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Sample records for 1,4-diaminobutane

  1. Phase equilibrium properties of binary aqueous solutions containing ethanediamine, 1,2-diaminopropane, 1,3-diaminopropane, or 1,4-diaminobutane at several temperatures

    Ahmed, Nouria Chiali-Baba [LATA2M, Laboratoire de Thermodynamique Appliquee et Modelisation Moleculaire, University AbouBekr Belkaid of Tlemcen, P.O. Box 119, Tlemcen 13000 (Algeria); Negadi, Latifa, E-mail: l_negadi@mail.univ-tlemcen.d [LATA2M, Laboratoire de Thermodynamique Appliquee et Modelisation Moleculaire, University AbouBekr Belkaid of Tlemcen, P.O. Box 119, Tlemcen 13000 (Algeria); Mokbel, Ilham; Jose, Jacques [LSA, Laboratoire des Sciences Analytiques, CNRS-UMR 5180, Universite Claude Bernard - Lyon I. 43, Bd du 11 Novembre 1918, Villeurbanne Cedex 69622 (France)

    2011-05-15

    Research highlights: Vapour pressures of ethanediamine (EDA), 1,2-diaminopropane, 1,3-diaminopropane (1,3-DAP), or 1,4-diaminobutane (1,4-DAB) aqueous solutions are reported between (293 and 363) K. The two first mixtures show negative azeotropic behaviour. The aqueous solutions of EDA, 1,2-DAP, or 1,3-DAP exhibit negative G{sup E} whereas the one containing 1,4-DAB shows either negative G{sup E} or sinusoidal shape for G{sup E}. - Abstract: The vapour pressures of {l_brace}ethanediamine (EDA) + water{r_brace}, {l_brace}1,2-diaminopropane (1,2-DAP) + water{r_brace}, {l_brace}1,3-diaminopropane (1,3-DAP) + water{r_brace} or {l_brace}1,4-diaminobutane (1,4-DAB) + water{r_brace} binary mixtures, and of pure EDA, 1,2-DAP, 1,3-DAP, 1,4-DAB, and water components were measured by means of two static devices at temperatures between (293 and 363) K. The data were correlated with the Antoine equation. From these data, the excess Gibbs function (G{sup E}) was calculated for several constant temperatures and fitted to a fourth-order Redlich-Kister equation using the Barker's method. The {l_brace}ethanediamine (EDA) + water{r_brace}, and {l_brace}1,2-diaminopropane (1,2-DAP) + water{r_brace} binary systems show negative azeotropic behaviour. The aqueous solutions of EDA, 1,2-DAP, or 1,3-DAP exhibit negative deviations in G{sup E} for all investigated temperatures over the whole composition range whereas the (1,4-DAB + water) binary mixture shows negative G{sup E} for temperatures (293.15 < T/K < 353.15) and a sinusoidal shape for G{sup E} at T = 363.15 K.

  2. Attempts at the production of more selective antitumourals. Part I. The antineoplastic activity of cyclophosphazenes linked to the polyamines 1,3-diaminopropane and 1,4-diaminobutane (putrescine)

    Labarre, Jean-François; Guerch, Guy; Sournies, François; Spreafico, Federico; Filippeschi, Stefania

    1984-06-01

    In an attempt to design antitumour cyclophosphazenes of improved specificity by linking them to some natural tumour finders, we studied the binding of gem-N 3P 3Az 4Cl 2 to 1,3-diaminopropane and 1,4-diaminobutane (putrescine). Synthesis, mass spectrum and NMR as well as X-ray crystal structures of the two spirocyclic N 3P 3Az 4 [HN(CH 2) 3,4NH] derivatives (in which the N 3P 3Az 4 active principle is linked to the diamine in a spiro configuration) are described. Results obtained with these compounds in 3 murine tumour systems (L1210 and P388 leukaemias and P815 mastocytoma), showing their potent antineoplastic activity in vivo obtainable at well-tolerated doses, are also described.

  3. Synthesis and X-ray structure analysis of a new binuclear Schiff base Co(II) complex with the ligand N,N'-bis(3-methoxysalicylidene)-1,4-butanediamine

    The title binuclear complex, tris[N,N-bis(3-methoxysalicylidene)-1,4-diaminobutane] dicobalt(II), C60H70Co2N6O15, was prepared by the reaction of the tetradentate Schiff base ligand bis(3-methoxysalicylidene)-1,4-diaminobutane and Co(CH3COO)2 . 4H2O in a ethanol solution and structurally characterized by single-crystal X-ray diffraction. This complex has a dinuclear structure where two Co(II) ions are bridged by one N0,N'-bis(3-methoxysalicylidene)-1,4-diaminobutane. The two Co(II) ions, have two distorted octahedral coordination involving two O and two N atoms.

