuclear magnetic resonance (1H NMR spectroscopy, dynamic light scattering (DLS, and elemental analysis (EA.

  8. Interactions of peptide amidation and copper: novel biomarkers and mechanisms of neural dysfunction.

    Science.gov (United States)

    Bousquet-Moore, Danielle; Prohaska, Joseph R; Nillni, Eduardo A; Czyzyk, Traci; Wetsel, William C; Mains, Richard E; Eipper, Betty A

    2010-01-01

    Mammalian genomes encode only a small number of cuproenzymes. The many genes involved in coordinating copper uptake, distribution, storage and efflux make gene/nutrient interactions especially important for these cuproenzymes. Copper deficiency and copper excess both disrupt neural function. Using mice heterozygous for peptidylglycine alpha-amidating monooxygenase (PAM), a cuproenzyme essential for the synthesis of many neuropeptides, we identified alterations in anxiety-like behavior, thermoregulation and seizure sensitivity. Dietary copper supplementation reversed a subset of these deficits. Wildtype mice maintained on a marginally copper-deficient diet exhibited some of the same deficits observed in PAM(+/-) mice and displayed alterations in PAM metabolism. Altered copper homeostasis in PAM(+/-) mice suggested a role for PAM in the cell type specific regulation of copper metabolism. Physiological functions sensitive to genetic limitations of PAM that are reversed by supplemental copper and mimicked by copper deficiency may serve as indicators of marginal copper deficiency.

  9. Optimized Reaction Conditions for Amide Bond Formation in DNA-Encoded Combinatorial Libraries.

    Science.gov (United States)

    Li, Yizhou; Gabriele, Elena; Samain, Florent; Favalli, Nicholas; Sladojevich, Filippo; Scheuermann, Jörg; Neri, Dario

    2016-08-08

    DNA-encoded combinatorial libraries are increasingly being used as tools for the discovery of small organic binding molecules to proteins of biological or pharmaceutical interest. In the majority of cases, synthetic procedures for the formation of DNA-encoded combinatorial libraries incorporate at least one step of amide bond formation between amino-modified DNA and a carboxylic acid. We investigated reaction conditions and established a methodology by using 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide, 1-hydroxy-7-azabenzotriazole and N,N'-diisopropylethylamine (EDC/HOAt/DIPEA) in combination, which provided conversions greater than 75% for 423/543 (78%) of the carboxylic acids tested. These reaction conditions were efficient with a variety of primary and secondary amines, as well as with various types of amino-modified oligonucleotides. The reaction conditions, which also worked efficiently over a broad range of DNA concentrations and reaction scales, should facilitate the synthesis of novel DNA-encoded combinatorial libraries.

  10. Synthesis and biological evaluation of some new amide moiety bearing quinoxaline derivatives as antimicrobial agents.

    Science.gov (United States)

    Abu Mohsen, U; Yurttaş, L; Acar, U; Özkay, Y; Kaplacikli, Z A; Karaca Gencer, H; Cantürk, Z

    2015-05-01

    In this study, we aimed to synthesize some new quinoxaline derivatives bearing amide moiety and to evaluate their antimicrobial activity. A set of 16 novel compounds of N-[2,3-bis(4-methoxy/methylphenyl)quinoxalin-6-yl]-substituted benzamide derivatives were synthesized by reacting 2,3-bis(4-methoxyphenyl)-6-aminoquinoxaline or 2,3-bis(4-methylphenyl)-6-aminoquinoxaline with benzoyl chloride derivatives in tetrahydrofuran and investigated for their antimicrobial activity. The structures of the obtained final compounds were confirmed by spectral data (IR, (1)H-NMR, (13)C-NMR and MS). The antimicrobial activity of the compounds were determined by using the microbroth dilution method. Antimicrobial activity results revealed that synthesized compounds exhibited remarkable activity against Candida krusei (ATCC 6258) and Candida parapsilosis (ATCC 22019).

  11. Comparative study to predict dipeptidyl peptidase IV inhibitory activity of β-amino amide scaffold

    Directory of Open Access Journals (Sweden)

    S Patil

    2015-01-01

    Full Text Available Comparative study was performed on 34 β-amino amide derivatives as dipeptidyl peptidase IV inhibitors in order to determine their structural requirement to enhance the antidiabetic activities. Hologram quantitative structure activity relationships models utilized specialized fragment fingerprints (hologram length 353 which showed good predictivity with cross-validated q 2 and conventional r 2 values of 0.971 and 0.971, respectively. Models were validated and optimized by a test set of eight compounds and gave satisfactory predictive ability. Hologram quantitative structure activity relationships maps were helpful in prediction of the structural features of the ligands to account for the activity in terms of positively and negatively contributing towards activity. The information obtained from maps could be effectively use as a guiding tool for further structure modifications and synthesis of new potent antidiabetic agents.

  12. A novel amide stationary phase for hydrophilic interaction liquid chromatography and ion chromatography.

    Science.gov (United States)

    Shen, Guobin; Zhang, Feifang; Yang, Bingcheng; Chu, Changhu; Liang, Xinmiao

    2013-10-15

    A novel amide stationary phase (ASP) for hydrophilic interaction liquid chromatography (HILIC) has been prepared via the Click chemistry method. It was based on the strategy that the amino group of Asparagine was easily transferred to the corresponding azido group and then clicked onto terminal alkyne-silica gel in the presence of Cu(I)-based catalyst. For the tested polar compounds including nucleosides and nucleic acid bases, ASP-based column has demonstrated good performance in terms of separation efficiency and column stability, and the retention mechanism was found to match well the typical HILIC retention. In addition, the ASP described here showed much better selectivity in separation of inorganic anions under ion chromatography mode relative to other kinds of commercial ASP.

  13. 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......, but that it is one of several slow steps in the catalytic cycle. Rapid scrambling of hydrogen and deuterium at the a position of the alcohol was observed with deuterium-labeled substrates, which implies that the catalytically active species is a ruthenium dihydride. The experimental results were supported...... by the characterization of a plausible catalytic cycle by using DFT/M06. Both cisdihydride and trans-dihydride intermediates were considered, but when the theoretical turnover frequencies (TOFs) were derived directly from the calculated DFT/M06 energies, we found that only the trans-dihydride pathway was in agreement...

  14. An integrated approach to detecting communicative intent amid hyperkinetic movements in children.

    Science.gov (United States)

    Lesperance, Andrea; Blain, Stefanie; Chau, Tom

    2011-09-01

    Children with hyperkinetic movement (HKM) often have limited access to traditional augmentative and alternative communication technologies (e.g., mechanical switches). To seek a communication solution for these children, this study explored the possibility that discernable biomechanical patterns, related to preference, exist amid HKM. We deployed a unified approach to analyse a child's movements, fusing caregiver and clinician observations with quantitative data (accelerations of the upper extremities). Two case studies were examined. In both, the accelerometer data identified preference at adjusted accuracies statistically above chance using a linear discriminant classifier. Visually, communicative movement patterns were identified in the first child (κ=0.25-0.27) but not in the second child (κ=0.03-0.11). Implications of this study include possible enhancement in communication and independence for these children.

  15. Synthesis and anion recognition properties of shape-persistent binaphthyl-containing chiral macrocyclic amides

    Directory of Open Access Journals (Sweden)

    Marco Caricato

    2012-06-01

    Full Text Available We report on the synthesis and characterization of novel shape-persistent, optically active arylamide macrocycles, which can be obtained using a one-pot methodology. Resolved, axially chiral binol scaffolds, which incorporate either methoxy or acetoxy functionalities in the 2,2' positions and carboxylic functionalities in the external 3,3' positions, were used as the source of chirality. Two of these binaphthyls are joined through amidation reactions using rigid diaryl amines of differing shapes, to give homochiral tetraamidic macrocycles. The recognition properties of these supramolecular receptors have been analyzed, and the results indicate a modulation of binding affinities towards dicarboxylate anions, with a drastic change of binding mode depending on the steric and electronic features of the functional groups in the 2,2' positions.

  16. CO2 permeation through poly(amide-6-b-ethylene oxide)-nanosilica membranes

    Science.gov (United States)

    Lovineh, Shirin Gh.; Asghari, Morteza; Khanbabaei, Ghader

    2014-11-01

    The organic-inorganic hybrids of poly(amide-6-b-ethylene oxide) (PEBA) and silica utilizing aminopropyltriethoxysilane (APTES) as precursor was prepared via sol-gel process and was compared with neat PEBA. The nanodispersed inorganic network produced in the organic matrix was structurally characterized using Fourier transform infrared (FT-IR) that revealed the existence of different chemical groups corresponding to the silica precursors. The single gas permeability was carried out for neat PEBA and PEBA-nano silica (10 wt.% precursor) membranes. CO2 permeability for the neat polymer membrane was higher than the nano-composite membrane and increased with pressure. Adding 10 wt.% of nanosilica filler into the polymeric matrix caused CO2 permeability to decrease.

  17. Synthesis and bio-physicochemical properties of amide-functionalized N-methylpiperazinium surfactants.

    Science.gov (United States)

    Chauhan, Vinay; Singh, Sukhprit; Mishra, Rachana; Kaur, Gurcharan

    2014-12-15

    Four new amide functionalized N-methylpiperazinium amphiphiles having tetradecyl, hexadecyl alkyl chain lengths and counterions; chloride or bromide have been synthesized and characterized by various spectroscopic techniques. These new surfactants have been investigated in detail for their self-assembling behavior by surface tension, conductivity and fluorescence measurements. The thermodynamic parameters of these surfactants indicate that micellization is exothermic and entropy-driven. The dynamic light scattering (DLS) and transmission electron microscopy (TEM) experiments have been performed to insight the aggregate size of these cationics. Thermal degradation of these new surfactants has also been evaluated by thermal gravimetric analysis (TGA). These new surfactants form stable complexes with DNA as acknowledged by agarose gel electrophoresis, ethidium bromide exclusion and zeta potential measurements. They have also been found to have low cytotoxicity by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay on the C6 glioma cell line.

  18. Solid-phase synthesis of lidocaine and procainamide analogues using backbone amide linker (BAL) anchoring.

    Science.gov (United States)

    Shannon, Simon K; Peacock, Mandy J; Kates, Steven A; Barany, George

    2003-01-01

    New solid-phase strategies have been developed for the synthesis of lidocaine (1) and procainamide (2) analogues, using backbone amide linker (BAL) anchoring. Both sets were prepared starting from a common resin-bound intermediate, followed by four general steps: (i) attachment of a primary aliphatic or aromatic amine to the solid support via reductive amination (as monitored by a novel test involving reaction of 2,4-dinitrophenylhydrazine with residual aldehyde groups); (ii) acylation of the resultant secondary amine; (iii) displacement of halide with an amine; and (iv) trifluoroacetic acid-mediated release from the support. A manual parallel strategy was followed to provide 60 novel compounds, of which two dozen have not been previously described. In most cases, initial crude purities were >80%, and overall isolated yields were in the 40-88% range.

  19. Poly(ester amide-Poly(ethylene oxide Graft Copolymers: Towards Micellar Drug Delivery Vehicles

    Directory of Open Access Journals (Sweden)

    Gregory J. Zilinskas

    2012-01-01

    Full Text Available Micelles formed from amphiphilic copolymers are promising materials for the delivery of drug molecules, potentially leading to enhanced biological properties and efficacy. In this work, new poly(ester amide-poly(ethylene oxide (PEA-PEO graft copolymers were synthesized and their assembly into micelles in aqueous solution was investigated. It was possible to tune the sizes of the micelles by varying the PEO content of the polymers and the method of micelle preparation. Under optimized conditions, it was possible to obtain micelles with diameters less than 100 nm as measured by dynamic light scattering and transmission electron microscopy. These micelles were demonstrated to encapsulate and release a model drug, Nile Red, and were nontoxic to HeLa cells as measured by an MTT assay. Overall, the properties of these micelles suggest that they are promising new materials for drug delivery systems.

  20. Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates.

    Science.gov (United States)

    Cao, Hujun; Richter, Theresia M M; Pistidda, Claudio; Chaudhary, Anna-Lisa; Santoru, Antonio; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

    2015-11-01

    The alkali metal amidozincates Li4 [Zn(NH2)4](NH2)2 and K2[Zn(NH2)4] were, to the best of our knowledge, studied for the first time as hydrogen storage media. Compared with the LiNH2-2 LiH system, both Li4 [Zn(NH2)4](NH2)2-12 LiH and K2[Zn(NH2)4]-8 LiH systems showed improved rehydrogenation performance, especially K2[Zn(NH2)4]-8 LiH, which can be fully hydrogenated within 30 s at approximately 230 °C. The absorption properties are stable upon cycling. This work shows that ternary amides containing transition metals have great potential as hydrogen storage materials.

  1. Synthesis of Novel Chiral 7-Amide Substituted-4-androstene-3,17-dione Derivatives

    Institute of Scientific and Technical Information of China (English)

    CHEN Shao-rui; ZHOU Xue-qin; LI Wei; LIU Dong-zhi

    2011-01-01

    A series of novel 7-amide substituted-4-androstene-3,17-dione derivatives(8βαa-8αh or 8βa-8βh) was synthesized from the important intermediates 5 by N-acylation and acidic hydrolysis.Compounds 5a and 5β were obtained through the reaction sequence including acetalization,allylic oxidation,oximation and reduction.The structures of the target compounds were characterized by MS,1H NMR,13C NMR and HRMS spectra and their stereo configurations were identified through DEPT(distortionless enhancement by polarization transfer),HMQC(heteronuclear multiple quantum coherence) and NOE(nuclear overhauser effect) correlation.

  2. Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers

    Science.gov (United States)

    Dingemans, Theodorus J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

    2009-01-01

    Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.

  3. Kinetic resolution and chemoenzymatic dynamic kinetic resolution of functionalized gamma-hydroxy amides.

    Science.gov (United States)

    Fransson, Ann-Britt L; Borén, Linnéa; Pàmies, Oscar; Bäckvall, Jan-E

    2005-04-01

    [reaction: see text] An efficient kinetic resolution of racemic gamma-hydroxy amides 1 was performed via Pseudomas cepacia lipase (PS-C)-catalyzed transesterification. The enzyme PS-C tolerates both variation in the chain length and different functionalities giving good to high enantioselectivity (E values of up to >250). The combination of enzymatic kinetic resolution with a ruthenium-catalyzed racemization led to a dynamic kinetic resolution. The use of 2,4-dimethyl-3-pentanol as a hydrogen source to suppress ketone formation in the dynamic kinetic resolution yields the corresponding acetates in good yield and good to high enantioselectivity (ee's up to 98%). The synthetic utility of this procedure was illustrated by the practical synthesis of the versatile intermediate gamma-lactone (R)-5-methyltetrahydrofuran-2-one.

  4. Interacting Blends of Novel Unsaturated Polyester Amide Resin with Vinyl Acetate

    Directory of Open Access Journals (Sweden)

    H. S. Patel

    2004-01-01

    Full Text Available Novel unsaturated poly (ester- amide resins (UPEAs were prepared by the reaction between an epoxy resin, namely diglycidyl ether of bisphenol–A (DGEBA and unsaturated aliphatic bisamic acids using a base catalyst. These UPEAs were then blended with a vinyl monomer namely, Vinyl acetate (VA to produce a homogeneous resin syrup. The curing of these UPEAs-VA resin blends was carried out by using benzoyl peroxide (BPO as an initiator for the radical polymerization and was monitored by using a differential scanning calorimeter (DSC. The glass fibre reinforced composites (i.e. laminates of these UPEA-VA resin blends were fabricated using the DSC data. The chemical, mechanical and electrical properties of the glass fibre composites have also been evaluated. The unreinforced cured samples of the UPEA-VA resin blends were also analyzed by thermogravimetry (TGA.

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

    Science.gov (United States)

    Yao, Lei; Wang, Ming-Yi; Wang, Xin-Ke; Liu, Yi-Jun; Chen, Hang-Fei; Zheng, Jun; Nie, Wei; Ding, Ai-Jun; Geng, Fu-Hai; Wang, Dong-Fang; Chen, Jian-Min; Worsnop, Douglas R.; Wang, Lin

    2016-11-01

    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.

  6. Aqueous Cation-Amide Binding: Free Energies and IR Spectral Signatures by Ab Initio Molecular Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Pluharova, Eva; Baer, Marcel D.; Mundy, Christopher J.; Schmidt, Burkhard; Jungwirth, Pavel

    2014-07-03

    Understanding specific ion effects on proteins remains a considerable challenge. N-methylacetamide serves as a useful proxy for the protein backbone that can be well characterized both experimentally and theoretically. The spectroscopic signatures in the amide I band reflecting the strength of the interaction of alkali cations and alkali earth dications with the carbonyl group remain difficult to assign and controversial to interpret. Herein, we directly compute the IR shifts corresponding to the binding of either sodium or calcium to aqueous N-methylacetamide using ab initio molecular dynamics simulations. We show that the two cations interact with aqueous N-methylacetamide with different affinities and in different geometries. Since sodium exhibits a weak interaction with the carbonyl group, the resulting amide I band is similar to an unperturbed carbonyl group undergoing aqueous solvation. In contrast, the stronger calcium binding results in a clear IR shift with respect to N-methylacetamide in pure water. Support from the Czech Ministry of Education (grant LH12001) is gratefully acknowledged. EP thanks the International Max-Planck Research School for support and the Alternative Sponsored Fellowship program at Pacific Northwest National Laboratory (PNNL). PJ acknowledges the Praemium Academie award from the Academy of Sciences. Calculations of the free energy profiles were made possible through generous allocation of computer time from the North-German Supercomputing Alliance (HLRN). Calculations of vibrational spectra were performed in part using the computational resources in the National Energy Research Supercomputing Center (NERSC) at Lawrence Berkeley National Laboratory. This work was supported by National Science Foundation grant CHE-0431312. CJM is supported by the U.S. Department of Energy`s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. PNNL is operated for the Department of Energy by Battelle. MDB is

  7. Spectroscopic and molecular modeling investigation on the binding of a synthesized steroidal amide to protein

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hua-xin, E-mail: h.x.zhang@yeah.net; Liu, E.

