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Sample records for 1,4-diaminobutane

  1. Three Contact Modes of Amino Terminal Groups on Gold in Single Molecular Junction of Au/1,4-Diaminobutane/Au

    NASA Astrophysics Data System (ADS)

    Omori, Yasuhiro; Tobita, Junichi; Kato, Yasuyuki; Akiba, Uichi; Fujihira, Masamichi

    2007-12-01

    The effect of the binding modes of two amino terminal groups present on two gold protrusions on currents passing through a single molecular junction of Au/1,4-diaminobutane/Au was studied via the repeated formation of a break junction using a scanning tunneling microscope (STM) under nitrogen at room temperature. In addition to the two reported (high and low) values of the single molecular conductance of diaminobutane, another lower conductance was found through a careful analysis of histograms in a low-current range (0-0.3 nA). The techniques used here to improve the determination of the values of single molecular conductance were the selection of valid i-s curves with current steps and the use of the robust statistical method to correct for the contribution of the background tunneling currents to the current histograms. These three single molecular conductance values are attributed to three different binding modes of the two terminal amino groups giving the three different contact resistances at room temperature. That is, each amino terminal group is likely to be bound to one or the other gold protrusion through a more or a less conductive contact mode. Thus, a single molecular junction between two gold electrodes has three different contact modes, i.e., i) more-more, ii) more-less (or less-more), and iii) less-less conductive contact modes at the two ends.

  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)

    NASA Astrophysics Data System (ADS)

    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. Antennal and behavioral responses of Anastrepha suspensa (Diptera: Tephritidae) to a series of homologous terminal diamines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Current monitoring programs for Anastrepha fruit flies use a two-component synthetic attractant consisting of ammonium acetate (AA) and putrescine (1,4-diaminobutane). Identification of additional attractant chemicals may improve trapping efficacy. We examined response of the Caribbean fruit fly, ...

  4. Electroantennogram and behavioral responses of Anastrepha suspensa (Diptera: Tephritidae) to putrescine and ammonium bicarbonate lures

    Technology Transfer Automated Retrieval System (TEKTRAN)

    At present, the most effective synthetic lures for pest Anastrepha fruit flies are multi-component blends that include an ammonia-emitting substrate and the diamine synergist, putrescine (1,4-diaminobutane). Both chemicals are regarded as protein-feeding cues which result in female-biased attractio...

  5. EAG and behavioral responses of the Caribbean fruit fly (Diptera:Tephritidae) to terminal diamines in a food-based lure.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Current monitoring programs for Anastrepha fruit flies utilize a food-based synthetic lure consisting of ammonium acetate and putrescine (1, 4 diaminobutane). Identification of additional attractant chemicals may lead to development of a more effective trapping system. This study, conducted with the...

  6. Response of Anastrepha suspensa (Diptera: Tephritidae) to terminal diamines in a food-based synthetic attractant.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A current trapping system for Anastrepha fruit flies utilizes a two-component food-based synthetic attractant consisting of ammonium acetate and putrescine (1,4-diaminobutane) lures. Development of more effective monitoring programs may be realized through identification of additional attractant ch...

  7. Plant alkaloids of the polymethyleneamine series

    NASA Astrophysics Data System (ADS)

    Rogoza, Ludmila N.; Salakhutdinov, Nariman F.; Tolstikov, Genrikh A.

    2005-04-01

    The published data on the structures and biological activities of the plant alkaloids of the biogenic polymethyleneamine series, viz., putrescine (1,4-diaminobutane), spermidine (1,8-diamino-4 -azaoctane), and spermine (1,12-diamino-4,9-diazadodecane), are considered and systematised. The structures and biological activities of some synthetic analogues of these alkaloids are also presented.

  8. An answer to the spiro versus ANSA dilemma in cyclophosphazenes. Part V. The Dispiro N 3P 3Cl 2 [HN(CH 2) 3,4NH] 2 and Trispiro N 3P 3 [HN(CH 2) 3NH] 3 derivatives

    NASA Astrophysics Data System (ADS)

    El Murr, Nada; Lahana, Roger; Labarre, Jean-Francois; Declercq, Jean-Paul

    1984-06-01

    The reaction of N 3P 3Cl 6 with 1,3-diaminopropane and 1,4-diaminobutane (putrescine) in suitable non-polar solvents allows the synthesis, with a very high yield of the PN HR-containing DISPIRO and TRISPIRO derivatives without any significant side-polymerization.

  9. Antennal responses of West Indian and Caribbean fruit flies (Diptera: Tephritidae) to ammonium bicarbonate and putrescine lures

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Efforts to monitor and detect tephritid fruit flies in the genus Anastrepha currently involve MultiLure traps baited with two food-based synthetic attractants; ammonium acetate and putrescine (1,4-diaminobutane). These baits are used in Central America, Florida, Texas, and the Caribbean, each region...