  4. The synthesis of 3H-putrescine and subsequent biosynthesis of 3H-jacobine, a pyrrolizidine alkaloid from Senecio jacobaea

    A new method was developed for the preparation of tritiated putrescine dihydrochloride ([2,3-3H]-1,4-diaminobutane dihydro-chloride) from succinonitrile (1,4-butanedinitrile) and 3H2O, with a radiochemical yield of 16%. Tritiated jacobine and other pyrrolizidine alkaloids were then biosynthesized in Senecio jacobaea using 3H-putrescine-2HCl as the precursor with a radiochemical yield of 0.9% into total pyrrolizidine alkaloids. Jacobine accounted for 36% of the total. This synthetic method provides a relatively inexpensive source for the preparation of these labelled compounds. (author)

  5. Thermal and structural study on the lattice compound 1,4-diammoniumbutane bis(theophyllinate)

    Crystalline title compound (1) prepared from aqueous solution of theophylline and 1,4-diaminobutane has been structurally and thermally characterized. Both the two-step TG decomposition curve and elemental analysis of the hexagonal crystals show that it consists of theophylline and 1,4-diaminobutane in 2:1 molar ratio. Actually, presence of one type of both theophyllinate anions and 1,4-diammoniumbutane dication have been indicated by FTIR spectroscopy. The molecular structure of lattice compound (1) has been determined by single crystal X-ray diffraction, where the hydrogen positions have been obtained from differential Fourier maps. It has confirmed that the crystal is really built up from these ionic constituents bound together with an extensive net of hydrogen bonds. The coupled TG-FTIR analysis of the evolved gases has revealed that the diamine is released as a whole molecule in the first decomposition step. Clathrate 1 and the proton migration in it might serve as a structural model of solid aminophylline whose crystal structure is still unknown

  6. Thermal and structural study on the lattice compound 1,4-diammoniumbutane bis(theophyllinate)

    Ban, Margit; Madarasz, Janos; Bombicz, Petra; Pokol, Gyoergy; Gal, Sandor

    2004-10-01

    Crystalline title compound (1) prepared from aqueous solution of theophylline and 1,4-diaminobutane has been structurally and thermally characterized. Both the two-step TG decomposition curve and elemental analysis of the hexagonal crystals show that it consists of theophylline and 1,4-diaminobutane in 2:1 molar ratio. Actually, presence of one type of both theophyllinate anions and 1,4-diammoniumbutane dication have been indicated by FTIR spectroscopy. The molecular structure of lattice compound (1) has been determined by single crystal X-ray diffraction, where the hydrogen positions have been obtained from differential Fourier maps. It has confirmed that the crystal is really built up from these ionic constituents bound together with an extensive net of hydrogen bonds. The coupled TG-FTIR analysis of the evolved gases has revealed that the diamine is released as a whole molecule in the first decomposition step. Clathrate 1 and the proton migration in it might serve as a structural model of solid aminophylline whose crystal structure is still unknown.

  7. Synthesis and characterization of NiPcTSTNa(L) thin films

    M E Sánchez-Vergara; V García-Montalvo; J Santoyo-Salazar; R J Fragoso-Soriano; O Jiménez-Sandoval

    2012-10-01

    NiPcTSTNa(L) [L=ethylenediamine (EDA); 1,4-diaminobutane (BDA); and 2,6-diamineanthraquinone (AqDA)] thin films were deposited by thermal evaporation. Their surface morphology was studied by AFM and SEM, and their chemical composition determined by EDS. Optical absorption studies of NiPcTSTNa(L) films were performed in the 200–1150 nm wavelength range. The optical bandgap of thin films was determined from the ( ℎ )1/2 vs ℎ plots for indirect allowed transitions. The temperature dependence of electrical conductivity shows a semiconducting behaviour. The amorphous semiconductor films show thermal activation energies of electrical conduction between 3.3 and 3.7 eV.

  8. The inhibition of anti-DNA binding to DNA by nucleic acid binding polymers.

    Nancy A Stearns

    Full Text Available Antibodies to DNA (anti-DNA are the serological hallmark of systemic lupus erythematosus (SLE and can mediate disease pathogenesis by the formation of immune complexes. Since blocking immune complex formation can attenuate disease manifestations, the effects of nucleic acid binding polymers (NABPs on anti-DNA binding in vitro were investigated. The compounds tested included polyamidoamine dendrimer, 1,4-diaminobutane core, generation 3.0 (PAMAM-G3, hexadimethrine bromide, and a β-cylodextrin-containing polycation. As shown with plasma from patients with SLE, NABPs can inhibit anti-DNA antibody binding in ELISA assays. The inhibition was specific since the NABPs did not affect binding to tetanus toxoid or the Sm protein, another lupus autoantigen. Furthermore, the polymers could displace antibody from preformed complexes. Together, these results indicate that NABPs can inhibit the formation of immune complexes and may represent a new approach to treatment.

  9. Synthesis of water-soluble, nonimmunogenic polyamide cross-linking agents.

    Hai, T T; Pereira, D E; Nelson, D J

    1998-01-01

    Novel polyamides were developed that can be used as cross-linking agents for proteins such as hemoglobin. Water-soluble, nonimmunogenic polyamides containing oxygen and sulfur atoms in the backbone were prepared by the polycondensation of the diacids bis(carboxymethyloxyacetyl)-1,4-diaminobutane (1a) or 3, 3'-thiodipropionic acid (1b) with diethylene glycol bis(3-aminopropyl) ether (2). The resulting alpha,omega-diacids were converted to the corresponding activated esters using any of a variety of carboxylic acid activating reagents including the novel reagent diphenyl(1-methylimidazol-2-thiyl)phosphonate (9). The resulting polyamides could be activated with a broad spectrum of groups that allow for the cross-linking and surface modification of proteins. PMID:9815156