    2014-09-15

    Owing to the various valuable biological activities, steroidal amides have become a hot topic in steroidal pharmaceutical chemistry. In this paper, an anti-tumor steroid derivate (DAAO) was synthesized and identified. The interaction between DAAO and human serum albumin (HSA) was studied by fluorescence spectra, circular dichroism (CD) spectra, molecular modeling and molecular probe techniques. The results suggested that DAAO had reacted with HSA through hydrogen bonds and van der Waals power. The formation of DAAO–HSA complex at ground state led to static quenching of HSA's fluorescence. The number of binding sites, binding constants, enthalpy change (ΔH{sup θ}), Gibbs free energy change (ΔG{sup θ}) and entropy change (ΔS{sup θ}) were calculated at different temperatures based on fluorescence quenching theory and classic equation. Molecular modeling investigation indicated that DAAO was more inclined to absorb on Sudlow's site I in subdomain IIA of HSA molecule on grounds of the lowest energy principle and steric hindrance effect. The binding location was further confirmed by fluorescence probe experiment using warfarin (site I probe) for displacement. Furthermore, the conformational changes of HSA in presence of DAAO were investigated by CD spectra. The results could provide new evidence explaining the relationship between the chemical structure and biological activity and may be useful for understanding the anti-cancer mechanism of steroidal drug. - Highlights: • A designed steroidal amide compound (DAAO) was synthesized by introducing amido bonds into a steroid nucleus. • DAAO binds to Sudlow's site I in HSA through hydrogen bonds and van der Waals power. • The interaction was a spontaneous and exothermic process with modest degree of reversibility. • The secondary structure of HSA and the microenvironment of TRP214 altered. • Amido bond in steroid nucleus (–NH–CO–) plays important role in stabling the structure of

  8. Settlement induction of Acropora palmata planulae by a GLW-amide neuropeptide

    Science.gov (United States)

    Erwin, P. M.; Szmant, A. M.

    2010-12-01

    Complex environmental cues dictate the settlement of coral planulae in situ; however, simple artificial cues may be all that is required to induce settlement of ex situ larval cultures for reef re-seeding and restoration projects. Neuropeptides that transmit settlement signals and initiate the metamorphic cascade have been isolated from hydrozoan taxa and shown to induce metamorphosis of reef-building Acropora spp. in the Indo-Pacific, providing a reliable and efficient settlement cue. Here, the metamorphic activity of six GLW-amide cnidarian neuropeptides was tested on larvae of the Caribbean corals Acropora palmata, Montastraea faveolata and Favia fragum. A. palmata planulae were induced to settle by the exogenous application of the neuropeptide Hym-248 (concentrations ≥1 × 10-6 M), achieving 40-80% attachment and 100% metamorphosis of competent planulae (≥6 days post-fertilization) during two spawning seasons; the remaining neuropeptides exhibited no activity. Hym-248 exposure rapidly altered larval swimming behavior (96% metamorphosis after 6 h. In contrast , M. faveolata and F. fragum planulae did not respond to any GLW-amides tested, suggesting a high specificity of neuropeptide activators on lower taxonomic scales in corals. Subsequent experiments for A. palmata revealed that (1) the presence of a biofilm did not enhance attachment efficiency when coupled with Hym-248 treatment, (2) neuropeptide-induced settlement had no negative effects on early life-history developmental processes: zooxanthellae acquisition and skeletal secretion occurred within 12 days, colonial growth occurred within 36 days, and (3) Hym-248 solutions maintained metamorphic activity following storage at room temperature (10 days), indicating its utility in remote field settings. These results corroborate previous studies on Indo-Pacific Acropora spp. and extend the known metamorphic activity of Hym-248 to Caribbean acroporids. Hym-248 allows for directed and reliable settlement of

  9. DFT-based simulations of IR amide I' spectra for a small protein in solution. Comparison of explicit and empirical solvent models.

    Science.gov (United States)

    Grahnen, Johan A; Amunson, Krista E; Kubelka, Jan

    2010-10-14

    Infrared (IR) amide I' spectra are widely used for investigations of the structural properties of proteins in aqueous solution. For analysis of the experimental data, it is necessary to separate the spectral features due to the backbone conformation from those arising from other factors, in particular the interaction with solvent. We investigate the effects of solvation on amide I' spectra for a small 40-residue helix-turn-helix protein by theoretical simulations based on density functional theory (DFT). The vibrational force fields and intensity parameters for the protein amide backbone are constructed by transfer from smaller heptaamide fragments; the side chains are neglected in the DFT calculations. Solvent is modeled at two different levels: first as explicit water hydrogen bonded to the surface amide groups, treated at the same DFT level, and, second, using the electrostatic map approach combined with molecular dynamics (MD) simulation. Motional narrowing of the spectral band shapes due to averaging over the fast solvent fluctuation is introduced by use of the time-averaging approximation (TAA). The simulations are compared with the experimental amide I', including two (13)C isotopically edited spectra, corrected for the side-chain signals. Both solvent models are consistent with the asymmetric experimental band shape, which arises from the differential solvation of the amide backbone. However, the effects of (13)C isotopic labeling are best captured by the gas-phase calculations. The limitations of the solvent models and implications for the theoretical simulations of protein amide vibrational spectra are discussed.

  10. A comparison of the effects of amide and acid groups at the C-terminus on the collision-induced dissociation of deprotonated peptides.

    Science.gov (United States)

    Bokatzian-Johnson, Samantha S; Stover, Michele L; Dixon, David A; Cassady, Carolyn J

    2012-09-01

    The dissociative behavior of peptide amides and free acids was explored using low-energy collision-induced dissociation and high level computational theory. Both positive and negative ion modes were utilized, but the most profound differences were observed for the deprotonated species. Deprotonated peptide amides produce a characteristic c(m-2)(-) product ion (where m is the number of residues in the peptide) that is either absent or in low abundance in the analogous peptide acid spectrum. Peptide acids show an enhanced formation of c(m-3)(-); however, this is not generally as pronounced as c(m-2)(-) production from amides. The most notable occurrence of an amide-specific product ion is for laminin amide (YIGSR-NH(2)) and this case was investigated using several modified peptides. Mechanisms involving 6- and 9-membered ring formation were proposed, and their energetic properties were investigated using G3(MP2) molecular orbital theory calculations. For example, with C-terminal deprotonation of pentaglycine amide, formation of c(m-2)(-) and a 6-membered ring diketopiperazine neutral requires >31.6 kcal/mol, which is 26.1 kcal/mol less than the analogous process involving the peptide acid. The end group specific fragmentation of peptide amides in the negative ion mode may be useful for identifying such groups in proteomic applications.

  11. A Comparison of the Effects of Amide and Acid Groups at the C-Terminus on the Collision-Induced Dissociation of Deprotonated Peptides

    Science.gov (United States)

    Bokatzian-Johnson, Samantha S.; Stover, Michele L.; Dixon, David A.; Cassady, Carolyn J.

    2012-09-01

    The dissociative behavior of peptide amides and free acids was explored using low-energy collision-induced dissociation and high level computational theory. Both positive and negative ion modes were utilized, but the most profound differences were observed for the deprotonated species. Deprotonated peptide amides produce a characteristic cm-2 - product ion (where m is the number of residues in the peptide) that is either absent or in low abundance in the analogous peptide acid spectrum. Peptide acids show an enhanced formation of cm-3 -; however, this is not generally as pronounced as cm-2 - production from amides. The most notable occurrence of an amide-specific product ion is for laminin amide (YIGSR-NH2) and this case was investigated using several modified peptides. Mechanisms involving 6- and 9-membered ring formation were proposed, and their energetic properties were investigated using G3(MP2) molecular orbital theory calculations. For example, with C-terminal deprotonation of pentaglycine amide, formation of cm-2 - and a 6-membered ring diketopiperazine neutral requires >31.6 kcal/mol, which is 26.1 kcal/mol less than the analogous process involving the peptide acid. The end group specific fragmentation of peptide amides in the negative ion mode may be useful for identifying such groups in proteomic applications.

  12. Combination of Peptide YY3–36 with GLP-17–36 amide Causes an Increase in First-Phase Insulin Secretion after IV Glucose

    Science.gov (United States)

    Tan, Tricia M.; Salem, Victoria; Troke, Rachel C.; Alsafi, Ali; Field, Benjamin C. T.; De Silva, Akila; Misra, Shivani; Baynes, Kevin C. R.; Donaldson, Mandy; Minnion, James; Ghatei, Mohammad A.; Godsland, Ian F.

    2014-01-01

    Context: The combination of peptide YY (PYY) and glucagon-like peptide-1 (GLP-1) has been proposed as a potential treatment for diabetes and obesity. However, the combined effects of these hormones, PYY3–36 and GLP-17–36 amide, on glucose homeostasis are unknown. Objective: This study sought to investigate the acute effects of PYY3–36 and GLP-17–36 amide, individually and in combination, on insulin secretion and sensitivity. Setting and Design: Using a frequently sampled iv glucose tolerance test (FSIVGTT) and minimal modeling, this study measured the effects of PYY3–36 alone, GLP-17–36 amide alone, and a combination of PYY3–36 and GLP-17–36 amide on acute insulin response to glucose (AIRg) and insulin sensitivity index (SI) in 14 overweight human volunteers, studied in a clinical research facility. Results: PYY3–36 alone caused a small but nonsignificant increase in AIRg. GLP-17–36 amide alone and the combination of PYY3–36 and GLP-17–36 amide did increase AIRg significantly. No significant differences in SI were observed with any intervention. Conclusions: PYY3–36 lacks any significant acute effects on first-phase insulin secretion or SI when tested using an FSIVGTT. Both GLP-17–36 amide alone and the combination of PYY3–36 and GLP-17–36 amide increase first-phase insulin secretion. There does not seem to be any additive or synergistic effect between PYY3–36 and GLP-17–36 amide on first-phase insulin secretion. Neither hormone alone nor the combination had any significant effects on SI. PMID:25144632

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

    Energy Technology Data Exchange (ETDEWEB)

    Kumaran, R., E-mail: kumaranwau@rediffmail.com [Department of Chemistry, Dwaraka Doss Goverdhan Doss Vaishnav College, Arumbakkam, Chennai 600106 (India); Ramamurthy, P. [National Centre for Ultrafast Processes, University of Madras, Sekhizar Campus, Taramani, Chennai 600113 (India)

    2014-04-15

    Addition. of amides containing a H-CO(NH{sub 2}) or CH{sub 3}-CO(NH{sub 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{sub 3}){sub 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{sub 2})), whereas a shift in the emission maximum only towards the red region results on the addition of acetamide (CH{sub 3}-CONH{sub 2}). Steady state emission spectral studies reveal that amides that possess a free NH{sub 2} and N(CH{sub 3}){sub 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 DMFamides. Amides act as a hydrogen-bonding donor and acceptor resulting in a hydrogen-bonding interaction with amino and carboxy moieties (amino acids) present in BSA. The fact that the –NH{sub 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:

  14. Kinetic Study of the Reaction of the Phthalimide-N-oxyl Radical with Amides: Structural and Medium Effects on the Hydrogen Atom Transfer Reactivity and Selectivity.

    Science.gov (United States)

    Bietti, Massimo; Forcina, Veronica; Lanzalunga, Osvaldo; Lapi, Andrea; Martin, Teo; Mazzonna, Marco; Salamone, Michela

    2016-12-02

    A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of secondary N-(4-X-benzyl)acetamides and tertiary amides to the phthalimide-N-oxyl radical (PINO) has been carried out. The results indicate that HAT is strongly influenced by structural and medium effects; in particular, the addition of Brønsted and Lewis acids determines a significant deactivation of C-H bonds α to the amide nitrogen of these substrates. Thus, by changing the reaction medium, it is possible to carefully control the regioselectivity of the aerobic oxidation of amides catalyzed by N-hydroxyphthalimide, widening the synthetic versatility of this process.

  15. 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

    Directory of Open Access Journals (Sweden)

    Ling-Na Wang

    2016-06-01

    Full Text Available 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.

  16. A conceptual DFT approach towards analysing feasibility of the intramolecular cycloaddition Diels-Alder reaction of triene amide in Lewis acid catalyst

    Indian Academy of Sciences (India)

    ABDELILAH BENALLOU; HABIB EL ALAOUI EL ABDALLAOUI; HOCINE GARMES

    2016-09-01

    The effect of Lewis acid catalysts, TiCl₄ and Et₂AlCl on the intramolecular cycloaddition Diels- Alder (IMDA) reaction of triene-amide have been studied theoretically using the DFT (Density Functional Theory) at the 6-31G(d,p) level of theory. The results obtained using the polar model of Domingo, electrophilicity, nucleophilicity indices and thermochemistry computations, demonstrate that these catalysts are coordinated with more nucleophilic atoms of diene fragment (nitrogen and oxygen of amide group). These catalysts affect negatively the feasibility of the reaction as well as the physico-chemical parameters of the IMDA reaction of triene-amide.

  17. Anion complexation with cyanobenzoyl substituted first and second generation tripodal amide receptors: crystal structure and solution studies.

    Science.gov (United States)

    Hoque, Md Najbul; Gogoi, Abhijit; Das, Gopal

    2015-09-14

    Anion complexation properties of two new tripodal amide receptors have been extensively studied here. Two tripodal receptors have been synthesized from the reaction of cyanobenzoyl acid chloride with two tri-amine building blocks such as (i) tris(2-aminoethyl)amine and (ii) tris(2-(4-aminophenoxy)ethyl)amine, which resulted in the first (L1) and second (L2) generation tripodal amides respectively. A detailed comparison of their coordination behavior with anions is also described by crystallographic and solution state experiments. The crystal structure demonstrates various types of spatial orientations of tripodal arms in two receptors and concomitantly interacts with anions distinctively. Intramolecular H-bonding between amide N–H and CO prevents opening of the receptor cavity in the crystal, which leads to a locked conformation of L1 having C(3v) symmetry and makes amide hydrogen unavailable for the anion which results in side cleft anion binding. However, in L2 we conveniently shift the anion binding sites to a distant position which increases cavity size as well as rules out any intramolecular H-bonding between amide N–H and CO. The crystal structure shows a different orientation of the arms in L2; it adopts a quasi-planar arrangement with C(2v) symmetry. In the crystal structure two arms are pointed in the same direction and while extending the contact the third arm is H-bonded with the apical N-atom through a –CN group, making a pseudo capsular cavity where the anion interacts. Most importantly spatial reorientation of the receptor L2 from a C(2v) symmetry to a folded conformation with a C(3v) symmetry was observed only in the presence of an octahedral SiF6(2-) anion and forms a sandwich type complex. Receptors L1 and L2 are explored for their solution state anion binding abilities. The substantial changes in chemical shifts were observed for the amide (-NH) and aromatic hydrogen (-CH) (especially for F(-)), indicating the role of these hydrogens in

  18. Halide, amide, cationic, manganese carbonylate, and oxide derivatives of triamidosilylamine uranium complexes.

    Science.gov (United States)