  10. Effect of membranes with various hydrophobic/hydrophilic properties on lipase immobilized activity and stability.

    PubMed

    Chen, Guan-Jie; Kuo, Chia-Hung; Chen, Chih-I; Yu, Chung-Cheng; Shieh, Chwen-Jen; Liu, Yung-Chuan

    2012-02-01

    In this study, three membranes: regenerated cellulose (RC), glass fiber (GF) and polyvinylidene fluoride (PVDF), were grafted with 1,4-diaminobutane (DA) and activated with glutaraldehyde (GA) for lipase covalent immobilization. The efficiencies of lipases immobilized on these membranes with different hydrophobic/hydrophilic properties were compared. The lipase immobilized on hydrophobic PVDF-DA-GA membrane exhibited more than an 11-fold increase in activity compared to its immobilization on a hydrophilic RC-DA-GA membrane. The relationship between surface hydrophobicity and immobilized efficiencies was investigated using hydrophobic/hydrophilic GF membranes which were prepared by grafting a different ratio of n-butylamine/1,4-diaminobutane (BA/DA). The immobilized lipase activity on the GF membrane increased with the increased BA/DA ratio. This means that lipase activity was exhibited more on the hydrophobic surface. Moreover, the modified PVDF-DA membrane was grafted with GA, epichlorohydrin (EPI) and cyanuric chloride (CC), respectively. The lipase immobilized on the PVDF-DA-EPI membrane displayed the highest specific activity compared to other membranes. This immobilized lipase exhibited more significant stability on pH, thermal, reuse, and storage than did the free enzyme. The results exhibited that the EPI modified PVDF is a promising support for lipase immobilization.

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

    NASA Astrophysics Data System (ADS)

    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).

  12. Structure investigation of fluorinated aluminophosphate ULM-3 Al templated by 3-methylaminopropylamine

    NASA Astrophysics Data System (ADS)

    Zabukovec Logar, Natasa; Mali, Gregor; Rajic, Nevenka; Jevtic, Sanja; Rangus, Mojca; Golobic, Amalija; Kaucic, Venceslav

    2010-05-01

    A single-crystal X-ray diffraction analysis of an open-framework aluminophosphate ULM-3 Al prepared by 3-methylaminopropylamine (MAPA) as structure-directing agent revealed an orthorhombic Pcab symmetry ( a=9.9949(4) Å, b=15.8229(7) Å, c=18.1963(5) Å, R=0.0648, Z=8, unit cell formula [Al 24P 24O 96F 16·C 32H 112N 16]), which differs from the Pbc2 1 symmetry of the structural analogue prepared in the presence of 1,4-diaminobutane. The 27Al, 31P, 19F, 13C and 1H NMR investigations, which were performed to study in detail MAPA arrangement inside the framework as well as the interactions of MAPA with the aluminophosphate host, confirmed the crystal symmetry and the proposed hydrogen bonding scheme between the template and the framework.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Structure investigation of fluorinated aluminophosphate ULM-3 Al templated by 3-methylaminopropylamine

    SciTech Connect

    Zabukovec Logar, Natasa; Mali, Gregor; Rajic, Nevenka; Jevtic, Sanja; Rangus, Mojca; Golobic, Amalija; Kaucic, Venceslav

    2010-05-15

    A single-crystal X-ray diffraction analysis of an open-framework aluminophosphate ULM-3 Al prepared by 3-methylaminopropylamine (MAPA) as structure-directing agent revealed an orthorhombic Pcab symmetry (a=9.9949(4) A, b=15.8229(7) A, c=18.1963(5) A, R=0.0648, Z=8, unit cell formula [Al{sub 24}P{sub 24}O{sub 96}F{sub 16}.C{sub 32}H{sub 112}N{sub 16}]), which differs from the Pbc2{sub 1} symmetry of the structural analogue prepared in the presence of 1,4-diaminobutane. The {sup 27}Al, {sup 31}P, {sup 19}F, {sup 13}C and {sup 1}H NMR investigations, which were performed to study in detail MAPA arrangement inside the framework as well as the interactions of MAPA with the aluminophosphate host, confirmed the crystal symmetry and the proposed hydrogen bonding scheme between the template and the framework. - Graphical abstract: The aluminophosphate analogue of open-framework gallophosphate ULM-3 was synthesized in the presence of 3-methylaminopropylamine. The Pcab crystal symmetry and hydrogen bonding scheme was determined by single-crystal X-ray diffraction and NMR spectroscopy.

  15. Studies on DNA binding behaviour of biologically active transition metal complexes of new tetradentate N2O2 donor Schiff bases: Inhibitory activity against bacteria

    NASA Astrophysics Data System (ADS)

    Sobha, S.; Mahalakshmi, R.; Raman, N.

    A series of Cu(II), Ni(II) and Zn(II) complexes of the type ML have been synthesized with Schiff bases derived from o-acetoacetotoluidide, 2-hydroxybenzaldehyde and o-phenylenediamine/1,4-diaminobutane. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytic in nature. All the six metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The analytical data helped to elucidate the structure of the metal complexes. The Schiff bases are found to act as tetradentate ligands using N2O2 donor set of atoms leading to a square-planar geometry for the complexes around all the metal ions. The binding properties of metal complexes with DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. Detailed analysis reveals that the metal complexes intercalate into the DNA base stack as intercalators. All the metal complexes cleave the pUC19 DNA in presence of H2O2. The Schiff bases and their complexes have been screened for their antibacterial activity against five bacterial strains (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, Klebsiella pneumoniae) by disk diffusion method. All the metal complexes have potent biocidal activity than the free ligands.