  10. Synthesis, characterization, thermal and electrical studies of poly schiff base chelates of VO(IV), MoO2(VI) and UO2(VI)

    Polychelates of VO (IV), MoO2 (VI) and UO2(VI) with Schiff base ligand 2,4 dihydoxy-5-acetyl acetophenone-1,4-diaminobutane (DHADAB) have been synthesized and characterized by elemental analysis, IR and electronic spectra, 1H-NMR spectra, magnetic susceptibility, electrical conductivity measurements and thermogravimetric analysis. An octahedral geometry has been assigned to MoO2(VI) and UO2(VI) complexes while square pyramidal geometry for VO(IV) complexes. The thermal behaviour of the chelates was studied and kinetic parameters were determined by Coats-Redfern method and suggest more ordered activated state in complex formation. The solid state electrical conductivity of the ligand and its polychelates have been studied and it increases with increasing the temperature indicates their semiconducting behaviour. (author)

  11. Synthesis and characterization of a novel versatile poly(amic acid) derived from ethylenediaminetetraacetic dianhydride

    The polycondensation reaction between ethylenediaminetetraacetic dianhydride and 1,4-diaminobutane in various aprotic polar solvents is being exploited to create a novel linear aliphatic polymer poly(amic acid) (PAA). PAA samples were characterized by Fourier transform infrared, Proton nuclear magnetic resonance and Carbon nuclear magnetic resonance spectroscopy resulting in the identification of characteristic absorption bands and thereby verifying successful synthesis. Gel permeation chromatography confirmed narrow molecular weight distributions with polydispersity indices ranging from 1.2 to 2.2 and reported low number average molecular weights ranging from 4000 to 6000 g mol-1. X-ray photoelectron spectroscopy and energy dispersive X-ray analysis showed the presence of nitrogen on the surface and also found nitrogen to be homogenously distributed throughout the bulk of the PAA samples.

  12. Attempts at the production of more selective antitumourals. Part II. The antineoplastic activity of cyclophosphazenes linked to spermine

    Sournies, François; Labarre, Jean-François; Spreafico, Federico; Filippeschi, Stefania; Quan Jin, Xing

    1986-09-01

    In an attempt to design antitumour cyclophosphazenes of improved specificity by linking them to some natural tumour finders, we studied the binding of gem-N 3P 3Az 4Cl 2 to spermine. Synthesis, NMR and mass spectra of the vectorized drug (in which two N 3P 3Az 4 active principles are linked to spermine in a DISPIROBINO configuration) are described. Results obtained with this compound in 6 murine tumour systems (L1210 and P388 leukaemias, 3LL carcinoma, M5076 reticulum cell sarcoma, B16 melanoma and line 16 mammary carcinoma), are also described and compared with results previously obtained about the targeting of gem-N 3P 3Az 4Cl 2 through 1,3-diaminopropane and 1,4-diaminobutane (putrescine).

  13. Synthetic, structural, thermal and electrical properties of some transition metal polymeric chelates of bis(mercaptoacetamido)diaminobutane

    Polymeric chelates of bis(mercaptoacetamido)-1,4-diaminobutane (BMADB) with manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) ions have been synthesized and characterized by elemental analysis, magnetic moment, infrared, electronic spectra and thermal analysis. In the present investigation the ligand BMADB exhibits bis-bidentate character and coordinates symmetrically with metal through nitrogen of amino and sulfur mercapto groups. The thermogravimetric studies indicate a two stage decomposition and the presence of water molecules. Thermal data have been analysed by Freeman-Carroll and Sharp-Wentworth methods and various kinetic and thermodynamic parameters have also be evaluated. Comparable values of parameters indicate common decomposition reaction mode of all chelates. Their d.c. electrical conductivity in pellet form over a wide range of temperatures have also been studied. (author)

  14. The immobilization of lipase on PVDF-co-HFP membrane

    Kayhan, Naciye; Eyüpoǧlu, Volkan; Adem, Şevki

    2016-04-01

    Lipase is an enzyme having a lot of different industrial applications such as biodiesel production, biopolymer synthesis, enantiopure pharmaceutical productions, agrochemicals, etc. Its immobilized form on different substances is more conventional and useful than its free form. Supporting material was prepared using PVDF-co-HFP in laboratory conditions and attached 1,4-diaminobutane (DA) and epichlorohydrin (EPI) ligands to the membrane to immobilize lipase enzyme. The immobilization conditions such as enzyme amount, pH, the concentration of salt, thermal stability and activity were stabilized for our experimental setup. Then, biochemical characterizations were performed on immobilized lipase PVDF-co-HFP regarding optimal pH activity, temperature and thermal stability. Also, the desorption ratios of immobilized enzyme in two different pathway were investigated to confirm immobilization stability for 24 hours.