    Gardner, Benedict M; Lewis, William; Blake, Alexander J; Liddle, Stephen T

    2011-10-03

    Treatment of the complex [U(Tren(TMS))(Cl)(THF)] [1, Tren(TMS) = N(CH(2)CH(2)NSiMe(3))(3)] with Me(3)SiI at room temperature afforded known crystalline [U(Tren(TMS))(I)(THF)] (2), which is reported as a new polymorph. Sublimation of 2 at 160 °C and 10(-6) mmHg afforded the solvent-free dimer complex [{U(Tren(TMS))(μ-I)}(2)] (3), which crystallizes in two polymorphic forms. During routine preparations of 1, an additional complex identified as [U(Cl)(5)(THF)][Li(THF)(4)] (4) was isolated in very low yield due to the presence of a slight excess of [U(Cl)(4)(THF)(3)] in one batch. Reaction of 1 with one equivalent of lithium dicyclohexylamide or bis(trimethylsilyl)amide gave the corresponding amide complexes [U(Tren(TMS))(NR(2))] (5, R = cyclohexyl; 6, R = trimethylsilyl), which both afforded the cationic, separated ion pair complex [U(Tren(TMS))(THF)(2)][BPh(4)] (7) following treatment of the respective amides with Et(3)NH·BPh(4). The analogous reaction of 5 with Et(3)NH·BAr(f)(4) [Ar(f) = C(6)H(3)-3,5-(CF(3))(2)] afforded, following addition of 1 to give a crystallizable compound, the cationic, separated ion pair complex [{U(Tren(TMS))(THF)}(2)(μ-Cl)][BAr(f)(4)] (8). Reaction of 7 with K[Mn(CO)(5)] or 5 or 6 with [HMn(CO)(5)] in THF afforded [U(Tren(TMS))(THF)(μ-OC)Mn(CO)(4)] (9); when these reactions were repeated in the presence of 1,2-dimethoxyethane (DME), the separated ion pair [U(Tren(TMS))(DME)][Mn(CO)(5)] (10) was isolated instead. Reaction of 5 with [HMn(CO)(5)] in toluene afforded [{U(Tren(TMS))(μ-OC)(2)Mn(CO)(3)}(2)] (11). Similarly, reaction of the cyclometalated complex [U{N(CH(2)CH(2)NSiMe(2)Bu(t))(2)(CH(2)CH(2)NSiMeBu(t)CH(2))}] with [HMn(CO)(5)] gave [{U(Tren(DMSB))(μ-OC)(2)Mn(CO)(3)}(2)] [12, Tren(DMSB) = N(CH(2)CH(2)NSiMe(2)Bu(t))(3)]. Attempts to prepare the manganocene derivative [U(Tren(TMS))MnCp(2)] from 7 and K[MnCp(2)] were unsuccessful and resulted in formation of [{U(Tren(TMS))}(2)(μ-O)] (13) and [MnCp(2)]. Complexes 3-13 have been

  19. Homochiral coordination polymers constructed from aminocarboxylate derivates: Effect of bipyridine on the amidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Chen Jianshan; Sheng Tianlu; Hu Shengmin; Xiang Shengchang; Fu Ruibiao; Zhu Qilong [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Wu Xintao, E-mail: wxt@fjirsm.ac.cn [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

    2012-08-15

    Using aminocarboxylate derivates (S)-N-(4-cyanobenzoic)-glutamic acid (denoted as cbg, 1a) and (S)-N-(4-nitrobenzoic)-glutamic acid (denoted as nbg, 1b) as chiral ligands, five new homochiral coordination polymers formulated as [Cu(cbg)(H{sub 2}O){sub 2}]{sub n} (3), [Cu(cbop){sub 2}(4,4 Prime -bipy)(H{sub 2}O)]{sub n} (4) (cbop=(S)-N-(4-cyanobenzoic)-5-oxoproline, 4,4 Prime -bipy=4,4 Prime -bipyridine), {l_brace}[Cu(nbop){sub 2}(4,4 Prime -bipy)]{center_dot}4H{sub 2}O{r_brace}{sub n} (5) (nbop=(S)-N-(4-nitrobenzoic)-5-oxoproline), {l_brace}[Cd(nbop){sub 2}(4,4 Prime -bipy)]{center_dot}2H{sub 2}O{r_brace}{sub n} (6), and [Ni(nbop){sub 2}(4,4 Prime -bipy)(H{sub 2}O){sub 2}]{sub n} (7) have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction study reveals that the original chirality of aminocarboxylate derivates is maintained in all these complexes. Complexes 3, 4, and 7 are one-dimensional infinite chain coordination polymers, while complexes 5 and 6 possess two-dimensional network structures. In situ cyclization of 1a and 1b was taken place in the formation of complexes 4-7, which may be due to the competition of 4,4 Prime -bipyridine with chiral ligands during the coordination process. Preliminary optical behavior investigation indicates that ligands 1a, 1b, and complexes 6, 7 are nonlinear optical active. - Graphical abstract: Using aminocarboxylate derivates as chiral ligands, five new homochiral coordination polymers possessing second harmonic generation activities have been hydrothermally synthesized. Highlights: Black-Right-Pointing-Pointer Two new chiral aminocarboxylate derivates were firstly synthesized. Black-Right-Pointing-Pointer Five new homochiral metal organic complexes were obtained hydrothermally based on these ligands. Black-Right-Pointing-Pointer Intramolecular amidation was taken place on the aminocarboxylate derivates during the formation of these complexes. Black-Right-Pointing-Pointer In situ

  20. Paracellular permeation-enhancing effect of AT1002 C-terminal amidation in nasal delivery

    Directory of Open Access Journals (Sweden)

    Song KH

    2015-03-01

    Full Text Available Keon-Hyoung Song,1 Sang-Bum Kim,2 Chang-Koo Shim,2 Suk-Jae Chung,2 Dae-Duk Kim,2 Sang-Ki Rhee,1 Guang J Choi,1 Chul-Hyun Kim,3 Kiyoung Kim4 1Department of Pharmaceutical Engineering, Soonchunhyang University, Asan, Republic of Korea; 2College of Pharmacy and Research Institute of Pharmaceutical Sciences, Seoul National University, Seoul, Republic of Korea; 3Department of Sports Medicine, 4Department of Medical Biotechnology, Soonchunhyang University, Asan, Republic of Korea Background: The identification of permeation enhancers has gained interest in the development of drug delivery systems. A six-mer peptide, H-FCIGRL-OH (AT1002, is a tight junction modulator with promising permeation-enhancing activity. AT1002 enhances the transport of molecular weight markers or agents with low bioavailability with no cytotoxicity. However, AT1002 is not stable in neutral pH or after incubation under physiological conditions, which is necessary to fully uncover its permeation-enhancing effect. Thus, we increased the stability or mitigated the instability of AT1002 by modifying its terminal amino acids and evaluated its subsequent biological activity.Methods: C-terminal-amidated (FCIGRL-NH2, Pep1 and N-terminal-acetylated (Ac-FCIGRL, Pep2 peptides were analyzed by liquid chromatography–mass spectrometry. We further assessed cytotoxicity on cell monolayers, as well as the permeation-enhancing activity following nasal administration of the paracellular marker mannitol.Results: Pep1 was nontoxic to cell monolayers and showed a relatively low decrease in peak area compared to AT1002. In addition, administration of mannitol with Pep1 resulted in significant increases in the area under the plasma concentration–time curve and peak plasma concentration at 3.63-fold and 2.68-fold, respectively, compared to mannitol alone. In contrast, no increase in mannitol concentration was shown with mannitol/AT1002 or mannitol/Pep2 compared to the control. Thus, Pep1 increased

  1. Pharmacokinetics and metabolism studies on the glucagon-like peptide-1 (GLP-1)-derived metabolite GLP-1(9-36)amide in male Beagle dogs.

    Science.gov (United States)

    Eng, Heather; Sharma, Raman; McDonald, Thomas S; Landis, Margaret S; Stevens, Benjamin D; Kalgutkar, Amit S

    2014-09-01

    Glucagon-like peptide-1 (GLP-1)(7-36)amide is a 30-amino acid peptide hormone that is secreted from intestinal enteroendocrine L-cells in response to nutrients. GLP-1(7-36)amide possesses potent insulinotropic actions in the augmentation of glucose-dependent insulin secretion. GLP-1(7-36)amide is rapidly metabolized by dipeptidyl peptidase-IV to yield GLP-1(9-36)amide as the principal metabolite. Contrary to the earlier notion that peptide cleavage products of native GLP-1(7-36)amide [including GLP-1(9-36)amide] are pharmacologically inactive, recent studies have demonstrated cardioprotective and insulinomimetic effects with GLP-1(9-36)amide in mice, dogs and humans. In the present work, in vitro metabolism and pharmacokinetic properties of GLP-1(9-36)amide have been characterized in dogs, since this preclinical species has been used as an animal model to demonstrate the in vivo vasodilatory and cardioprotective effects of GLP-1(9-36)amide. A liquid chromatography tandem mass spectrometry assay was developed for the quantitation of the intact peptide in hepatocyte incubations as opposed to a previously reported enzyme-linked immunosorbent assay. Although GLP-1(9-36)amide was resistant to proteolytic cleavage in dog plasma and bovine serum albumin (t1/2>240 min), the peptide was rapidly metabolized in dog hepatocytes with a t1/2 of 110 min. Metabolite identification studies in dog hepatocytes revealed a variety of N-terminus cleavage products, most of which, have also been observed in human and mouse hepatocytes. Proteolysis at the C-terminus was not observed in GLP-1(9-36)amide. Following the administration of a single intravenous bolus dose (20 µg/kg) to male Beagle dogs, GLP-1(9-36)amide exhibited a mean plasma clearance of 15 ml/min/kg and a low steady state distribution volume of 0.05 l/kg, which translated into a short elimination half life of 0.05 h. Following subcutaneous administration of GLP-1(9-36)amide at 50 µg/kg, systemic exposure of

  2. 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...

  3. Synthesis of Eu(Ⅲ) and Tb(Ⅲ) Complexes with New Aryl Amide Type Tetrapodal Ligand and Their Luminescence Properties

    Institute of Scientific and Technical Information of China (English)

    蔡正洪; 谭民裕

    2002-01-01

    A new aryl amide type tetrapodal ligand L (1, 1, 1, 1-tetrakis-{[(2-benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.

  4. H-Bonding Self-assembled Template-directed Synthesis of a Reactive Amide-bridged Ladder Polyvinylsiloxane

    Institute of Scientific and Technical Information of China (English)

    You Zhi WAN; Ying Hua LIU; Ping XIE; Rong Ben ZHANG

    2006-01-01

    A novel, reactive amide-bridged ladder polyvinylsiloxane (abbr. LP) with Mn = 2.4×104was synthesized for the first time by means of aryl amide H-bonding self-assembled template.The regularity of LP was characterized by the XRD, 29Si NMR and DSC methods. XRD analysis demonstrated the ladder width w = 9.09 A and the ladder thickness t = 3.89 A, respectively, which are approximately consistent with the molecular simulation-calculated ones: w'= 10.60 A and t'=3.06 A. 29Si NMR displayed a resonance peak with small half peak width, △1/2 ~ 4 ppm, for the moiety [=Si(Vi)O2/2-]n of LP. Besides, as a collateral evidence, DSC measurement revealed a high glass transition temperature Tg = 225℃, suggesting high stiffness of the ladder main chain of LP.

  5. Palladium-Catalyzed N-Alkylation of Amides and Amines with Alcohols Employing the Aerobic Relay Race Methodology

    Institute of Scientific and Technical Information of China (English)

    余小春; 姜澜; 李强; 谢嫒媛; 徐清

    2012-01-01

    Possibly because homogeneous palladium catalysts are not typical borrowing hydrogen catalysts and ligands are thus ineffective in catalyst activation under conventional anaerobic conditions, they had not been used in the N-alkylation reactions of amines/amides with alcohols in the past. By employing the aerobic relay race methodol- ogy with Pd-catalyzed aerobic alcohol oxidation being a more effective protocol for alcohol activation, ligand-free homogeneous palladiums are successfully used as active catalysts in the dehydrative N-alkylation reactions, giving high yields and selectivities of the alkylated amides and amines. Mechanistic studies implied that the reaction most probably proceeds via the novel relay race mechanism we recently discovered and proposed.

  6. Design, Synthesis and Antimycobacterial Activity of Novel Imidazo[1,2-a]pyridine Amide-Cinnamamide Hybrids.

    Science.gov (United States)

    Li, Linhu; Li, Zhuorong; Liu, Mingliang; Shen, Weiyi; Wang, Bin; Guo, Huiyuan; Lu, Yu

    2015-12-30

    We report herein the design and synthesis of a series of novel imidazo[1,2-a]pyridine amide-cinnamamide hybrids linked via an alkyl carbon chain. All 38 new hybrids were evaluated for their antimycobacterial activity against M. tuberculosis (MTB) H37Rv ATCC 27294 using the microplate Alamar Blue assay (MABA). Although the hybrids are less active than the two reference compounds, the promising activity (MICs: 4 μg/mL) of 2,6-dimethylimidazo[1,2-a]pyridine amide-cinnamamide hybrids 11e and 11k could be a good starting point to further find new lead compounds against multi-drug-resistant tuberculosis.

  7. Dianthosaponins A-F, triterpene saponins, flavonoid glycoside, aromatic amide glucoside and γ-pyrone glucoside from Dianthus japonicus.

    Science.gov (United States)

    Nakano, Takahiro; Sugimoto, Sachiko; Matsunami, Katsuyoshi; Otsuka, Hideaki

    2011-01-01

    From aerial parts of Dianthus japonicus, six new and seven known oleanane-type triterpene saponins were isolated. The structures of the new saponins, named dianthosaponins A-F, were elucidated by means of high resolution mass spectrometry, and extensive inspection of one- and two-dimensional NMR spectroscopic data. A new C-glycosyl flavone, a glycosidic derivative of anthranilic acid amide and a maltol glucoside were also isolated.

  8. Isolation and Total Synthesis of Stolonines A–C, Unique Taurine Amides from the Australian Marine Tunicate Cnemidocarpa stolonifera

    OpenAIRE

    Trong D. Tran; Ngoc B. Pham; Merrick Ekins; Hooper, John N. A.; Quinn, Ronald J.

    2015-01-01

    Cnemidocarpa stolonifera is an underexplored marine tunicate that only occurs on the tropical to subtropical East Coast of Australia, with only two pyridoacridine compounds reported previously. Qualitative analysis of the lead-like enhanced fractions of C. stolonifera by LC-MS dual electrospray ionization coupled with PDA and ELSD detectors led to the identification of three new natural products, stolonines A–C (1–3), belonging to the taurine amide structure class. Structures of the new compo...

  9. Tertiary amides of Salinomycin: A new group of antibacterial agents against Bacillus anthracis and methicillin-resistant Staphylococcus epidermidis.

    Science.gov (United States)

    Stefańska, Joanna; Antoszczak, Michał; Stępień, Karolina; Bartoszcze, Michał; Mirski, Tomasz; Huczyński, Adam

    2015-01-01

    For the first time, a series of tertiary amides of polyether antibiotic-Salinomycin have been obtained and screened for their antibacterial activity against different strains of bacteria, including Bacillus anthracis and clinical methicillin-resistant Staphylococcus epidermidis (MRSE). Moreover, biofilm inhibition of MRSE and genotoxicity tests against Bacillus subtilis have been performed. Our studies show that Salinomycin and its some derivatives are active against tested bacteria and exhibited definitely bacteriostatic, not bactericidal activity.

  10. Cationic Group 3 Alkyl Complexes with Isopropyl-Substituted Triazacyclononane-amide Ligands : Synthesis, Structure, and Thermal Decomposition Processes

    NARCIS (Netherlands)

    Bambirra, Sergio; Meetsma, Auke; Hessen, Bart; Bruins, Andries P.

    2006-01-01

    Yttrium and lanthanum dialkyl complexes with the isopropyl-substituted triazacyclononane-amide monoanionic ligands [iPr2TACN-(B)-NtBu] (B = (CH2)2, L1; SiMe2, L2) are described. For Y, these were obtained by reaction of Y(CH2SiMe3)2(THF)2 with HL, whereas for La in situ peralkylation of LaBr3(THF)4

  11. P4 capped amides and lactams as HCV NS3 protease inhibitors with improved potency and DMPK profile

    Energy Technology Data Exchange (ETDEWEB)

    Nair, Latha G.; Sannigrahi, Mousumi; Bogen, Stephane; Pinto, Patrick; Chen, Kevin X.; Prongay, Andrew; Tong, Xiao; Cheng, K.-C.; Girijavallabhann, Viyyoor; Njoroge, F. George (Merck)

    2010-09-03

    SAR studies on the extension of P3 unit of Boceprevir (1, SCH 503034) with amides and lactams and their synthesis is described. Extensive SAR studies resulted in the identification of 36 bearing 4,4-dimethyl lactam as the new P4 cap unit with improved potency (K*{sub i}, EC 90 = 70 nM) and pharmacokinetic properties (Rat AUC (PO) = 3.52 {micro}M h) compared to 1.

  12. Microwave Assisted Synthesis Spectral and Antibacterial Investigations on Complexes of Mn(II) With Amide Containing Ligands

    OpenAIRE

    N. Bhojak; D. D. Gudasaria; N. Khiwani; Jain, R.

    2007-01-01

    The present research work describes the synthesis, spectral and antibacterial studies on the complexes of Mn(II) with amide group containing ligands. Synthesis of complexes has been carried out by conventional method as well as by microwave method. The complexes have been characterized on the basis of elemental analysis, infrared, electronic spectra and magnetic susceptibility studies. The diffuse reflectance spectrums of the complexes show bands in the region 20,000 cm-1 to 26,000 cm-1 ass...

  13. 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....

  14. Solid phase synthesis of fatty acid modified glucagon-like peptide-1(7-36) amide under thermal and controlled microwave irradiation

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Fatty acid modified glucagon-like peptide-1(7-36) amide was synthesized efficiently on Rink-Amide-MBHA resin by microwave-assisted solid phase method.The method of thermal and controlled microwave irradiation provided impressive enhancements in product yield,selectivity,and reaction rate.The coupling time was dramatically decreased to 6 min,and the desired products were obtained in high yield and purity.

  15. 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.