  15. Synthesis and Properties of pH and Temperature Responsive Copolymer with Pesudorotaxane Structure

    MA Qiang; YANG Hui; XU Wen-chao; TAN Ye-bang

    2012-01-01

    pH and temperature responsive copolymers PNAM4VBCB of N-isopropyl acrylamide(NAM) and complex pseudorotaxane monomer N1-(4-vinylbenzyl)-1,4-diaminobutane dihydrochloride with cucurbit[6]uril(CB[6])threaded(4VBCB) were prepared via free-radical polymerization in aqueous solution.The copolymers were characterized by 1H NMR,Fourier transform infrared(FTIR) spectrometry,elemental analysis,and static light scattering.The thermodynamic properties of the copolymers were studied by thermogravimetric analysis(TGA),and the effects of pH and the concentration of the copolymer on the average hydrodynamic radius(Rh) were studied by dynamic light scattering(DLS).In addition,the thermal sensitivities of the copolymers were studied by DLS and UV-Vis.The experiment data show that CB[6] beads are localized on 1,4-diaminobutane units in the side chains of the copolymer.TGA data show that thermal stability of the copolymers increases with the adding of CB[6] threaded because of the enhanced rigidity and the bulky steric hindrance of 4VBCB in the side chain of PNAM4VBCB.DLS data show that the average hydrodynamic radius of copolymer increases with the increase of the copolymer concentration and has a jump with adjusting pH due to the existing of the small size CB[6] dethreaded from the copolymer with increasing pH.Both pH and electrical conductivity curves of the solution of PNAM4VBCB-4 have a jump because CB[6] could dethread from the copolymers with the addition of NaOH.In addition,the copolymers have thermal sensitivity and their phase-change temperatures could be controlled by adjusting the molar ratio of NAM to 4VBCB in the copolymers.

  16. Preliminary studies of 99mTc-BnAO and its analogues: synthesis, radiolabeling and in vitro cell uptake

    Introduction: 99mTc-BnAO is one of the nonnitroimidazole hypoxia markers with the highest citation and could be potentially useful in both oncology and other clinical applications. However, it appears inferior in vitro due to lower absolute accumulation and smaller anoxic/normoxic uptake ratio. It is possible that the analogues of 99mTc-BnAO have higher hypoxia selectivity after the ligand of 99mTc-BnAO is modified. Methods: 2,2'-(1,4-Diaminobutane)bis(2-methyl-3-butanone) dioxime (BnAO or HL91) and three novel analogues were synthesized and radiolabeled with technetium-99m. The cellular uptake of the radiolabeled complexes was determined in murine sarcoma S180 cell lines under anoxic and normoxic conditions. Results: 99mTc-BnAO and its three novel analogues continuously accumulated in anoxic cells but not in normoxic ones, while the analogues showed earlier hypoxia selectivity and greater anoxic/normoxic differential. Conclusions: The analogues are superior to 99mTc-BnAO in terms of in vitro hypoxia selectivity and are viable candidates for further development as new nonnitroimidazole hypoxia markers in the future.

  17. Transition metal ion directed supramolecular assembly of one- and two-dimensional polyrotaxanes incorporating cucurbituril.

    Park, Ki-Min; Whang, Dongmok; Lee, Eunsung; Heo, Jungseok; Kim, Kimoon

    2002-01-18

    This paper reports a synthetic strategy to construct one- and two-dimensional (1D and 2D) polyrotaxanes, in which a number of rings are threaded onto a coordination polymer, by the combination of self-assembly and coordination chemistry. Our approach to construct polyrotaxanes with high structural regularity involves threading a cucurbituril (CB) "bead" with a short "string" to form a stable pseudorotaxane, followed by linking the pseudorotaxanes with metal ions as "linkers" to organize into a 1D or 2D polyrotaxane. A 4- or 3-pyridylmethyl group is attached to each end of 1,4-diaminobutane or 1,5-diaminopentane to produce the short "strings", which then react with the cucurbituril "bead" to form stable pseudorotaxanes. The reaction of the pseudorotaxanes with various transition metal ions including CuII, CoII, NiII, AgI, and CdII produces 1D or 2D polyrotaxanes, in which many molecular "beads" are threaded onto 1D or 2D coordination polymers as confirmed by X-ray crystallography. The overall structure of a polyrotaxane is the result of interplay among various factors that include the coordination preferences of the metal ion, spatial disposition of the donor atoms with respect to the CB beads in the pseudorotaxane, and the size and coordination ability of the counteranion. PMID:11843162

  18. Systems strategies for developing industrial microbial strains.

    Lee, Sang Yup; Kim, Hyun Uk

    2015-10-01

    Industrial strain development requires system-wide engineering and optimization of cellular metabolism while considering industrially relevant fermentation and recovery processes. It can be conceptualized as several strategies, which may be implemented in an iterative fashion and in different orders. The key challenges have been the time-, cost- and labor-intensive processes of strain development owing to the difficulties in understanding complex interactions among the metabolic, gene regulatory and signaling networks at the cell level, which are collectively represented as overall system performance under industrial fermentation conditions. These challenges can be overcome by taking systems approaches through the use of state-of-the-art tools of systems biology, synthetic biology and evolutionary engineering in the context of industrial bioprocess. Major systems metabolic engineering achievements in recent years include microbial production of amino acids (L-valine, L-threonine, L-lysine and L-arginine), bulk chemicals (1,4-butanediol, 1,4-diaminobutane, 1,5-diaminopentane, 1,3-propanediol, butanol, isobutanol and succinic acid) and drugs (artemisinin). PMID:26448090

  19. Synthesis and characterization of nido-carborane-cobalamin conjugates

    Three vitamin B12 (cyanocobalamin) conjugates bearing one nido-carborane molecule or two nido-carborane molecules linked to the propionamide side chains via a four carbon linker have been synthesized. Reaction of o-carboranoylchloride with 1,4-diaminobutane in pyridine produced nido-carboranoyl(4-amidobutyl)amine, which was linked to the b- and d-monocarboxylic acids and the b,d-dicarboxylic acid of cyanocobalamin. Mass spectrometry analysis as well as 11B nuclear magnetic resonance demonstrated that during the reaction of o-carboranonylchloride with diaminobutane one of the boron atoms was eliminated. In vitro biological activity of the cyanocobalamin-nido-carborane conjugates was assessed by the unsaturated vitamin B12 binding capacity assay. When compared with 57Co cyanocobalamin, the biological activity of cyanocobalamin-b-nido-carborane, cyanocobalamin-d-nido-carborane, and cyanocobalamin-b-d-bis-nido-carborane conjugates were 92.93%, 35.75%, and 37.02%, respectively. These findings suggest that the 10B cobalamin conjugates might be useful agents in treating malignant tumors via neutron capture therapy

  20. Vibrational Spectroscopy of Intramolecular Hydrogen Bonds in the Infrared and Near-Infrared Regions

    Schrøder, Sidsel Dahl

    This PhD thesis describes the gas phase studies of four intramolecular hydrogen bonds: O-H···O (in methyl lactate), O-H···π (in methallyl carbinol and allyl carbinol), O-H···N (in methylated and triuoromethylated 2-aminoethanol) and N-H···N (in the diamines 1,2-diaminoethane, 1,3-diaminopropane and...... 1,4-diaminobutane). Experimentally, the hydrogen bonds have been studied with vibrational spectroscopy in the infrared and near-infrared regions. The focus is primarily on spectra recorded in the near-infrared regions, which in these studies are dominated by O-H and N-H stretching overtones...... spectra. The experimental characterization of hydrogen bonds have been complemented by theoretical analyzes. These analyzes are based on the electron density topology, natural bond orbital theory and visualization of the distribution of electrostatic potential energy in the molecules. In these studies...

  1. Olfaction in dragonflies: electrophysiological evidence.

    Rebora, Manuela; Salerno, Gianandrea; Piersanti, Silvana; Dell'otto, Alessandro; Gaino, Elda

    2012-02-01

    The problem of olfaction in Paleoptera (Odonata, Ephemeroptera) cannot be considered fully elucidated until now. These insects have been traditionally considered anosmic, because their brain lacks glomerular antennal lobes, typically involved in Neoptera odor perception. In order to understand if the presumed coeloconic olfactory receptors described on the antennal flagellum of adult Odonata are really functioning, we performed an electrophysiological investigation with electroantennogram (EAG) and single cell recordings (SCR), using Libellula depressa L. (Odonata, Libellulidae) as a model species. Odors representing different chemical classes such as (Z)-3-hexenyl acetate (acetate ester), (E)-2-hexenal, octanal (aldehydes), (Z)-3-hexen-1-ol (alcohol), propionic acid, butyric acid (carboxylic acids), and 1,4-diaminobutane (amine) were tested. Most of the tested chemicals elicited depolarizing EAG responses in both male and female antennae; SCR show unambiguously for the first time the presence of olfactory neurons in the antennae of L. depressa and strongly support the olfactory function of the coeloconic sensilla located on the antennal flagellum of this species. Electrophysiological activity may not necessarily indicate behavioral activity, and the biological role of olfactory responses in Odonata must be determined in behavioral bioassays. This study represents a starting point for further behavioral, electrophysiological, neuroanatomical and molecular investigation on Odonata olfaction, a research field particularly interesting owing to the basal position of Paleoptera, also for tracing evolutionary trends in insect olfaction. PMID:22154954

  2. Synthesis and characterization of nido-carborane-cobalamin conjugates

    Hogenkamp, Harry P.C. E-mail: hogen001@tc.umn.edu; Collins, Douglas A.; Live, David; Benson, Linda M.; Naylor, Stephen

    2000-01-01

    Three vitamin B{sub 12} (cyanocobalamin) conjugates bearing one nido-carborane molecule or two nido-carborane molecules linked to the propionamide side chains via a four carbon linker have been synthesized. Reaction of o-carboranoylchloride with 1,4-diaminobutane in pyridine produced nido-carboranoyl(4-amidobutyl)amine, which was linked to the b- and d-monocarboxylic acids and the b,d-dicarboxylic acid of cyanocobalamin. Mass spectrometry analysis as well as {sup 11}B nuclear magnetic resonance demonstrated that during the reaction of o-carboranonylchloride with diaminobutane one of the boron atoms was eliminated. In vitro biological activity of the cyanocobalamin-nido-carborane conjugates was assessed by the unsaturated vitamin B{sub 12} binding capacity assay. When compared with {sup 57}Co cyanocobalamin, the biological activity of cyanocobalamin-b-nido-carborane, cyanocobalamin-d-nido-carborane, and cyanocobalamin-b-d-bis-nido-carborane conjugates were 92.93%, 35.75%, and 37.02%, respectively. These findings suggest that the {sup 10}B cobalamin conjugates might be useful agents in treating malignant tumors via neutron capture therapy.