  16. Unravelling exceptional acetylene and carbon dioxide adsorption within a tetra-amide functionalized metal-organic framework

    Science.gov (United States)

    Moreau, Florian; da Silva, Ivan; Al Smail, Nada H.; Easun, Timothy L.; Savage, Mathew; Godfrey, Harry G. W.; Parker, Stewart F.; Manuel, Pascal; Yang, Sihai; Schröder, Martin

    2017-01-01

    Understanding the mechanism of gas-sorbent interactions is of fundamental importance for the design of improved gas storage materials. Here we report the binding domains of carbon dioxide and acetylene in a tetra-amide functionalized metal-organic framework, MFM-188, at crystallographic resolution. Although exhibiting moderate porosity, desolvated MFM-188a exhibits exceptionally high carbon dioxide and acetylene adsorption uptakes with the latter (232 cm3 g−1 at 295 K and 1 bar) being the highest value observed for porous solids under these conditions to the best of our knowledge. Neutron diffraction and inelastic neutron scattering studies enable the direct observation of the role of amide groups in substrate binding, representing an example of probing gas-amide binding interactions by such experiments. This study reveals that the combination of polyamide groups, open metal sites, appropriate pore geometry and cooperative binding between guest molecules is responsible for the high uptakes of acetylene and carbon dioxide in MFM-188a. PMID:28176793

  17. 酰胺类阴离子受体的研究进展%Research on the amide anion receptors

    Institute of Scientific and Technical Information of China (English)

    李玉玲; 刘克成; 孙红先; 李闯

    2012-01-01

    阴离子识别是现代化学重要的研究内容之一,其关键环节是构筑可识别阴离子的结合受体,以非共价键力如静电作用、疏水作用、氢键等与阴离子结合.本文主要评述了芳香酰胺类受体分子和杂环酰胺类受体分子两种酰胺类受体的合成及其在阴离子识别中的应用.%The recognition and sensing of anion have been developed into an important research subject in modern chemistry.Its key link is the combination of constructing identifiable anions in a covalent bond,the receptor electrostatic interactions,such as force of hydrophobic functions,hydrogen anion binding.The paper mainly reviews the following two amide class receptors in their synthesis and application of anionic recognition:(1) the balmy amide receptor molecules,(2) heterocyclic amide receptor molecules.

  18. Phenyl amide linker improves the pharmacokinetics and pharmacodynamics of N-terminally mono-PEGylated human growth hormone.

    Science.gov (United States)

    Wu, Ling; Ji, Shaoyang; Shen, Lijuan; Hu, Tao

    2014-09-02

    Human growth hormone (hGH) suffers from a short plasma half-life of ∼15 min, necessitating frequent injections to maintain its physiological effect. PEGylation, conjugation of polyethylene glycol (PEG), is an effective strategy to prolong the plasma half-life of hGH. However, PEGylation can significantly decrease the bioactivity of hGH. Thus, a new PEGylation approach is desired to improve the pharmacokinetics (PK) and pharmacodynamics (PD) of the PEGylated hGH. In the present study, two N-terminally mono-PEGylated hGHs were prepared using aldehyde chemistry. Phenyl amide and ethyl moieties were used as the linkers between PEG and hGH, respectively. The hydrodynamic volume, proteolytic sensitivity, and immunogenicity of the PEGylated hGH with phenyl amide linker (hGH-phenyl-PEG) were lower than those of the one with propyl linker (hGH-prop-PEG). In addition, hGH-phenyl-PEG showed a higher in vitro bioactivity and better PK and PD than hGH-prop-PEG. The better PK of hGH-phenyl-PEG was mainly due to its lower proteolytic sensitivity and low immunogenicity. The better PD of hGH-phenyl-PEG was mainly due to its higher in vitro bioactivity. Thus, the phenyl amide linker can improve the overall pharmacological profiles of the PEGylated hGH. Our study is expected to advance the development of long-acting protein biotherapeutics with high therapeutic efficacy.

  19. Synthesis and structural studies of amino amide salts derived from 2-(aminomethyl)benzimidazole and α-amino acids

    Science.gov (United States)

    Avila-Montiel, Concepción; Tapia-Benavides, Antonio R.; Falcón-León, Martha; Ariza-Castolo, Armando; Tlahuext, Hugo; Tlahuextl, Margarita

    2015-11-01

    2-{[(Ammoniumacetyl)amino]methyl}-1H-benzimidazol-3-ium dichloride 4, 2-{[(2-ammoniumpropanoyl)amino]methyl}-1H-benzimidazol-3-ium dichloride 5, and 2-{[(2-ammonium-3-phenylpropanoyl)amino]methyl}-1H-benzimidazol-3-ium dichloride 6 amino amides were synthesized via condensation of 2AMBZ dihydrochloride with the corresponding amino acid. Compounds 7-12 were obtained by replacing chloride ions (in salts 4-6) with nitrate or tetrachlorozincate ions. The results of X-ray diffraction crystallographic studies indicated that the geometries, charges and sizes of the anions are essential for the formation of the strong hydrogen bond interactions of compounds 4, 5, 9-12. Moreover, in most cases, the presence of water and solvent molecules stabilizes the supramolecular structures of these compounds. Nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy indicated that the presence of chloride or tetrachlorozincate anions increases the acidity of the benzimidazolic and amide groups more significantly than the presence of nitrate anions. However, Quantum Theory of Atoms in Molecules (QTAIM) computations of the crystal structures demonstrate that amino amides interact more strongly with NO3- than with Cl- and ZnCl42- anions; this difference explains the spectroscopic results.

  20. Quantitative and structural analysis of amides and lignans in Zanthoxylum armatum by UPLC-DAD-ESI-QTOF-MS/MS.

    Science.gov (United States)

    Kumar, Vishal; Kumar, Shiv; Singh, Bikram; Kumar, Neeraj

    2014-06-01

    A rapid and simple ultra performance liquid chromatography-diode array detection (UPLC-DAD) method has been developed for the simultaneous quantification of four biologically important furofuran lignans, asarinin, sesamin, fargesin and kobusin, and an amide, armatamide in Zanthoxylum armatum within 7min. The separation was carried out on a BEH C18 column (2.1mm×100mm, 1.7μm particle size) with 0.05% formic acid aqueous solution and acetonitrile as mobile phase under gradient conditions at 25°C. The method was validated and found to be linear (R(2)≥0.9997), precise in terms of peak areas (intra-day RSDs≤0.62% and inter-day RSDs≤2.95%) and accurate (95.6-104.0%). The developed method was applied to the quality assessment of different parts (leaves, bark and seeds) of Z. armatum including locational variation of leaves samples. Significant variation in the amount of amides and furofuran lignans was observed. Tandem electrospray ionization-mass spectrometry (UPLC-DAD-ESI-MS/MS) of samples led to the identification of sixteen compounds in the category of amides and furofuran lignans.

  1. Surface modification of polypiperazine-amide membrane by self-assembled method for dye wastewater treatment☆

    Institute of Scientific and Technical Information of China (English)

    Yong Zhou; Zhenan Dai; Ding Zhai; Congjie Gao

    2015-01-01

    Polypiperazine-amide membranes were modified with poly(ethyleneimine) (PEI) by self-assembled method, through which PEI molecules were fixed on the membrane surface by ionic interaction. In the experiments, the PEI concentration ranged from 50 to 2000 mg·L−1 while the depositing time was fixed at 20 min. The results showed that low PEI concentration resulted in a slight increase of pure water flux, which was attributed to the enhanced membrane surface hydrophilicity. The PEI adsorption on membrane surface had less effect on the re-jections to neutral PEG and sucrose, but improved the rejections to divalent cationic ions and methylene blue as the result of reversion of the membrane surface charge from negative to positive according to the XPS analysis and zeta potential measurements. The membrane modified at PEI=1500 mg·L−1 exhibited high rejection to methylene blue (MB) and is potential to be applied in the treatment of effluents containing positively charged dyes.

  2. Polyvinyl acetate/poly(amide-12-b-ethylene oxide) blend membranes for carbon dioxide separation

    Institute of Scientific and Technical Information of China (English)

    Shichao; Feng; Jizhong; Ren; Hui; Li; Kaisheng; Hua; Xinxue; Li; Maicun; Deng

    2013-01-01

    In this paper,blend membranes from polyvinyl acetate(PVAc)and block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074)are prepared by solution casting and solvent evaporation method.Although they are homogeneous on a macro-scale,the observations from DSC and SEM indicate micro-phase separation for PVAc/Pebax1074 blend membranes.With the increase of Pebax1074 content,gas permeabilities of CO2,H2,N2and CH4all increase greatly.PVAc/Pebax1074 blend membranes with high PVAc content are appropriate for CO2/CH4separation.The temperature dependence of gas permeability is divided into rubbery region and glassy region.The activation energies of permeation in rubbery region are smaller than those in glassy region,and they all decrease with increasing Pebax1074 content.For N2,H2and CH4,their gas permeation properties are mainly influenced by the dual-mode sorption and hydrostatic pressure effect.But for CO2,its permeability increases with the increase of pressure due to CO2-induced plasticization effect,which is more obvious for PVAc/Pebax1074 blend membranes with high PVAc content.

  3. Crystal structure of glycidamide: the mutagenic and genotoxic metabolite of acryl-amide.

    Science.gov (United States)

    Hemgesberg, Melanie N; Bonck, Thorsten; Merz, Karl-Heinz; Sun, Yu; Schrenk, Dieter

    2016-08-01

    The title compound, glycidamide (systematic name: oxirane-2-carboxamide), C3H5NO2, is the mutagenic and genotoxic metabolite of acryl-amide, a food contaminant and industrial chemical that has been classified as being probably carcinogenic to humans. Synthesized via the reaction of acrylo-nitrile and hydrogen peroxide, it crystallizes with both enanti-omers occurring as two crystallographically independent mol-ecules (A and B) in the asymmetric unit. They have similar conformations with an r.m.s. deviation of 0.0809 Å for mol-ecule B inverted on mol-ecule A. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds, which lead to the formation of β-sheet structures enclosing R 2 (2)(8) and R 4 (2)(8) loops. The β-sheets are linked by weaker C-H⋯O hydrogen bonds, forming a supra-molecular three-dimensional structure.

  4. Genetic engineering activates biosynthesis of aromatic fumaric acid amides in the human pathogen Aspergillus fumigatus.

    Science.gov (United States)

    Kalb, Daniel; Heinekamp, Thorsten; Lackner, Gerald; Scharf, Daniel H; Dahse, Hans-Martin; Brakhage, Axel A; Hoffmeister, Dirk

    2015-03-01

    The Aspergillus fumigatus nonribosomal peptide synthetase FtpA is among the few of this species whose natural product has remained unknown. Both FtpA adenylation domains were characterized in vitro. Fumaric acid was identified as preferred substrate of the first and both l-tyrosine and l-phenylalanine as preferred substrates of the second adenylation domain. Genetically engineered A. fumigatus strains expressed either ftpA or the regulator gene ftpR, encoded in the same cluster of genes, under the control of the doxycycline-inducible tetracycline-induced transcriptional activation (tet-on) cassette. These strains produced fumaryl-l-tyrosine and fumaryl-l-phenylalanine which were identified by liquid chromatography and high-resolution mass spectrometry. Modeling of the first adenylation domain in silico provided insight into the structural requirements to bind fumaric acid as peptide synthetase substrate. This work adds aromatic fumaric acid amides to the secondary metabolome of the important human pathogen A. fumigatus which was previously not known as a producer of these compounds.

  5. Amide proton transfer-weighted MRI detection of traumatic brain injury in rats.

    Science.gov (United States)

    Zhang, Hong; Wang, Wenzhu; Jiang, Shanshan; Zhang, Yi; Heo, Hye-Young; Wang, Xianlong; Peng, Yun; Wang, Jian; Zhou, Jinyuan

    2017-01-01

    The purpose of this study was to explore the capability and uniqueness of amide proton transfer-weighted (APTw) imaging in the detection of primary and secondary injury after controlled cortical impact (CCI)-induced traumatic brain injury (TBI) in rats. Eleven adult rats had craniotomy plus CCI surgery under isoflurane anesthesia. Multi-parameter MRI data were acquired at 4.7 T, at eight time points (1, 6 h, and 1, 2, 3, 7, 14, and 28 days after TBI). At one and six hours post-injury, average APTw signal intensities decreased significantly in the impacted and peri-lesional areas due to tissue acidosis. A slightly high APTw signal was seen in the core lesion area with respect to the peri-lesional area, which was due to hemorrhage, as shown by T2*w. After the initial drop, the APTw signals dramatically increased in some peri-lesional areas at two and three days post-injury, likely due to the secondary inflammatory response. The use of APTw MRI has the potential to introduce a novel molecular neuroimaging approach for the simultaneous detection of ischemia, hemorrhage, and neuroinflammation in TBI.

  6. Improved speciation of dissolved organic nitrogen in natural waters: amide hydrolysis with fluorescence derivatization

    Institute of Scientific and Technical Information of China (English)

    Ryan L.Firnmen; Tamara D.Trouts; Daniel D.Richter Jr.; Dharni Vasudevan

    2008-01-01

    The objective of this study was to improve primary-amine nitrogen (1°-N) quantification in dissolved organic matter (DOM)originating from natural waters where inorganic forms of N, which may cause analytical interference, are commonly encountered.Efforts were targeted at elucidating organic-N structural criteria influencing the response of organic amines to known colorimetric andfluorescent reagents and exploring the use of divalent metal-assisted amide hydrolysis in combination with fluorescence analyses.We found that reaction of o-phthaldialdehyde (OPA) with primary amines is significantly influenced by steric factors, whereasfluorescamine (FLU) lacks sensitivity to steric factors and allows for the detection of a larger suite of organic amines, includingdi- and tri-peptides and sterically hindered 1°-N. Due to the near quantitative recovery of dissolved peptides with the FLU reagent andlack of analytical response to inorganic nitrogen, we proposed that FLU be utilized for the quantification of primary amine nitrogen.In exploring the application of divalent metal promoted peptide hydrolysis to the analysis of organic forms of nitrogen in DOM, wefound that Zn(Ⅱ) reaction increased the total fraction of organic-N detectable by both OPA and FLU reagents. Zn-hydrolysis improvedrecovery of organic-N in natural waters from<5% to 35%. The above method, coupled with standard inorganic-N analyses, allows forenhanced resolution of dissolved organic nitrogen (DON) speciation in natural waters.

  7. Microcalorimetric Study on the Inhibition of Escherichia coil by Some Novel Pyridine Amide Schiff Base Derivatives

    Institute of Scientific and Technical Information of China (English)

    LI Chao-Hong; ZHANG Li-Xia; CAI Li-Hua; LIU Yi; HU Pei-Zhi

    2008-01-01

    The antibacterial effect of a series of novel pyridine amide Schiff base compounds on Escherichia coli was investigated by a microcalorimetric method at 37℃.The metabolic power-time curves of the bacteria treated by the compounds were obtained,and the thermokinetic parameters were analyzed,from which the antibacterial activities of these compounds were evaluated.The results show that two compounds F and G have good activity on aerobic multiplying metabolism of E.coli,with the value of IC50 106 and 113 mg/L respectively,but have no effective action on the fermentation metabolism of E.coli.The action of the compounds on the non-multiplying metabolism was investigated by taking the heat output of E.coli in the stationary phase as the guideline of the activity.The experimental results revealed that the hydrophilicity of these Schiff bases had a great influence on their antibacterial activity,which results from the bacterial cell wall structure.The antibacterial structure-activity relationship of these Schiff base derivatives was also briefly discussed.The antibacterial activity of the compounds against E.coli was as follows:compound F>G>C>D>E>B>A.

  8. Amide Proton Transfer (APT) MR imaging and Magnetization Transfer (MT) MR imaging of pediatric brain development

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hong; Kang, Huiying; Peng, Yun [Beijing Children' s Hospital, Capital Medical University, Imaging Center, Department of Radiology, Beijing (China); Zhao, Xuna [Philips Healthcare, Beijing (China); Jiang, Shanshan; Zhang, Yi; Zhou, Jinyuan [Johns Hopkins University, Division of MR Research, Department of Radiology, Baltimore, MD (United States)

    2016-10-15

    To quantify the brain maturation process during childhood using combined amide proton transfer (APT) and conventional magnetization transfer (MT) imaging at 3 Tesla. Eighty-two neurodevelopmentally normal children (44 males and 38 females; age range, 2-190 months) were imaged using an APT/MT imaging protocol with multiple saturation frequency offsets. The APT-weighted (APTW) and MT ratio (MTR) signals were quantitatively analyzed in multiple brain areas. Age-related changes in MTR and APTW were evaluated with a non-linear regression analysis. The APTW signals followed a decreasing exponential curve with age in all brain regions measured (R{sup 2} = 0.7-0.8 for the corpus callosum, frontal and occipital white matter, and centrum semiovale). The most significant changes appeared within the first year. At maturation, larger decreases in APTW and lower APTW values were found in the white matter. On the contrary, the MTR signals followed an increasing exponential curve with age in the same brain regions measured, with the most significant changes appearing within the initial 2 years. There was an inverse correlation between the MTR and APTW signal intensities during brain maturation. Together with MT imaging, protein-based APT imaging can provide additional information in assessing brain myelination in the paediatric population. (orig.)

  9. Low antiplasmodial activity of alkaloids and amides from the stem bark of Zanthoxylum rubescens (Rutaceae

    Directory of Open Access Journals (Sweden)

    Penali L.

    2007-06-01

    Full Text Available The stem bark of Zanthoxylum rubescens (syn. Fagara rubescens is used for treating fevers associated with malaria in the Ivory Coast. Three alkaloids: N-nornitidine, 7,9-dimethoxy-2,3- methylenedioxybenzophenanthridine, and bis[6-(5,6- dihydrochelerythrinyl] ether; and two amides: zanthomamide and lemairamide, were isolated from the stem bark of this plant. These compounds were screened in vitro against the chloroquine-sensitive 3D7 strain and the chloroquine-resistant FCM29 strain of P. falciparum. N-nornitidine was found to be inactive. 7,9- dimethoxy-2,3-methylenedioxybenzophenanthridine, lemairamide and zanthomamide showed weak activity with average IC50 values ranging from 45.6 μM to 149.9 μM. Bis[6-(5,6- dihydrochelerythrinyl] ether was the most active of the tested compounds with mean IC50s of 14.9 ± 1.4 μM in FCM29 strain and 15.3 ± 3.4 μM in 3D7 strain (~ 58 to ~ 1130 times less active than chloroquine respectively. The anti-Plasmodium activities of the tested alkaloids of Z. rubescens were low; and do not encourage the use of this plant as antimalarial.

  10. Protein backbone dynamics revealed by quasi spectral density function analysis of amide N-15 nuclei.

    Science.gov (United States)

    Ishima, R; Nagayama, K

    1995-03-14

    Spectral density functions J(0), J(omega N), and J(omega H + omega N) of individual amide N-15 nuclei in proteins were approximated by a quasi spectral density function (QSDF). Using this function, the backbone dynamics were analyzed for seven protein systems on which data have been published. We defined J(0; omega N) as the difference between the J(0) and the J(omega N) values, which describes motions slower than 50 (or 60) MHz, and J(omega N; omega H+N) as the difference between the J(omega N) and the J(omega H + omega N) values, which describes motions slower than 450 (or 540) MHz. The QSDF analysis can easily extract the J(0; omega N) of protein backbones, which have often some relation to biologically relevant reactions. Flexible N-terminal regions in eglin c and glucose permease IIA and a loop region in eglin c showed smaller values of both the J(0; omega N) and the J(omega N; omega H+N) as compared with the other regions, indicating increases in motions faster than nanosecond. The values of the J(0; omega N) for the backbone of the FK506 binding protein showed a large variation in the apoprotein but fell in a very narrow range after the binding of FK506. Characteristic increase or decrease in the values of J(0) and J(omega N) was observed in two or three residues located between secondary structures.

  11. Crosslinked poly(ether block amide) composite membranes for organic solvent nanofiltration applications

    KAUST Repository

    Aburabie, Jamaliah

    2016-10-01

    Poly(ether block amide) – Pebax® – based membranes are well described for gas separation applications. But only a few publications exist for their application in pressure driven liquid applications like ultrafiltration and nanofiltration. Here we use the commercially available Pebax® 1657 for the preparation of membranes for the filtration of organic solvents. Porous polyacrylonitrile membranes were coated with Pebax® 1657 which was then crosslinked. Toluene diisocyanate (TDI) was used as a crosslinker agent for the coating. Reaction time and crosslinker concentration were optimized for the aimed application. The Pebax® coating and the impact of the TDI on the resulting crosslinked membranes were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). SEM analysis shows a uniform thin coating of the PEBAX that covers the pores of the PAN membranes. FTIR and DSC analysis confirm the crosslinking reaction. Crosslinked Pebax® membranes show high stability toward ethanol propanol, acetone and even dimethylformamide (DMF). In the case of DMF applications, the standard PAN was replaced by crosslinked PAN developed in our laboratory. In order to increase the membranes permeances, graphene oxide (GO) nanosheets were incorporated in the Pebax® coating. These GO containing membranes showed strongly increased permeances for selected solvents. © 2016 Elsevier B.V.

  12. Determination of Mercury (II Ion on Aryl Amide-Type Podand-Modified Glassy Carbon Electrode

    Directory of Open Access Journals (Sweden)

    Sevgi Güney

    2011-01-01

    Full Text Available A new voltammetric sensor based on an aryl amide type podand, 1,8-bis(o-amidophenoxy-3,6-dioxaoctane, (AAP modified glassy carbon electrode, was described for the determination of trace level of mercury (II ion by cyclic voltammetry (CV and differential pulse voltammetry (DPV. A well-defined anodic peak corresponding to the oxidation of mercury on proposed electrode was obtained at 0.2 V versus Ag/AgCl reference electrode. The effect of experimental parameters on differential voltammetric peak currents was investigated in acetate buffer solution of pH 7.0 containing 1 × 10−1 mol L−1 NaCl. Mercury (II ion was preconcentrated at the modified electrode by forming complex with AAP under proper conditions and then reduced on the surface of the electrode. Interferences of Cu2+, Pb2+, Fe3+, Cd2+, and Zn2+ ions were also studied at two different concentration ratios with respect to mercury (II ions. The modified electrode was applied to the determination of mercury (II ions in seawater sample.

  13. Toughening polylactide with polyether-block-amide and thermoplastic starch acetate: Influence of starch esterification degree.

    Science.gov (United States)

    Zhou, Linyao; Zhao, Guiyan; Feng, Yulin; Yin, Jinghua; Jiang, Wei

    2015-01-01

    Native corn starch was esterified with acetic anhydride and plasticized with glycerol to give the thermoplastic starch acetate (TPSA). TPSA was blended with polylactide (PLA) and polyether-block-amide-graft-glycidyl methacrylate (PEBA-g-GMA) to obtain biodegradable PLA/PEBA-g-GMA/TPSA blends with high notched impact resistance and low cost. Compared with PLA/PEBA-g-GMA blends, as much as 9 wt% expensive PEBA-g-GMA elastomer could be substituted by the slightly acetylated thermoplastic starch while retaining high impact strength. The mechanical properties depended on the esterification degree of starch acetate. The impact strength, tensile strength and elongation at break increased to the peak value with increasing the esterification degree from 0 to 0.04, thereafter they decreased on further increasing the esterification degree. The morphological results showed that the TPSA particles were smaller and more uniform at the optimum esterification degree of 0.04, leading to the peak value of the mechanical properties.

  14. An investigation into the suitability of amidated pectin hydrogel beads as a delivery matrix for chloroquine.

    Science.gov (United States)

    Munjeri, O; Hodza, P; Osim, E E; Musabayane, C T

    1998-08-01

    The aim of the present study was to delay the release of chloroquine to distal parts of the gastrointestinal tract by using a multiparticulate hydrogel formulation. Amidated pectin chloroquine beads (PC) with varying pectin-to-chloroquine ratios (PC) w/w loadings of 4:1, 2:1, and 1:1 in the dried beads were prepared by the gelation of drug-loaded pectin solutions in the presence of calcium. In vitro release studies of chloroquine from pectin-chloroquine hydrogel beads and chloroquine diphosphate powder were carried out in simulated gastric and intestinal fluids. The total release of the entrapped chloroquine from the hydrogel beads was achieved between 4 and 7 h in simulated intestinal fluid, but total release was not achieved in simulated gastric fluid. However, total release from chloroquine diphosphate powder was achieved by 1.5 and 2 h in gastric and intestinal fluids, respectively. The plasma pharmacokinetics of chloroquine from pectin hydrogel beads and chloroquine diphosphate solution following single or repeated dosing were compared in male Sprague-Dawley rats over a period of 60 h. Oral administration of the hyrogel beads to rats produced maximum plasma concentrations by 7 h, but highest plasma concentrations following chloroquine solution administration were observed by 2 h. The dissolution data and appearance of significant plasma concentrations of chloroquine 2 to 4 h after oral administration suggests release in duodenum, jejunum, or ileum.

  15. Symmetrical and unsymmetrical α,ω-nucleobase amide-conjugated systems

    Directory of Open Access Journals (Sweden)

    Sławomir Boncel

    2010-04-01

    Full Text Available We present the synthesis and selected physicochemical properties of several novel symmetrical and unsymmetrical α,ω-nucleobase mono- and bis-amide conjugated systems containing aliphatic, aromatic or saccharidic linkages. The final stage of the synthesis involves condensation of a subunit bearing carboxylic group with an amine subunit. 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl-4-methylmorpholinium chloride (DMT-MM was found to be a particularly effective condensing agent. The subunits containing carboxylic groups were obtained by acidic hydrolysis of N-1 Michael adducts of uracils or N-9 Michael adducts of 6-chloropurine with methyl acrylate. The amines used were aliphatic/aromatic diamines, adenine, 5-substituted 1-(ω-aminoalkyluracils and 5′-amino-2′,5′-dideoxythymidine. The title compounds may find application as antiprotozoal agents. Moreover, preliminary microscopy TEM studies of supramolecular behaviour showed that target molecules with bolaamphiphilic structures were capable of forming highly ordered assemblies, mainly nanofibres.

  16. Magnetization Transfer and Amide Proton Transfer MRI of Neonatal Brain Development

    Directory of Open Access Journals (Sweden)

    Yang Zheng

    2016-01-01

    Full Text Available Purpose. This study aims to evaluate the process of brain development in neonates using combined amide proton transfer (APT imaging and conventional magnetization transfer (MT imaging. Materials and Methods. Case data were reviewed for all patients hospitalized in our institution’s neonatal ward. Patients underwent APT and MT imaging (a single protocol immediately following the routine MR examination. Single-slice APT/MT axial imaging was performed at the level of the basal ganglia. APT and MT ratio (MTR measurements were performed in multiple brain regions of interest (ROIs. Data was statistically analyzed in order to assess for significant differences between the different regions of the brain or correlation with patient gestational age. Results. A total of 38 neonates were included in the study, with ages ranging from 27 to 41 weeks’ corrected gestational age. There were statistically significant differences in both APT and MTR measurements between the frontal lobes, basal ganglia, and occipital lobes (APT: frontal lobe versus occipital lobe P=0.031 and other groups P=0.00; MTR: frontal lobe versus occipital lobe P=0.034 and other groups P=0.00. Furthermore, APT and MTR in above brain regions exhibited positive linear correlations with patient gestational age. Conclusions. APT/MT imaging can provide valuable information about the process of the neonatal brain development at the molecular level.

  17. Preparation of composite poly(ether block amide) membrane for CO2 capture

    Institute of Scientific and Technical Information of China (English)

    Lianjun Wang; Yang Li; Shuguang Li; Pengfei Ji; Chengzhang Jiang

    2014-01-01

    In this study, a poly(ether block amide) (Pebax 1657) composite membrane applied for CO2 capture was prepared by coating Pebax 1657 solution on polyacrylonitrile (PAN) ultrafiltration membrane. Ethanol/water mixture was used as the solvent of Pebax and the effects of ethanol/water mass ratios and Pebax concentration on the permeation properties of composite membrane were studied. To enhance the com-posite membrane permeance, the gutter layer, made from reactive amino silicone crosslinking with polydimethylsiloxane (PDMS), was de-signed. The influence of crosslinking degree of the gutter layer on membrane performance was investigated. As a result, a Pebax/amino-PDMS/PAN multilayer membrane with hexane resistance was developed, showing CO2 permeance of 350 GPU and CO2/N2 selectivity over 50. The blend of polyethylene glycol dimethyl ether (PEG-DME) with Pebax as coating material was studied to further improve the membrane performance. After being combined with PEG-DME additive, CO2 permeance of the final Pebax-PEG-DME/amino-PDMS/PAN composite membrane reached 400 GPU above with CO2/N2 selectivity over 65.

  18. A new acylamidase from Rhodococcus erythropolis TA37 can hydrolyze N-substituted amides.

    Science.gov (United States)

    Lavrov, K V; Zalunin, I A; Kotlova, E K; Yanenko, A S

    2010-08-01

    A new acylamidase was isolated from Rhodococcus erythropolis TA37 and characterized. N-Substituted acrylamides (isopropyl acrylamide, N,N-dimethyl-aminopropyl acrylamide, and methylene-bis-acrylamide), acid para-nitroanilides (4'-nitroacetanilide, Gly-pNA, Ala-pNA, Leu-pNA), and N-acetyl derivatives of glycine, alanine, and leucine are good substrates for this enzyme. Aliphatic amides (acetamide, acrylamide, isobutyramide, n-butyramide, and valeramide) are also used as substrates but with less efficiency. The enzyme subunit mass by SDS-PAGE is 55 kDa. Maximal activity is exhibited at pH 7-8 and 55°C. The enzyme is stable for 15 h at 22°C and for 0.5 h at 45°C. The Michaelis constant (K(m)) is 0.25 mM with Gly-pNA and 0.55 mM with Ala-pNA. The acylamidase activity is suppressed by inhibitors of serine proteases (phenylmethylsulfonyl fluoride and diisopropyl fluorophosphate) but is not suppressed by inhibitors of aliphatic amidases (acetaldehyde and nitrophenyl disulfides). The N-terminal amino acid sequence of the acylamidase is highly homologous to those of two putative amidases detected from sequenced R. erythropolis genomes. It is suggested that the acylamidase together with the detected homologs forms a new class within the amidase signature family.

  19. Synthesis of novel nanostructured chiral poly(amide-imide)s containing dopamine and natural amino acids

    Indian Academy of Sciences (India)

    Shadpour Mallakpour; Amin Zadehnazari

    2013-01-01

    Four new thermally stable and optically active poly(amide-imide)s (PAI)s with good inherent viscosities were synthesized from the direct polycondensation reaction of N,N'-(pyromellitoyl)-bis-L--amino acids with 3,5-diamino-N-(3,4-dihydroxy-phen-ethyl)benzamide in a medium consisting of a molten salt, tetrabutylammonium bromide, and triphenyl phosphite as the activator. The polymerization reactions produced a series of novel PAIs containing dopamine segment in the side chain in high yield with inherent viscosities between 0.33 and 0.49 dL/g. The obtained polymers were typically characterized by means of FT-IR, 1HNMR spectroscopy, elemental analyses, powder X-ray diffraction, field emission scanning electronmicroscopy, inherent viscosity, and solubility tests. Thermal properties and flame retardant behaviour of the PAIs were also investigated using thermal gravimetric analysis (TGA and DTG) and limiting oxygen index (LOI). Data obtained by thermal analysis revealed that these polymers showed good thermal stability. Furthermore, high char yield in TGA and good LOI values indicated that the obtained polymers were capable of exhibiting good flame retardant properties.

  20. An efficient phase-selective gelator for aromatic solvents recovery based on a cyanostilbene amide derivative.

    Science.gov (United States)

    Zhang, Yuping; Ma, Yao; Deng, Mengyu; Shang, Hongxing; Liang, Chunshuang; Jiang, Shimei

    2015-07-07

    Two novel low molecular weight organogelators (LMOGs) 1 and 2 composed of a cholesteryl group, an amide group and various terminal cyanostilbene moieties were synthesized. They could form stable gels in p-xylene. In particular, 2 with more extended π-conjugation length showed remarkable gelation ability in many aromatic solvents, chloroform and chloroform-containing mixed solvents at a relatively low concentration. FT-IR and XRD spectra indicated that the difference between 1 and 2 in the gelation properties may result from the deviation of the intermolecular hydrogen bonding and π–π stacking as driving forces for the formation of the gels. Significantly, 2 can function as an efficient room-temperature phase-selective gelator (PSG) for potential application in the separation and recovery of various aromatic solvents from its mixture with water. Meanwhile, the gelator can be easily recovered and reused several times. Furthermore, the phase-selective gelation properties of 2 can provide a simple and feasible approach for the removal of the rhodamine B (RhB) dye from water.

  1. Detection of Formamide, the Simplest but Crucial Amide, in a Solar-type Protostar

    Science.gov (United States)

    Kahane, C.; Ceccarelli, C.; Faure, A.; Caux, E.

    2013-02-01

    Formamide (NH2CHO), the simplest possible amide, has recently been suggested to be a central species in the synthesis of metabolic and genetic molecules, the chemical basis of life. In this Letter, we report the first detection of formamide in a protostar, IRAS 16293-2422, which may be similar to the Sun and solar system progenitor. The data combine spectra from the millimeter and submillimeter TIMASSS survey with recent, more sensitive observations at the IRAM 30 m telescope. With an abundance relative to H2 of ~10-10, formamide appears as abundant in this solar-type protostar as in the two high-mass star-forming regions, Orion-KL and SgrB2, where this species has previously been detected. Given the largely different UV-illuminated environments of the three sources, the relevance of UV photolysis of interstellar ices in the synthesis of formamide is therefore questionable. Assuming that this species is formed in the gas phase via the neutral-neutral reaction between the radical NH2 and H2CO, we predict an abundance in good agreement with the value derived from our observations. The comparison of the relative abundance [NH2CHO]/[H2O] in IRAS 16293-2422 and in the coma of the comet Hale-Bopp supports the similarity between interstellar and cometary chemistry. Our results thus suggest that the abundance of some cometary organic volatiles could reflect gas phase rather than grain-surface interstellar chemistry.