  3. Biotechnological production of polyamines by bacteria: recent achievements and future perspectives.

    Schneider, Jens; Wendisch, Volker F

    2011-07-01

    In Bacteria, the pathways of polyamine biosynthesis start with the amino acids L-lysine, L-ornithine, L-arginine, or L-aspartic acid. Some of these polyamines are of special interest due to their use in the production of engineering plastics (e.g., polyamides) or as curing agents in polymer applications. At present, the polyamines for industrial use are mainly synthesized on chemical routes. However, since a commercial market for polyamines as well as an industry for the fermentative production of amino acid exist, and since bacterial strains overproducing the polyamine precursors L-lysine, L-ornithine, and L-arginine are known, it was envisioned to engineer these amino acid-producing strains for polyamine production. Only recently, researchers have investigated the potential of amino acid-producing strains of Corynebacterium glutamicum and Escherichia coli for polyamine production. This mini-review illustrates the current knowledge of polyamine metabolism in Bacteria, including anabolism, catabolism, uptake, and excretion. The recent advances in engineering the industrial model bacteria C. glutamicum and E. coli for efficient production of the most promising polyamines, putrescine (1,4-diaminobutane), and cadaverine (1,5-diaminopentane), are discussed in more detail. PMID:21552989

  4. Nucleophilic substitution in preparation and surface modification of hypercrosslinked stationary phases.

    Janků, Simona; Škeříková, Veronika; Urban, Jiří

    2015-04-01

    Four linear diaminoalkanes (1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, and 1,8-diaminooctane) have been used to hypercrosslink poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene) monolithic stationary phases by nucleophilic substitution reaction. The column efficiency of polymer monoliths improved with longer diaminoalkane with 1,8-diaminoctane providing the highest efficiency. The concentration of 1,8-diaminoctane, together with hypercrosslinking time and temperature has been optimized. To improve the permeability of prepared columns, the hypercrosslinking modification has been combined with an early termination of polymerization reaction and decrease in polymerization temperature. The optimal column has been prepared by a polymerization reaction for 2h at 65°C and hypercrosslinked in the presence of 3% 1,8-diaminooctane for 2h at 95°C. The repeatability study of the presented protocol provided relative standard deviation for nine columns prepared independently out of three individual polymerization mixtures in between 2.0-12.0% for retention factors and 1.5-6.5% for plate heights, respectively. Further, we have modified residual chloromethyl groups with 2-aminoethanesulfonic acid (taurine) to prepare monolithic columns suitable for separation of small polar molecules in hydrophilic interaction chromatography. The highest retention of polar thiourea showed the column modified at 70°C for 20 h. Taurine-modified hypercrosslinked column showed the minimum of van Deemter curve of 20 μm. The prepared column provided dual-retention mechanism, including hydrophilic interaction and reversed-phase liquid chromatography that can be controlled by the composition of the mobile phase. The prepared column has been successfully used for an isocratic separation of low-molecular phenolic acids. PMID:25728663

  5. Genetic and Functional Analysis of the Biosynthesis of a Non-Ribosomal Peptide Siderophore in Burkholderia xenovorans LB400.

    María José Vargas-Straube

    Full Text Available B. xenovorans LB400 is a model bacterium for the study of the metabolism of aromatic compounds. The aim of this study was the genomic and functional characterization of a non-ribosomal peptide synthetase containing gene cluster that encodes a siderophore in B. xenovorans LB400. The mba gene cluster from strain LB400 encodes proteins involved in the biosynthesis and transport of a hydroxamate-type siderophore. Strain LB400 has a unique mba gene organization, although mba gene clusters have been observed in diverse Burkholderiales. Bioinformatic analysis revealed the presence of promoters in the mba gene cluster that strongly suggest regulation by the ferric uptake regulator protein (Fur and by the alternative RNA polymerase extracytoplasmic function sigma factor MbaF. Reverse transcriptase PCR analyses showed the expression of iron-regulated transcriptional units mbaFGHIJKL, mbaN, mbaABCE, mbaO, mbaP and mbaD genes under iron limitation. Chrome azurol S (CAS assay strongly suggests that strain LB400 synthesized a siderophore under iron limitation. Mass spectrometry ESI-MS and MALDI-TOF-MS analyses revealed that the siderophore is a non-ribosomal peptide, and forms an iron complex with a molecular mass of 676 Da. Based on bioinformatic prediction, CAS assay and MS analyses, we propose that the siderophore is L-Nδ-hydroxy-Nδ-formylOrn-D-β-hydroxyAsp-L-Ser-L-Nδ-hydroxy-Nδ-formylOrn-1,4-diaminobutane that is closely related to malleobactin-type siderophores reported in B. thailandensis.

  6. Structural Investigations of N-carbamoylputrescine Amidohydrolase from Medicago truncatula: Insights into the Ultimate Step of Putrescine Biosynthesis in Plants.

    Sekula, Bartosz; Ruszkowski, Milosz; Malinska, Maura; Dauter, Zbigniew

    2016-01-01

    Putrescine, 1,4-diaminobutane, is an intermediate in the biosynthesis of more complexed polyamines, spermidine and spermine. Unlike other eukaryotes, plants have evolved a multistep pathway for putrescine biosynthesis that utilizes arginine. In the final reaction, N-carbamoylputrescine is hydrolyzed to putrescine by N-carbamoylputrescine amidohydrolase (CPA, EC 3.5.1.53). During the hydrolysis, consecutive nucleophilic attacks on the substrate by Cys158 and water lead to formation of putrescine and two by-products, ammonia and carbon dioxide. CPA from the model legume plant, Medicago truncatula (MtCPA), was investigated in this work. Four crystal structures were determined: the wild-type MtCPA in complex with the reaction intermediate, N-(dihydroxymethyl)putrescine as well as with cadaverine, which is a longer analog of putrescine; and also structures of MtCPA-C158S mutant unliganded and with putrescine. MtCPA assembles into octamers, which resemble an incomplete left-handed helical twist. The active site of MtCPA is funnel-like shaped, and its entrance is walled with a contribution of the neighboring protein subunits. Deep inside the catalytic cavity, Glu48, Lys121, and Cys158 form the catalytic triad. In this studies, we have highlighted the key residues, highly conserved among the plant kingdom, responsible for the activity and selectivity of MtCPA toward N-carbamoylputrescine. Moreover, since, according to previous reports, a close MtCPA relative from Arabidopsis thaliana, along with several other nitrilase-like proteins, are subjected to allosteric regulation by substrates, we have used the structural information to indicate a putative secondary binding site. Based on the docking experiment, we postulate that this site is adjacent to the entrance to the catalytic pocket. PMID:27066023

  7. SYNTHESIS AND PROPERTIES OF COPOLYMERS CONTAINING CUCURBIT[6]URIL-BASED PSEUDOROTAXANE STRUCTURE

    Qiang Ma; Hui Yang; Kimoon Kim; Ye-bang Tan

    2012-01-01

    Novel copolymers based on acrylamide (AM) and complex pseudorotaxane monomer N'-(3-vinylbenzyl)-l,4-diaminobutane dihydrochloride with cucurbit[6]uril (CB[6]) (3VBCB) were prepared via free-radical polymerization in aqueous solution,and characterized by 1H-NMR,FT-IR,elemental analysis and static light scattering.The compositions of the copolymers (PAM3VBCB) with pseudorotaxane units were determined by 1H-NMR and elemental analysis.Thermal properties of the copolymers were studied by TGA,and the effects of the copolymer concentration and pH on the average hydrodynamic radius (Rh) of the copolymer molecules were studied by dynamic light scattering (DLS).The experiment data show that CB[6] beads are localized on 1,4-diaminobutane units in side chains of the copolymers.TGA results show that thermal stability of the copolymer increases with increasing the content of pseudorotaxane unit because of the enhanced rigidity and the bulky steric hindrance of 3VBCB in side chains of PAM3VBCB.DLS data show that the average hydrodynamic radius of copolymer molecules increases with the increase in the copolymer concentration,and both the pH and electrical conductivity of PAM3VBCB solutions demonstrate an acute change with addition of NaOH because of CB[6]dethreading from the side chains of PAM3VBCB.CB[6] threading and dethreading of PAM3VBCB could be controlled by addition of BaCl2 and Na2SO4.

  8. Synthetic Development of New 3-(4-Arylmethylaminobutyl-5-arylidene-rhodanines under Microwave Irradiation and Their Effects on Tumor Cell Lines and against Protein Kinases

    Camille Déliko Dago

    2015-07-01

    Full Text Available A new route to 3-(4-arylmethylaminobutyl-5-arylidene-2-thioxo-1,3-thiazolidine-4-one 9 was developed in six steps from commercial 1,4-diaminobutane 1 as starting material. The key step of this multi-step synthesis involved a solution phase “one-pot two-steps” approach assisted by microwave dielectric from N-(arylmethylbutane-1,4-diamine hydrochloride 6a–f (as source of the first point diversity and commercial bis-(carboxymethyl-trithiocarbonate reagent 7 for construction of the rhodanine platform. This platform was immediately functionalized by Knoevenagel condensation under microwave irradiation with a series of aromatic aldehydes 3 as second point of diversity. These new compounds were prepared in moderate to good yields and the fourteen synthetic products 9a–n have been obtained with a Z-geometry about their exocyclic double bond. These new 5-arylidene rhodanines derivatives 9a–n were tested for their kinase inhibitory potencies against four protein kinases: Human cyclin-dependent kinase 5-p25, HsCDK5-p25; porcine Glycogen Synthase Kinase-3, GSK-3α/β; porcine Casein Kinase 1, SsCK1 and human HsHaspin. They have also been evaluated for their in vitro inhibition of cell proliferation (HuH7 D12, Caco 2, MDA-MB 231, HCT 116, PC3, NCI-H727, HaCat and fibroblasts. Among of all these compounds, 9j presented selective micromolar inhibition activity on SsCK1 and 9i exhibited antitumor activities in the HuH7 D12, MDA-MBD231 cell lines.