  2. Residual Cooling and Persistent Star Formation amid AGN Feedback in Abell 2597

    CERN Document Server

    Tremblay, G R; Baum, S A; Clarke, T E; Sarazin, C L; Bregman, J N; Combes, F; Donahue, M; Edge, A C; Fabian, A C; Ferland, G J; McNamara, B R; Mittal, R; Oonk, J B R; Quillen, A C; Russell, H R; Sanders, J S; Salomé, P; Voit, G M; Wilman, R J; Wise, M W

    2012-01-01

    New Chandra X-ray and Herschel FIR observations enable a multiwavelength study of active galactic nucleus (AGN) heating and intracluster medium (ICM) cooling in the brightest cluster galaxy of Abell 2597. The new Chandra observations reveal the central < 30 kiloparsec X-ray cavity network to be more extensive than previously thought, and associated with enough enthalpy to theoretically inhibit the inferred classical cooling flow. Nevertheless, we present new evidence, consistent with previous results, that a moderately strong residual cooling flow is persisting at 4%-8% of the classically predicted rates in a spatially structured manner amid the feedback-driven excavation of the X-ray cavity network. New Herschel observations are used to estimate warm and cold dust masses, a lower-limit gas-to-dust ratio, and a star formation rate consistent with previous measurements. The cooling time profile of the ambient X-ray atmosphere is used to map the locations of the observational star formation entropy threshold...

  3. Synthesis and Antibacterial Testing of Silver/Poly (Ether Amide Composite Nanofibers with Ultralow Silver Content

    Directory of Open Access Journals (Sweden)

    Shuai Liang

    2014-01-01

    Full Text Available Antimicrobial materials have attracted much attention all over the world. Herein, a new kind of antimicrobial material, poly (ether amide (PebaxⓇ nanofibers containing Ag nanoparticles, was prepared by electrospinning method. The Ag/PebaxⓇ composites were characterized by scanning electron microscopy (SEM, transmission electron microscopy (TEM, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, differential scanning calorimetry (DSC, and thermogravimetric analyzer (TGA measurements. The antimicrobial properties of Ag/PebaxⓇ composites against Escherichia coli (E. coli; ATCC25922 and avirulent and Staphylococcus aureus (S. aureus; ATCC6538 and avirulent were evaluated by membrane adhering method. It was found that the Ag content played an important part in the antimicrobial ability of Ag/PebaxⓇ composites. When the mass ratio of AgNO3 to PebaxⓇ in the precursor was 0.15‰, the inhibition rate can reach >99.9% and antimicrobial activity against E. coli and S. aureus was 5.8 and 5.6, respectively, exceeding the antimicrobial testing standards JIS Z 2801. The above results indicated that the Ag/PebaxⓇ composite was a promising antimicrobial material that can be used in many applications.

  4. Picosecond pulsed infrared laser tuned to amide I band dissociates polyglutamine fibrils in cells.

    Science.gov (United States)

    Kawasaki, Takayasu; Ohori, Gaku; Chiba, Tomoyuki; Tsukiyama, Koichi; Nakamura, Kazuhiro

    2016-09-01

    Amyloid fibrils are causal substances for serious neurodegenerative disorders and amyloidosis. Among them, polyglutamine fibrils seen in multiple polyglutamine diseases are toxic to neurons. Although much efforts have been made to explore the treatments of polyglutamine diseases, there are no effective drugs to block progression of the diseases. We recently found that a free electron laser (FEL), which has an oscillation wavelength at the amide I band (C = O stretch vibration mode) and picosecond pulse width, was effective for conversion of the fibril forms of insulin, lysozyme, and calcitonin peptide into their monomer forms. However, it is not known if that is also the case in polyglutamine fibrils in cells. We found in this study that the fibril-specific β-sheet conformation of polyglutamine peptide was converted into nonfibril form, as evidenced by the infrared microscopy and scanning-electron microscopy after the irradiation tuned to 6.08 μm. Furthermore, irradiation at this wavelength also changed polyglutamine fibrils to their nonfibril state in cultured cells, as shown by infrared mapping image of protein secondary structure. Notably, infrared thermography analysis showed that temperature increase of the cells during the irradiation was within 1 K, excluding thermal damage of cells. These results indicate that the picosecond pulsed infrared laser can safely reduce amyloid fibril structure to the nonfibril form even in cells.

  5. Extraction of cobalt(II) from aqueous solution by N,N'-carbonyl difatty amides

    Institute of Scientific and Technical Information of China (English)

    Emad A. Jaffar Al-Mulla; Khalid Waleed S. Al-Janabi

    2011-01-01

    The development of economic and environmentally friendly extractants to recover cobalt metal is required due to the increasing demand for this metal. In this study, solvent extraction of Co(Ⅱ) from aqueous solution using a mixture of N,N'-carbonyl difatty amides (CDFAs) synthesised from palm oil as the extractant was carried out. The effects of various parameters such as acid, contact time, extractant concentration, metal ion concentration and stripping agent and the separation of Co(Ⅱ) from other metal ions such as Fe(Ⅱ), Ni(Ⅱ), Zn(Ⅲ) and Cd(Ⅱ) were investigated. It was found that the extraction of Co(Ⅱ) into the organic phase involved the formation of 1:1 complexes. Co(Ⅱ) was successfully separated from commonly associated metal ions such as Fe(Ⅱ), Ni(Ⅱ), Zn(Ⅲ) and Cd(Ⅱ). Co(Ⅱ) stripping from the loaded organic phase was studied in aqueous solution. These results are useful to recover Co(Ⅱ) from aqueous solution utilising (CDFAs) as an extractant.

  6. Versatile Biodegradable Poly(ester amides Derived from α-Amino Acids for Vascular Tissue Engineering

    Directory of Open Access Journals (Sweden)

    Pooneh Karimi

    2010-03-01

    Full Text Available Biodegradable poly(ester amide (PEA biomaterials derived from α-amino acids, diols, and diacids are promising materials for biomedical applications such as tissue engineering and drug delivery because of their optimized properties and susceptibility for either hydrolytic or enzymatic degradation. The objective of this work was to synthesize and characterize biodegradable PEAs based on the α-amino acids L-phenylalanine and L-methionine. Four different PEAs were prepared using 1,4-butanediol, 1,6-hexanediol, and sebacic acid by interfacial polymerization. High molecular weight PEAs with narrow polydispersity indices and excellent film-forming properties were obtained. The incubation of these PEAs in PBS and chymotrypsin indicated that the polymers are biodegradable. Human coronary artery smooth muscle cells were cultured on PEA films for 48 h and the results showed a well-spread morphology. Porous 3D scaffolds fabricated from these PEAs were found to have excellent porosities indicating the utility of these polymers for vascular tissue engineering.

  7. 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.

  8. 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

    2016-10-01

    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.

  9. 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

    Energy Technology Data Exchange (ETDEWEB)

    Vora, Rohitkumar H., E-mail: rohitvora@apr-technologies.co [Advanced Polymers Research and Technologies, High Performance Polymers and Nanocomposites, 8080 Heritage Drive, Alburtis, PA 18011 (United States)

    2010-04-15

    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

  10. Antimicrobial hyperbranched poly(ester amide)/polyaniline nanofiber modified montmorillonite nanocomposites.

    Science.gov (United States)

    Pramanik, Sujata; Bharali, Pranjal; Konwar, B K; Karak, Niranjan

    2014-02-01

    There has been growing interest in the use of nanomaterials featuring potent of antimicrobial activity in the biomedical domain. It still remains a challenge for the researchers to develop an efficient nanocomposite possessing antimicrobial efficacy against broad spectrum microbes including bacteria, fungi as well as algal consortium, posing serious challenges for the human survival. In addressing the above problem, we report the fabrication of bio-based hyperbranched poly(ester amide) (HBPEA)/polyaniline nanofiber modified montmorillonite (MMT) nanocomposites by an ex-situ polymerization technique at varied weight percentages (1, 2.5, 5 wt.%) of the modified MMT (nanohybrid). The Fourier transform infrared spectroscopy confirmed the structural changes upon interaction of the nanohybrid with HBPEA. A probable mechanism is proposed for the formation of nanocomposites with partially exfoliated nanoplatelet structure, which was further confirmed from the high resolution transmission electron microscopic analyses. The prepared nanocomposites exhibited potent efficacy against gram positive bacteria like Bacillus subtilis and Staphylococcus aureus as compared to the gram negative ones like Pseudomonas aeruginosa and Escherichia coli. The nanocomposites showed significant antifungal activity against Aspergillus niger, Fusarium oxysporum and Coleotricum capcii and antialgal activity against algal consortium comprising of Chlorella, Hormidium and Cladophorella species. The formation of thermosetting nanocomposites resulted in the acceptable improvement of desired physico-chemical and mechanical properties including thermostability. Thus pronounced antimicrobial activity of the nanocomposites against a spectrum of bacterial and fungal strains as well as a consortium of algal species along with other desired performance vouched them as potent antimicrobial materials in the realm of health and biomedical industry.

  11. Interaction of amidated single-walled carbon nanotubes with protein by multiple spectroscopic methods

    Energy Technology Data Exchange (ETDEWEB)

    Li, Lili [China Pharmaceutical University, Nanjing 210009 (China); The Nursing College of Pingdingshan University, Pingdingshan 467000 (China); Lin, Rui [Yancheng Health Vocational and Technical College, Yancheng 224005 (China); He, Hua, E-mail: dochehua@163.com [China Pharmaceutical University, Nanjing 210009 (China); Key Laboratory of Drug Quality Control and Pharmacovigilance, Ministry of Education, China Pharmaceutical University, Nanjing 210009 (China); Sun, Meiling, E-mail: sml-nir@sohu.com [China Pharmaceutical University, Nanjing 210009 (China); Jiang, Li; Gao, Mengmeng [China Pharmaceutical University, Nanjing 210009 (China)

    2014-01-15

    The aim of this work was to investigate the detailed interaction between BSA and amidated single walled carbon nanotubes (e-SWNTs) in vitro. Ethylenediamine (EDA) was successfully linked on the surface of single-walled carbon nanotubes (SWNTs) via acylation to improve their dispersion and to introduce active groups. Bovine serum albumin (BSA) was selected as the template protein to inspect the interaction of e-SWNTs with protein. Decreases in fluorescence intensity of BSA induced by e-SWNTs demonstrated the occurrence of interaction between BSA and e-SWNTs. Quenching parameters and different absorption spectra for e-SWNTs–BSA show that the quenching effect of e-SWNTs was static quenching. Hydrophobic force had a leading contribution to the binding roles of BSA on e-SWNTs, which was confirmed by positive enthalpy change and entropy change. The interference of Na{sup +} with the quenching effect of e-SWNTs authenticated that electrostatic force existed in the interactive process simultaneously. The hydrophobicity of amino acid residues markedly increased with the addition of e-SWNTs viewed from UV spectra of BSA. The content of α-helix structure in BSA decreased by 6.8% due to the addition of e-SWNTs, indicating that e-SWNTs have an effect on the secondary conformation of BSA. -- Highlights: • The interaction between e-SWNTs and BSA was investigated by multiple spectroscopic methods. • Quenching mechanism was static quenching. • Changes in structure of BSA were inspected by synchronous fluorescence, UV–vis and CD spectrum.

  12. Effects of valproate derivatives I. Antiepileptic efficacy of amides, structural analogs and esters.

    Science.gov (United States)

    Redecker, C; Altrup, U; Hoppe, D; Düsing, R; Speckmann, E J

    2000-01-04

    Derivatives of the antiepileptic drug valproate (VPA, 2-propylpentanoic acid) have been synthesized and tested in order to improve the intracellular availability of VPA. The buccal ganglia of Helix pomatia were used as a test nervous system and antiepileptic efficacies were reconfirmed using rat cortex in vivo. Epileptiform activities consisted of typical paroxysmal depolarization shifts (PDS) which appeared in the identified neuron B3 with application of pentylenetetrazol. Epileptiform activities were found to be accelerated, unaffected or blocked. (i) The Amide-derivatives 2-propylpentanamide and N,N-dipropyl-2-propylpentanamide, and short chain ester derivatives 1-O-(2-propylpentanoyl)-2,3-propandiol, 2,2-di(hydroxymethyl)-1-O-(2-propylpentanoyl)-1,3-propanediol and 2,2-di(hydroxymethyl)-1,3-di-O-(2-propylpentanoyl)-1,3-propanediol accelerated epileptiform activities. Membrane potential often shifted to a permanent depolarization which corresponded to the PDS-inactivation level. (ii) The structural analogs 1-cycloheptene-1-carboxylic acid and cyclooctanecarboxylic acid accelerated epileptiform activities only slightly or were without effects. (iii) The small VPA-ester, 2-propylpentanoic acid ethyl ester, decreased the epileptiform activities in a way that is comparable to the effects of VPA well known from previous studies. It thus could be thought as a VPA-pro-drug. (iv) The mannitol-esters 1-O-(2-propylpentanoyl)-D-mannitol and 3,4;5,6-Di-O-isopropylidene-1-O-(2-propylpentanoyl)-D-mannitol blocked the PDS in a way which is different from the known effects of VPA. These substances are interpreted not to exert their effects after being metabolized to VPA and thus they are thought to be new antiepileptic substances.

  13. Analgesic effects of fatty acid amide hydrolase inhibition in a rat model of neuropathic pain.

    Science.gov (United States)

    Jhaveri, Maulik D; Richardson, Denise; Kendall, David A; Barrett, David A; Chapman, Victoria

    2006-12-20

    Cannabinoid-based medicines have therapeutic potential for the treatment of pain. Augmentation of levels of endocannabinoids with inhibitors of fatty acid amide hydrolase (FAAH) is analgesic in models of acute and inflammatory pain states. The aim of this study was to determine whether local inhibition of FAAH alters nociceptive responses of spinal neurons in the spinal nerve ligation model of neuropathic pain. Electrophysiological studies were performed 14-18 d after spinal nerve ligation or sham surgery, and the effects of the FAAH inhibitor cyclohexylcarbamic acid 3-carbamoyl biphenyl-3-yl ester (URB597) on mechanically evoked responses of spinal neurons and levels of endocannabinoids were determined. Intraplantar URB597 (25 microg in 50 microl) significantly (p < 0.01) attenuated mechanically evoked responses of spinal neurons in sham-operated rats. Effects of URB597 were blocked by the cannabinoid 1 receptor (CB1) antagonist AM251 [N-1-(2,4-dichlorophenyl)-5-(4-iodophenyl)-4-methyl-N-1-piperidinyl-1H-pyrazole-3-carboxamide] (30 microg in 50 microl) and the opioid receptor antagonist naloxone. URB597 treatment increased levels of anandamide, 2-arachidonyl glycerol, and oleoyl ethanolamide in the ipsilateral hindpaw of sham-operated rats. Intraplantar URB597 (25 microg in 50 microl) did not, however, alter mechanically evoked responses of spinal neurons in spinal nerve ligated (SNL) rats or hindpaw levels of endocannabinoids. Intraplantar injection of a higher dose of URB597 (100 microg in 50 microl) significantly (p < 0.05) attenuated evoked responses of spinal neurons in SNL rats but did not alter hindpaw levels of endocannabinoids. Spinal administration of URB597 attenuated evoked responses of spinal neurons and elevated levels of endocannabinoids in sham-operated and SNL rats. These data suggest that peripheral FAAH activity may be altered or that alternative pathways of metabolism have greater importance in SNL rats.

  14. The Cyclicity of the Development of the Global Economic System amid Present-Day Globalization

    Directory of Open Access Journals (Sweden)

    Mihail N. Dudin

    2014-10-01

    Full Text Available The relevance of this topic is associated with the diversity of causes behind crisis processes in economics and the individuality of each particular crisis. This necessitates classifying them in a detailed fashion. The present downturn is a manifestation of the cyclicity of the development of the global economic system amid present-day globalization and the established architecture of the institutional space. The formal (legislation, contractual rules, corporate norms, etc. and non-formal institutes (rules, customs, traditions, behavior as a whole, etc., undergoing changes in their structure and mechanisms, caused the emergence of financial innovations whose yield surpassed that of the real sector of the economy multifold. This facilitated the concentration of money in financial markets and transforming them into a thing-in-itself. The theory of economic cycles is one of the theories of economic dynamics which explain the movement of the national economy. While the theory of economic growth explores factors and conditions for growth as a long-term trend, the theory of cycles deals with causes behind fluctuations in economic activity through time. Results. In accordance with the aims of this study, the authors established that crises can have the following causes: objective, which are associated with the cyclical development of the system, modernization and restructuring needs, and the impact of external factors, and subjective, which reflect errors in management, shortcomings in the organization of production, and the imperfections of innovation and investment policy. A crisis can take its course manifestly and be easily detected or can be inconspicuous and take its course in a latent form. The most dangerous are crises that affect the system as a whole. In a situation of this kind, there forms a train of complex issues resolving which depends on the timeliness of detecting them and professionalism in managing the organization, municipal

  15. The in vitro metabolism of phospho-sulindac amide, a novel potential anticancer agent.

    Science.gov (United States)

    Xie, Gang; Cheng, Ka-Wing; Huang, Liqun; Rigas, Basil

    2014-09-15

    Phospho-sulindac amide (PSA) is a novel potential anti-cancer and anti-inflammatory agent. Here we report the metabolism of PSA in vitro. PSA was rapidly hydroxylated at its butane-phosphate moiety to form two di-hydroxyl-PSA and four mono-hydroxyl-PSA metabolites in mouse and human liver microsomes. PSA also can be oxidized or reduced at its sulindac moiety to form PSA sulfone and PSA sulfide, respectively. PSA was mono-hydroxylated and cleared more rapidly in mouse liver microsomes than in human liver microsomes. Of eight major human cytochrome P450s (CYPs), CYP3A4 and CYP2D6 exclusively catalyzed the hydroxylation and sulfoxidation reactions of PSA, respectively. We also examined the metabolism of PSA by three major human flavin monooxygenases (FMOs). FMO1, FMO3 and FMO5 were all capable of catalyzing the sulfoxidation (but not hydroxylation) of PSA, with FMO1 being by far the most active isoform. PSA was predominantly sulfoxidized in human kidney microsomes because FMO1 is the dominant isoform in human kidney. PSA (versus sulindac) is a preferred substrate of both CYPs and FMOs, likely because of its greater lipophilicity and masked-COOH group. Ketoconazole (a CYP3A4 inhibitor) and alkaline pH strongly inhibited the hydroxylation of PSA, but moderately suppressed its sulfoxidation in liver microsomes. Together, our results establish the metabolic pathways of PSA, identify the major enzymes mediating its biotransformations and reveal significant inter-species and inter-tissue differences in its metabolism.

  16. Business return in New Orleans: decision making amid post-Katrina uncertainty.

    Directory of Open Access Journals (Sweden)

    Nina S N Lam

    Full Text Available BACKGROUND: Empirical observations on how businesses respond after a major catastrophe are rare, especially for a catastrophe as great as Hurricane Katrina, which hit New Orleans, Louisiana on August 29, 2005. We analyzed repeated telephone surveys of New Orleans businesses conducted in December 2005, June 2006, and October 2007 to understand factors that influenced decisions to re-open amid post-disaster uncertainty. METHODOLOGY/PRINCIPAL FINDINGS: Businesses in the group of professional, scientific, and technical services reopened the fastest in the near term, but differences in the rate of reopening for businesses stratified by type became indistinguishable in the longer term (around two years later. A reopening rate of 65% was found for all businesses by October 2007. Discriminant analysis showed significant differences in responses reflecting their attitudes about important factors between businesses that reopened and those that did not. Businesses that remained closed at the time of our third survey (two years after Katrina ranked levee protection as the top concern immediately after Katrina, but damage to their premises and financing became major concerns in subsequent months reflected in the later surveys. For businesses that had opened (at the time of our third survey, infrastructure protection including levee, utility, and communications were the main concerns mentioned in surveys up to the third survey, when the issue of crime became their top concern. CONCLUSIONS/SIGNIFICANCE: These findings underscore the need to have public policy and emergency plans in place prior to the actual disaster, such as infrastructure protection, so that the policy can be applied in a timely manner before business decisions to return or close are made. Our survey results, which include responses from both open and closed businesses, overcome the "survivorship bias" problem and provide empirical observations that should be useful to improve micro

  17. Transdermal delivery of chloroquine by amidated pectin hydrogel matrix patch in the rat.

    Science.gov (United States)

    Musabayane, C T; Munjeri, O; Matavire, T P

    2003-07-01

    The aim of the present study was to investigate the suitability of amidated pectin matrix patch for transdermal chloroquine delivery in an effort to mask the bitter taste when orally administered. Chloroquine has easily measurable outputs that are linked to increased renal Na+ excretion. We thus monitored urinary Na+ output in separate groups intravenously administered chloroquine or topically applied pectin hydrogel chloroquine matrix patch. Male groups of anesthetized Sprague-Dawley rats were placed on a continuous jugular infusion of 0.077 M NaCl at 150 microL min(-1). After 3 h equilibration period, consecutive 20 min urine collections were made over the subsequent 4 h of 1 h control, 1 h 20 min treatment, and 1 h 40 min recovery periods for measurements of urine flow and Na+ and K+ excretion rates. The effects of intravenous chloroquine infusion or topical application of pectin hydrogel chloroquine matrix patch were examined in rats in which the drug was added to the infusate or patch applied onto the shaved area during the 1 h 20 min treatment period. The animals were switched back to the infusate alone for the final 1 h 40 min recovery period. Vehicle infused animals acted as controls. Trunk blood was collected after the treatment period from parallel groups for chloroquine measurements. The plasma chloroquine concentrations following iv chloroquine or application of pectin chloroquine hydrogel matrix patch were 9.3 +/- 0.8 mg L(-1) and 7.3 +/- 1.1 mg L(-1) respectively (n = 7 in both groups). Chloroquine infusion and pectin chloroquine patch significantly (p pectin chloroquine patch matrix preparation has potential applications for transdermal delivery of chloroquine and perhaps in the management of malaria.

  18. Ligand assisted carbon dioxide activation and hydrogenation using molybdenum and tungsten amides.

    Science.gov (United States)

    Chakraborty, Subrata; Blacque, Olivier; Berke, Heinz

    2015-04-14

    The hepta-coordinated isomeric M(NO)Cl3(PN(H)P) complexes {M = Mo, ; W, , PN(H)P = (iPr2PCH2CH2)2NH, (HN atom of PN(H)P syn and anti to the NO ligand)} and the paramagnetic species M(NO)Cl2(PN(H)P) (M = Mo, ; W, ) could be prepared via a new synthetic pathway. The pseudo trigonal bipyramidal amides M(NO)(CO)(PNP) {M = Mo, ; W, ; [PNP](-) = [(iPr2PCH2CH2)2N](-)} were reacted with CO2 at room temperature with CO2 approaching the M[double bond, length as m-dash]N double bond in the equatorial (CO,NO,N) plane trans to the NO ligand and forming the pseudo-octahedral cyclic carbamates M(NO)(CO)(PNP)(OCO) (M = Mo, ; W = ). DFT calculations revealed that the approach to form the isomer is kinetically determined. The amine hydrides M(NO)H(CO)(PN(H)P) {M = Mo, ; W, }, obtained by H2 addition to , insert CO2 (2 bar) at room temperature into the M-H bond generating isomeric mixtures of the η(1)-formato complexes M(NO)(CO)(PN(H)P)(η(1)-OCHO), (M = Mo, ; M = W, ). Closing the stoichiometric cycles for sodium formate formation the isomeric mixtures were reacted with 1 equiv. of Na[N(SiMe3)2] regenerating . Attempts to turn the stoichiometric formate production into catalytic CO2 hydrogenation using in the presence of various types of sterically congested bases furnished yields of formate salts of up to 4%.

  19. Temperature dependence of C-terminal carboxylic group IR absorptions in the amide I' region.

    Science.gov (United States)

    Anderson, Benjamin A; Literati, Alex; Ball, Borden; Kubelka, Jan

    2015-01-01

    Studies of structural changes in peptides and proteins using IR spectroscopy often rely on subtle changes in the amide I' band as a function of temperature. However, these changes can be obscured by the overlap with other absorptions, namely the side-chain and terminal carboxylic groups. The former were the subject of our previous report (Anderson et al., 2014). In this paper we investigate the IR spectra of the asymmetric stretch of α-carboxylic groups for amino acids representing all major types (Gly, Ala, Val, Leu, Ser, Thr, Asp, Glu, Lys, Asn, His, Trp, Pro) as well as the C-terminal groups of three dipeptides (Gly-Gly, Gly-Ala, Ala-Gly) in D₂O at neutral pH. Experimental temperature dependent IR spectra were analyzed by fitting of both symmetric and asymmetric pseudo-Voigt functions. Qualitatively the spectra exhibit shifts to higher frequency, loss in intensity and narrowing with increased temperature, similar to that observed previously for the side-chain carboxylic groups of Asp. The observed dependence of the band parameters (frequency, intensity, width and shape) on temperature is in all cases linear: simple linear regression is therefore used to describe the spectral changes. The spectral parameters vary between individual amino acids and show systematic differences between the free amino acids and dipeptides, particularly in the absolute peak frequencies, but the temperature variations are comparable. The relative variations between the dipeptide spectral parameters are most sensitive to the C-terminal amino acid, and follow the trends observed in the free amino acid spectra. General rules for modeling the α-carboxylic IR absorption bands in peptides and proteins as the function of temperature are proposed.

  20. Temperature dependence of C-terminal carboxylic group IR absorptions in the amide I‧ region

    Science.gov (United States)

    Anderson, Benjamin A.; Literati, Alex; Ball, Borden; Kubelka, Jan

    2015-01-01

    Studies of structural changes in peptides and proteins using IR spectroscopy often rely on subtle changes in the amide I‧ band as a function of temperature. However, these changes can be obscured by the overlap with other absorptions, namely the side-chain and terminal carboxylic groups. The former were the subject of our previous report (Anderson et al., 2014). In this paper we investigate the IR spectra of the asymmetric stretch of α-carboxylic groups for amino acids representing all major types (Gly, Ala, Val, Leu, Ser, Thr, Asp, Glu, Lys, Asn, His, Trp, Pro) as well as the C-terminal groups of three dipeptides (Gly-Gly, Gly-Ala, Ala-Gly) in D2O at neutral pH. Experimental temperature dependent IR spectra were analyzed by fitting of both symmetric and asymmetric pseudo-Voigt functions. Qualitatively the spectra exhibit shifts to higher frequency, loss in intensity and narrowing with increased temperature, similar to that observed previously for the side-chain carboxylic groups of Asp. The observed dependence of the band parameters (frequency, intensity, width and shape) on temperature is in all cases linear: simple linear regression is therefore used to describe the spectral changes. The spectral parameters vary between individual amino acids and show systematic differences between the free amino acids and dipeptides, particularly in the absolute peak frequencies, but the temperature variations are comparable. The relative variations between the dipeptide spectral parameters are most sensitive to the C-terminal amino acid, and follow the trends observed in the free amino acid spectra. General rules for modeling the α-carboxylic IR absorption bands in peptides and proteins as the function of temperature are proposed.

  1. Antimicrobial hyperbranched poly(ester amide)/polyaniline nanofiber modified montmorillonite nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Pramanik, Sujata [Advanced Polymer and Nanomaterial Laboratory, Department of Chemical Sciences, Tezpur University, Tezpur 784028 (India); Bharali, Pranjal; Konwar, B.K. [Department of Molecular Biology and Biotechnology, Tezpur University, Tezpur 784028 (India); Karak, Niranjan, E-mail: karakniranjan@yahoo.com [Advanced Polymer and Nanomaterial Laboratory, Department of Chemical Sciences, Tezpur University, Tezpur 784028 (India)

    2014-02-01

    There has been growing interest in the use of nanomaterials featuring potent of antimicrobial activity in the biomedical domain. It still remains a challenge for the researchers to develop an efficient nanocomposite possessing antimicrobial efficacy against broad spectrum microbes including bacteria, fungi as well as algal consortium, posing serious challenges for the human survival. In addressing the above problem, we report the fabrication of bio-based hyperbranched poly(ester amide) (HBPEA)/polyaniline nanofiber modified montmorillonite (MMT) nanocomposites by an ex-situ polymerization technique at varied weight percentages (1, 2.5, 5 wt.%) of the modified MMT (nanohybrid). The Fourier transform infrared spectroscopy confirmed the structural changes upon interaction of the nanohybrid with HBPEA. A probable mechanism is proposed for the formation of nanocomposites with partially exfoliated nanoplatelet structure, which was further confirmed from the high resolution transmission electron microscopic analyses. The prepared nanocomposites exhibited potent efficacy against gram positive bacteria like Bacillus subtilis and Staphylococcus aureus as compared to the gram negative ones like Pseudomonas aeruginosa and Escherichia coli. The nanocomposites showed significant antifungal activity against Aspergillus niger, Fusarium oxysporum and Coleotricum capcii and antialgal activity against algal consortium comprising of Chlorella, Hormidium and Cladophorella species. The formation of thermosetting nanocomposites resulted in the acceptable improvement of desired physico-chemical and mechanical properties including thermostability. Thus pronounced antimicrobial activity of the nanocomposites against a spectrum of bacterial and fungal strains as well as a consortium of algal species along with other desired performance vouched them as potent antimicrobial materials in the realm of health and biomedical industry. - Highlights: • A possible approach for fabrication of the

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

    Directory of Open Access Journals (Sweden)

    Neal D. Teaster

    2012-02-01

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

  3. Influences of hyperbranched poly(amide-ester) on the properties of poly(butylene succinate)

    Energy Technology Data Exchange (ETDEWEB)

    Run, Mingtao, E-mail: lhbx@hbu.cn [Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry and Environmental Science, Hebei University, Baoding 071002 (China); Wang, Jian; Yao, Meng; Guo, Lijie; Wang, Hai-jun [Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry and Environmental Science, Hebei University, Baoding 071002 (China); Ba, Xinwu, E-mail: baxw@hbu.cn [Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry and Environmental Science, Hebei University, Baoding 071002 (China)

    2013-05-15

    The polymer blends of hyperbranched poly(amide-ester) and poly(butylene succinate) (HBP/PBS) were prepared by melt-blending method. The molecular interaction within the blends, phase morphology, crystal morphology, mechanical, rheological and dynamic mechanical properties were investigated by using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), tensile machine, polarized optical microscopy, rotational rheometer and dynamic mechanical analyzer (DMA), respectively. The results suggest that PBS and HBP have a certain compatibility at amorphous state. A certain number of H-bonding was detected between PBS and HBP phases and it influences the material properties. HBP not only serves partially as a nucleating agent for the crystallization of PBS but also plays a role of plasticizer for the rheology of PBS. The glass transition temperatures of the blends slightly decrease with increasing HBP content. The proper amount of HBP (4–6%) has a reinforcement effect on the PBS matrix at glassy state. However, the blend with 10%HBP content has an improved impact strength mainly due to the plasticization effect or H-bonding effect of HBP on PBS matrix. The storage modulus is increased with increasing HBP contents, and the loss modulus is much smaller than the storage modulus in each blend at glassy state. At rubbery state the storage modulus of different samples is independent of HBP content. The complex viscosity of the melt decreases with increasing HBP content; however, the blend with 10%HBP is a special sample because of its abnormal larger complex viscosity at low shear frequencies. In addition, the melt’s elasticity behavior increases slightly with increasing HBP content. - Highlights: ► H-bonding was detected between PBS and HBP phases by FTIR. ► HBP serves partly as a nucleating agent for the crystallization of PBS. ► HBP plays a role of plasticizer for PBS. ► The blend with 10%HBP has abnormal larger complex viscosity.

  4. The Reaction and Applied Study of the Amide and P2S5

    Institute of Scientific and Technical Information of China (English)

    Guan zuowu; Ma Zhuang; Liu Xing; Cheng Tie-ming

    2004-01-01

    It is usually reported that reaction between carbonyl and P2S5 produce thiono group compound. The Products from carbonyl after ammonolysis and hydrazinolysis have the very import applied value in the synthesize of heterocyclic compound. Sulfuration reation if a nucleophilic attack,SPS2 anionsid obtained from P2S5 in the organic sovent, rather easier than thereationsof scheeren's reagent. The reation mechanism is as follows:The reation speed has something todo with the electronegative of R1R2 can be aliphatic group or aromatic group. The reaction can take place in the polar solvent or non-polar solent.But it is seldom reported that cyclic amide can be sulfured. In 1964, G.A, Archer et made the 7-chloro-1,3-dihyhro-5-phenyl 2H-1,4-ebnzodiazepin-2-thioue and in the reation of pyridine solent with 7-chloro-1,3-dilydro-5-phenyl-2H-1,4-benzodiazepin-2-one and P2S5. And the yield rate reached 40%. This reaction is very important in the pharmaceutical compound, but has quite low yield rate and high cost with present method. And the application is restricted duo to the pyridine,but it is a feasible way indeed. So we undertook further the deep studyof this, made P2S5 catalytic sulfurization in the proper solvent. And the yield rate of the reation has raised a lot. The quality of this product has been affirmed by UV. IR. 1HMNR.MS chart. This method successfully has been applied for the pharmaceutical compound, such as, Estazolam, Trithlozine Alprazolam, Triazolam Clozapine. This has been applied for manufacturing with obvious economic and social benefit.

  5. Evidence for a Phe-Gly-Leu-amide-like allatostatin in the beetle Tenebrio molitor.

    Science.gov (United States)

    Elliott, Karen L; Chan, Kuen Kuen; Stay, Barbara

    2010-03-01

    The allatostatins (ASTs) with Phe-Gly-Leu-amide C-terminal sequence are multifunctional neuropeptides discovered as inhibitors of juvenile hormone (JH) synthesis by corpora allata (CA) of cockroaches. Although these ASTs inhibit JH synthesis only in cockroaches, crickets, termites and locusts, isolation of peptides or of cDNA/genomic DNA or analysis of genomes indicates their occurrence in many orders of insects with the exception of coleopterans. The gene for these ASTs has not been found in the genome of the red flour beetle Tribolium castaneum (Family Tenebrionidae). Yet, in view of widespread occurrence of these peptides in insects, crustaceans and nematodes, they would be expected to occur in beetles. This study provides evidence for the presence of FGLa-like ASTs in the tenebrionid beetle, Tenebrio molitor, and scarabid beetle, Popillia japonica. Extract of brain from both beetles inhibited JH synthesis by cockroach CA dose dependently and reversibly. 20 brain equivalents of T. molitor and P. japonica extracts inhibited JH synthesis 64+/-5 and 65+/-0.6% respectively. Antibody against cockroach allatostatin (Diploptera punctata AST-7) used in an enzyme-linked immunosorbent assay reacted with brain extract of these beetles. Antibody against D. punctata AST-5 localized FGLa-like ASTs in the brain and subesophageal ganglion of T. molitor and P. japonica. In addition, pretreatment of T. molitor brain extract with anti-D. punctata AST-5 reduced the inhibition of JH synthesis and pretreatment of anti-D. punctata AST-5 with D. punctata AST-5 diminished the immunoreactivity of the antibody. Thus we predict that FGLa-like allatostatins will be found in beetles.