  9. Designed self-assembly of molecular necklaces.

    Park, Ki-Min; Kim, Soo-Young; Heo, Jungseok; Whang, Dongmok; Sakamoto, Shigeru; Yamaguchi, Kentaro; Kim, Kimoon

    2002-03-13

    This paper reports an efficient strategy to synthesize molecular necklaces, in which a number of small rings are threaded onto a large ring, utilizing the principles of self-assembly and coordination chemistry. Our strategy involves (1) threading a molecular "bead" with a short "string" to make a pseudorotaxane and then (2) linking the pseudorotaxanes with a metal complex with two cis labile ligands acting as an "angle connector" to form a cyclic product (molecular necklace). A 4- or 3-pyridylmethyl group is attached to each end of 1,4-diaminobutane or 1,5-diaminopentane to produce the short "strings" (C4N4(2+), C4N3(2+), C5N4(2+), and C5N3(2+)), which then react with a cucurbituril (CB) "bead" to form stable pseudorotaxanes (PR44(2+), PR43(2+), PR54(2+), and PR53(2+), respectively). The reaction of the pseudorotaxanes with Pt(en)(NO(3))(2) (en = ethylenediamine) produces a molecular necklace [4]MN, in which three molecular "beads" are threaded on a triangular framework, and/or a molecular necklace [5]MN, in which four molecular "beads" are threaded on a square framework. Under refluxing conditions, the reaction with PR44(2+) or PR54(2+) yields exclusively [4]MN (MN44T or MN54T, respectively), whereas that with PR43(2+) or PR53(2+) produces exclusively [5]MN (MN43S or MN53S, respectively). The products have been characterized by various methods including X-ray crystallography. At lower temperatures, on the other hand, the reaction with PR44(2+) or PR54(2+) affords both [4]MN and [5]MN. The supermolecules reported here are the first series of molecular necklaces obtained as thermodynamic products. The overall structures of the molecular necklaces are strongly influenced by the structures of pseudorotaxane building blocks, which is discussed in detail on the basis of the X-ray crystal structures. The temperature dependence of the product distribution observed in this self-assembly process is also discussed. PMID:11878967

  10. Mediterranean fruit fly female attractant studies in support of the sterile insect technique: trapping experiments conducted on the island of Chios, Greece

    This paper contains information on a four-year research programme co-ordinated by the International Atomic Energy Agency. The main objective of the programme was to develop a trapping system for females of the Mediterranean fruit fly (medfly), Ceratitis capitata (Diptera: Tephritidae), for practical use in Sterile Insect Technique (SIT) programs and to design and evaluate a trap to obtain eggs from wild female medflies in order to estimate sterility induction in the field population. The experiments were conducted from July to September 1994-1997 on the island of Chios, Greece, in citrus orchards with low to medium medfly populations. Different trap types and several trap treatments consisting of sex and food based attractants were tested, following a standard coordinated experimental protocol. The most extensively tested were three food based 'female' attractants (FA-3), namely ammonium acetate (AA), 1,4 diaminobutane (putrescine) and trimethylamine, all formulated in dispensers lasting one month. These attractants were evaluated in combinations of two (AA + putrescine, termed FA-2) or three (FA-3) dispensers in various traps, including dry (provided with DDVP) or wet (provided with water and 0.01% surfactant) plastic International Pheromone's McPhail traps (IPMT). Among the various traps and treatments tested, the most effective for medfly capture was the wet IPMT, baited with FA-3 attractants. This treatment captured predominantly females and was relatively selective for medflies. In dry IPMT traps, the FA-3 were as effective as the standard 300 ml aqueous solution of 9% of the protein NuLure and 3% borax, but much more medfly selective. Dry IPMT traps were also more selective than wet ones. FA-3 baited wet Tephri traps (a Spanish modification of the McPhail trap), performed somewhat poorer than IPMT traps. Other dry trap types tested were not effective. Additional experiments showed that certain insecticide formulations used in dry traps may have a repellent

  11. Evaluation of the efficiency of various medfly female trapping combinations in Costa Rica in support of the sterile insect technique

    This report contains information from a four-year research programme co-ordinated by the International Atomic Energy Agency. The objective of the programme was to develop a trapping system for females of the Mediterranean fruit fly (medfly), Ceratitis capitata (Diptera: Tephritidae), for practical use in Sterile Insect Technique (SIT) programs and to design and evaluate a trap to obtain eggs from wild female medflies in order to estimate sterility induction in the field population. The study was carried out at two different Agricultural Research Stations of the University of Costa Rica, the Fabio Baudrit Agricultural Research Station (FBS) and Laguna de Fraijanes Agricultural Research Station (LFS), and in a privately-owned coffee and orange plantation in Grecia canton (Coope-Victoria Farm). Female medfly attractants tested were three food based 'female' attractants (FA-3), namely ammonium acetate (AA), 1,4 diaminobutane (putrescine) and trimethylamine, all formulated to last at least one month. These attractants were evaluated either in combinations of two (AA + putrescine, termed FA-2) or all three (termed FA-3). The attractants were tested in various traps including the plastic International Pheromone's McPhail traps (IPMT) and Tephri traps, a Spanish trap similar to the IPMT. Traps were used either as a dry trap (provided with DDVP) or a wet trap (provided with water and 0.01% surfactant). Jackson traps with Trimedlure (JT,TML), a routinely used male medfly trapping system, was also used. Trapping experiments conducted in the citrus plantation of the FBS resulted in the following fly/trap/day indices (F/T/D): 7.18 with JT,TML; 4.62 with open bottom dry traps (OBDT) baited with FA-3; 4.18 with OBDT (PVC) baited with FA-3; 7.73 with IPMT baited with FA-3, wet; 8.245 with IPMT baited with FA-3, dry; 5.27 with IPMT baited with NuLure; 4.79 with Tephri baited with FA-3, wet; and 5.42 with Tephri, FA-3, dry. The F/T/D indices at the Coope-Victoria Farm, in coffee