  6. 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.

  7. 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.

  8. Amide cis-trans isomerization in aqueous solutions of methyl N-formyl-D-glucosaminides and methyl N-acetyl-D-glucosaminides: chemical equilibria and exchange kinetics.

    Science.gov (United States)

    Hu, Xiaosong; Zhang, Wenhui; Carmichael, Ian; Serianni, Anthony S

    2010-04-07

    Amide cis-trans isomerization (CTI) in methyl 2-deoxy-2-acylamido-d-glucopyranosides was investigated by (1)H and (13)C NMR spectroscopy. Singly (13)C-labeled methyl 2-deoxy-2-formamido-d-glucopyranoside (MeGlcNFm) anomers provided standard (1)H and (13)C chemical shifts and (1)H-(1)H and (13)C-(13)C spin-coupling constants for cis and trans amides that are detected readily in aqueous solution. Equipped with this information, doubly (13)C-labeled methyl 2-deoxy-2-acetamido-d-glucopyranoside (MeGlcNAc) anomers were investigated, leading to the detection and quantification of cis and trans amides in this biologically important aminosugar. In comparison to MeGlcNFm anomers, the percentage of cis amide in aqueous solutions of MeGlcNAc anomers is small ( approximately 23% for MeGlcNFm versus approximately 1.8% for MeGlcNAc at 42 degrees C) but nevertheless observable with assistance from (13)C-labeling. Temperature studies gave thermodynamic parameters DeltaG degrees , DeltaH degrees , and DeltaS degrees for cis-trans interconversion in MeGlcNFm and MeGlcNAc anomers. Cis/trans equilibria depended on anomeric configuration, with solutions of alpha-anomers containing less cis amide than those of beta-anomers. Confirmation of the presence of cis amide in MeGlcNAc solutions derived from quantitative (13)C saturation transfer measurements of CTI rate constants as a function of solution temperature, yielding activation parameters E(act), DeltaG degrees (), DeltaH degrees (), and DeltaS degrees () for saccharide CTI. Rate constants for the conversion of trans to cis amide in MeGlcNFm and MeGlcNAc anomers ranged from 0.02 to 3.59 s(-1) over 31-85 degrees C, compared to 0.24-80 s(-1) for the conversion of cis to trans amide over the same temperature range. Energies of activation ranged from 16-19 and 19-20 kcal/mol for the cis --> trans and trans --> cis processes, respectively. Complementary DFT calculations on MeGlcNFm and MeGlcNAc model structures were conducted to evaluate

  9. Unraveling the degradation of artificial amide bonds in nylon oligomer hydrolase: from induced-fit to acylation processes.

    Science.gov (United States)

    Baba, Takeshi; Boero, Mauro; Kamiya, Katsumasa; Ando, Hiroyuki; Negoro, Seiji; Nakano, Masayoshi; Shigeta, Yasuteru

    2015-02-14

    To elucidate how the nylon oligomer hydrolase (NylB) acquires its peculiar degradation activity towards non-biological amide bonds, we inspected the underlying enzymatic processes going from the induced-fit upon substrate binding to acylation. Specifically we investigated the mutational effects of two mutants, Y170F and D181G, indicated in former experiments as crucial systems because of their specific amino acid residues. Therefore, by adopting first-principles molecular dynamics complemented with metadynamics we provide a detailed insight into the underlying acylation mechanism. Our results show that while in the wild type (WT) the Tyr170 residue points the NH group towards the proton-acceptor site of an artificial amide bond, hence ready to react, in the Y170F this does not occur. The reason is ascribed to the absence of Tyr170 in the mutant, which is replaced by phenylalanine, which is unable to form hydrogen bond with the amide bond; thus, resulting in an increase in the activation barrier of more than 10 kcal mol(-1). Nonetheless, despite the lack of hydrogen bonding between the Y170F and the substrate, the highest free energy barrier for the induced-fit is similar to that of WT. This seems to suggest that in the induced-fit process, kinetics is little affected by the mutation. On the basis of additional structural homology analyses on the enzymes of the same family, we suggest that natural selection is responsible for the development of the peculiar hydrolytic activity of Arthrobacter sp. KI72.

  10. Synthesis of monomeric and polymeric alkali and alkaline earth metal complexes using a phosphinoselenoic amide ligand in metal coordination sphere

    Indian Academy of Sciences (India)

    Jayeeta Bhattacharjee; Ravi K Kottalanka; Harinath Adimulam; Tarun K Panda

    2014-09-01

    We report the monomeric complexes of magnesium and calcium of composition [M(THF){2-Ph2P(Se)N(CMe3)}2] [M= Mg (3), n = 1 andM = Ca (4), n = 2)] and polymeric complexes of potassium and barium of composition [K(THF)2{Ph2P(Se)N(CMe3)}] (2) and [K(THF)Ba{Ph2P(Se)N(CMe3)}3](5) respectively. The potassium complex 2 was readily prepared by the reaction of potassium bis(trimethylsilyl)amide with phosphinoselenoic amide ligand (1) at ambient temperature. The calcium complex 4 was prepared by two synthetic routes: in the first method, commonly known as salt metathesis reaction, the potassium complex 2 was made to react with alkaline earth metal diiodide at room temperature to afford the corresponding calcium complex. The metal bis(trimethylsilyl)amides were made to react with protic ligand 1 in the second method to eliminate the volatile bis(trimethyl)silyl amine. The magnesium complex 3 and barium complex 5 were prepared only through the first method. Solid-state structures of all the new complexes were established by single crystal X-ray diffraction analysis. The smaller ionic radii of Mg2+ (0.72Å) and Ca2+ (0.99Å) ions form the monomeric complex, whereas the larger ions K+ (1.38Å) and Ba2+ (1.35Å) were found to form onedimensional polymeric complexes with monoanionic ligand 1. Compound 2 serves an example of magnesium complex with a Mg-Se direct bond.

  11. Quantification of in vivo pH-weighted amide proton transfer (APT) MRI in acute ischemic stroke

    Science.gov (United States)

    Zhou, Iris Y.; Igarashi, Takahiro; Guo, Yingkun; Sun, Phillip Z.

    2015-03-01

    Amide proton transfer (APT) imaging is a specific form of chemical exchange saturation transfer (CEST) MRI that probes the pH-dependent amide proton exchange.The endogenous APT MRI is sensitive to tissue acidosis, which may complement the commonly used perfusion and diffusion scans for characterizing heterogeneous ischemic tissue damage. Whereas the saturation transfer asymmetry analysis (MTRasym) may reasonably compensate for direct RF saturation, in vivo MTRasym is however, susceptible to an intrinsically asymmetric shift (MTR'asym). Specifically, the reference scan for the endogenous APT MRI is 7 ppm upfield from that of the label scan, and subjects to concomitant RF irradiation effects, including nuclear overhauser effect (NOE)-mediated saturation transfer and semisolid macromolecular magnetization transfer. As such, the commonly used asymmetry analysis could not fully compensate for such slightly asymmetric concomitant RF irradiation effects, and MTRasym has to be delineated in order to properly characterize the pH-weighted APT MRI contrast. Given that there is very little change in relaxation time immediately after ischemia and the concomitant RF irradiation effects only minimally depends on pH, the APT contrast can be obtained as the difference of MTRasym between the normal and ischemic regions. Thereby, the endogenous amide proton concentration and exchange rate can be solved using a dual 2-pool model, and the in vivo MTR'asym can be calculated by subtracting the solved APT contrast from asymmetry analysis (i.e., MTR'asym =MTRasym-APTR). In addition, MTR'asym can be quantified using the classical 2-pool exchange model. In sum, our study delineated the conventional in vivo pH-sensitive MTRasym contrast so that pHspecific contrast can be obtained for imaging ischemic tissue acidosis.

  12. CURING KINETICS AND THERMAL STABILITY OF EPOXY BLENDS CONTAINING PHOSPHOROUS-OXIRANE WITH AROMATIC AMIDE-AMINE AS CURING AGENTS

    Institute of Scientific and Technical Information of China (English)

    Geeta Durga; A.K.Narula

    2012-01-01

    This article describes the synthesis of a series of aromatic amide-amines and their potential use as epoxy hardeners.These amines were synthesized by the reaction of L-phenylalanine (PA) with diamines of different structures i.e.1,4-phenylene diamine (PD),1,5-diamino naphthalene (N),4,4′-(9-fluorenyllidene)-dianiline (F),4,4′-diaminodiphenyl sulphide (DS) and 3,4′-oxydianiline (O) in a stoichiometric ratio (1∶1).Structural characterization of synthesized amide-amines was done with the help of elemental analysis and spectroscopic techniques viz.FT-IR,1H-NMR and 13C-NMR.An epoxy blend was prepared by mixing tris(glycidyloxy) phosphine oxide (TGPO) with conventional epoxy i.e.diglycidyl ether of bisphenol-A (DGEBA) in an equivalent ratio of 2∶3 to incorporate phosphorous into the main chain.The curing kinetics of the epoxy blend with synthesized aromatic amide-amines was investigated by non-isothermal DSC technique using multiple heating rate method (5,10,15 and 20 K/min.).The activation energies were determined by fitting the experimental data into Kissinger and Ozawa kinetic models.The activation energies obtained through Ozawa method were slightly higher than those of Kissinger method but were comparable.However,both the energies were found to be dependent on the structure of amines.The thermal stability and weight loss behavior of isothermally cured thermosets were also investigated using thermogravimetric analysis (TGA) in nitrogen atmosphere.All the samples showed improved thermal stability in terms of char yield than using only amines as hardeners.

  13. Halochromism, ionochromism, solvatochromism and density functional study of a synthesized copper(II) complex containing hemilabile amide derivative ligand.

    Science.gov (United States)

    Golchoubian, Hamid; Moayyedi, Golasa; Reisi, Neda

    2015-03-05

    This study investigates chromotropism of newly synthesized 3,3'-(ethane-1,2-diylbis(benzylazanediyl))dipropanamide copper(II) perchlorate complex. The compound was structurally characterized by physico-chemical and spectroscopic methods. X-ray crystallography of the complex showed that the copper atom achieved a distorted square pyramidal environment through coordination of two amine N atoms and two O atoms of the amide moieties. The pH effect on the visible absorption spectrum of the complex was studied which functions as pH-induced "off-on-off" switches through protonation and deprotonation of amide moieties along with the CuO to CuN bond rearrangement at room temperature. The complex was also observed to show solvatochromism and ionochromism. The distinct solution color changes mainly associated with hemilability of the amide groups. The solvatochromism of the complex was investigated with different solvent parameter models using stepwise multiple linear regression method. The results suggested that the basicity power of the solvent has a dominant contribution to the shift of the d-d absorption band of the complex. Density functional theory, DFT calculations were performed in order to study the electronic structure of the complex, the relative stabilities of the CuN/CuO isomers, and to understand the nature of the halochromism processes taking place. DFT computational results buttressed the experimental observations indicating that in the natural pH (5.8) the CuO isomer is more stable than its linkage isomer and conversely in alkaline aqueous solution.

  14. Halochromism, ionochromism, solvatochromism and density functional study of a synthesized copper(II) complex containing hemilabile amide derivative ligand

    Science.gov (United States)

    Golchoubian, Hamid; Moayyedi, Golasa; Reisi, Neda

    2015-03-01

    This study investigates chromotropism of newly synthesized 3,3‧-(ethane-1,2-diylbis(benzylazanediyl))dipropanamide copper(II) perchlorate complex. The compound was structurally characterized by physico-chemical and spectroscopic methods. X-ray crystallography of the complex showed that the copper atom achieved a distorted square pyramidal environment through coordination of two amine N atoms and two O atoms of the amide moieties. The pH effect on the visible absorption spectrum of the complex was studied which functions as pH-induced "off-on-off" switches through protonation and deprotonation of amide moieties along with the Cusbnd O to Cusbnd N bond rearrangement at room temperature. The complex was also observed to show solvatochromism and ionochromism. The distinct solution color changes mainly associated with hemilability of the amide groups. The solvatochromism of the complex was investigated with different solvent parameter models using stepwise multiple linear regression method. The results suggested that the basicity power of the solvent has a dominant contribution to the shift of the d-d absorption band of the complex. Density functional theory, DFT calculations were performed in order to study the electronic structure of the complex, the relative stabilities of the Cusbnd N/Cusbnd O isomers, and to understand the nature of the halochromism processes taking place. DFT computational results buttressed the experimental observations indicating that in the natural pH (5.8) the Cusbnd O isomer is more stable than its linkage isomer and conversely in alkaline aqueous solution.

  15. 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.

  16. Development of a novel amide-silica stationary phase for the reversed-phase HPLC separation of different classes of phytohormones.

    Science.gov (United States)

    Aral, Hayriye; Aral, Tarık; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

    2013-11-15

    A novel amide-bonded silica stationary phase was prepared starting from N-Boc-phenylalanine, cyclohexylamine and spherical silica gel (4 µm, 60 Å). The amide ligand was synthesised with high yield. The resulting amide bonded stationary phase was characterised by SEM, IR and elemental analysis. The resulting selector bearing a polar amide group is used for the reversed-phase chromatography separation of different classes of thirteen phytohormones (plant hormones). The chromatographic behaviours of these analytes on the amide-silica stationary phase were compared with those of RP-C18 column under same conditions. The effects of different separation conditions, such as mobile phase, pH value, flow rate and temperature, on the separation and retention behaviours of the 13 phytohormones in this system were studied. The optimum separation was achieved using reversed-phase HPLC gradient elution with an aqueous mobile phase containing pH=6.85 potassium phosphate buffer (20 mM) and acetonitrile with a 22 °C column temperature. Under these experimental conditions, the 12 phytohormones could be separated and detected at 230 or 270 nm within 26 min.

  17. Design and synthesis of peptide YY analogues with c-terminal backbone amide-to-ester modifications

    DEFF Research Database (Denmark)

    Albertsen, Louise; Andersen, J.J.; Paulsson, J.F.;

    2013-01-01

    Peptide YY (PYY) is a gut hormone that activates the G protein-coupled neuropeptide Y (NPY) receptors, and because of its appetite reducing actions, it is evaluated as an antiobesity drug candidate. The C-terminal tail of PYY is crucial for activation of the NPY receptors. Here, we describe...... the design and preparation of a series of PYY(3-36) depsipeptide analogues, in which backbone amide-to-ester modifications were systematically introduced in the C-terminal. Functional NPY receptor assays and circular dichroism revealed that the ψ(CONH) bonds at positions 30-31 and 33-34 are particularly...

  18. Evaluation of enthalpy change due to hydrogen desorption for lithium amide/imide system by differential scanning calorimetry

    OpenAIRE

    2008-01-01

    Enthalpy change (ΔH) due to hydrogen desorption (H-desorption) for the lithium amide/imide system was evaluated by differential scanning calorimetry (DSC) measurement. In order to obtain the accurate and precise value of ΔH, we have paid special attention to following two points for correcting raw experimental data. One is to determine a cell constant of DSC equipment, which was evaluated by using the TiO2-doped MgH2 compound as a reference because of its quite similar hydrogen desorption pro...

  19. The structure of geminal imidazolium bis(trifluoromethylsulfonyl)amide ionic liquids: a theoretical study of the gas phase ionic complexes.

    Science.gov (United States)

    Bodo, E; Caminiti, R

    2010-12-02

    In this work we report molecular mechanics and ab initio calculations on the geminal di-imidazolium bis(trifluoromethylsulfonyl)amide ionic liquid in the gas phase. We report the likely energetically preferred geometries of the ionic complex and its main features in terms of charge distribution, electronic density, structure, and energetics. We find that the gas phase structure of the ionic complex is quite compact and that the alkyl chain connecting the two imidazolium charged rings is strongly bent in order to maximize their electrostatic interactions with the two anions.

  20. Processing of pro-opiomelanocortin-derived amidated joining peptide and glycine-extended precursor in monkey pituitary

    DEFF Research Database (Denmark)

    Fenger, M

    1991-01-01

    The molecular forms of proopiomelanocortin (POMC) derived amidated and C-terminal glycine-extended joining peptide from monkey (Macaca mulatta) pituitary were determined. The predominant forms of joining peptide found were the low molecular peptides POMC(76-105) and POMC(76-106), respectively...... sequence of monkey and human POMC extremely conserved, but also the processing patterns are similar. The monkey therefore serves as a suitable model for studying regulation of the processing of POMC and the hypothalamus-pituitary-adrenal axis in man....