  16. Characterization of a novel spermidine/spermine acetyltransferase, BltD, from Bacillus subtilis.

    PubMed Central

    Woolridge, D P; Martinez, J D; Stringer, D E; Gerner, E W

    1999-01-01

    Overexpression of the BltD gene in Bacillus subtilis causes acetylation of the polyamines spermidine and spermine. BltD is co-regulated with another gene, Blt, which encodes a multidrug export protein whose overexpression facilitates spermidine export [Woolridge, Vazquez-Laslop, Markham, Chevalier, Gerner and Neyfakh (1997) J. Biol. Chem. 272, 8864-8866]. Here we show that BltD acetylates both spermidine and spermine at primary propyl amine moieties, with spermine being the preferred substrate. In the presence of saturating concentrations of acetyl CoA, BltD rapidly acetylates spermine at both the N1 and N12 positions. The Km (app) values for spermine, spermidine and N1-acetylspermine are 1, 4-diaminobutane) and N8-acetylspermidine were competitive inhibitors of spermidine acetylation by BltD, with Ki values of 0.25 and 5.76 mM, respectively. CoA competitively inhibited both spermidine and acetyl-CoA interactions with BltD. These data and other results indicate that the mechanism of spermidine and spermine acetylation by BltD is a random-order mechanism of bi-molecular kinetics. PMID:10359661

  17. Response of Anastrepha suspensa (Diptera: Tephritidae) to terminal diamines in a food-based synthetic attractant.

    PubMed

    Kendra, Paul E; Epsky, Nancy D; Montgomery, Wayne S; Heath, Robert R

    2008-10-01

    A current trapping system for Anastrepha fruit flies uses a two-component food-based synthetic attractant consisting of ammonium acetate and putrescine (1,4-diaminobutane). Development of more effective monitoring programs may be realized through identification of additional attractant chemicals. This study examined response of the Caribbean fruit fly, Anastrepha suspensa (Loew), to putrescine and four homologous terminal diamines, differing only in carbon chain length. Using a fixed dose of each diamine substrate, electroantennogram (EAG) responses from mature females to putrescine and cadaverine (1,5-diaminopentane) were not significantly different from each other but were significantly greater than responses to longer chain diamines. Over a range of doses tested, mean female EAG response was greater than male response to both putrescine and cadaverine. In an initial field test, capture of female flies in traps baited with ammonium acetate and either putrescine or cadaverine was higher than in traps baited with ammonium acetate and any of the other diamines. In a subsequent field test, traps baited with putrescine, cadaverine, or 1,6-diaminohexane in combination with ammonium acetate captured more female flies than traps baited with ammonium acetate alone. A significantly greater synergistic effect on female captures was observed with either putrescine or cadaverine than with 1,6-diaminohexane. Thus, of the diamines evaluated, cadaverine elicited both antennal and behavioral responses comparable to that of putrescine and will be studied further as a potential attractant for pest Anastrepha species.

  18. Next generation PhotoCORMs: polynuclear tricarbonylmanganese(I)-functionalized polypyridyl metallodendrimers.

    PubMed

    Govender, Preshendren; Pai, Sandesh; Schatzschneider, Ulrich; Smith, Gregory S

    2013-05-06

    The first CO-releasing metallodendrimers, based on polypyridyl dendritic scaffolds functionalized with Mn(CO)3 moieties, of the general formula [DAB-PPI-{MnBr(bpy(CH3,CH═N))(CO)3}n], where DAB = 1,4-diaminobutane, PPI = poly(propyleneimine), bpy = bipyridyl, and n = 4 for first- or n = 8 for second-generation dendrimers, were synthesized and comprehensively characterized by analytical (HR-ESI mass spectrometry and elemental analysis) and spectroscopic ((1)H, (13)C{(1)H}-NMR, infrared, and UV/vis spectroscopy) methods. The CO-release properties of these compounds were investigated in pure buffer and using the myoglobin assay. Both metallodendrimer generations are stable in the dark in aqueous buffer for up to 16 h but show photoactivated CO release upon excitation at 410 nm, representing a novel class of macromolecular photoactivatable CO-releasing molecules (PhotoCORMs). No scaling effects were observed since both metallodendrimers release ∼65% of the total number of CO ligands per molecule, regardless of the generation number. In addition, the mononuclear model complex [MnBr(bpy(CH3,CH═NCH2CH2CH3))(CO)3] was prepared and comprehensively studied, including DFT/TDDFT calculations. These metallodendrimer-based PhotoCORMs afford new methods of targeted delivery of large amounts of carbon monoxide to cellular systems.

  19. Olfaction in dragonflies: electrophysiological evidence.

    PubMed

    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.

  20. STABILIZATION OF PROTOPLASTS AND SPHEROPLASTS BY SPERMINE AND OTHER POLYAMINES

    PubMed Central

    Tabor, Celia W.

    1962-01-01

    Tabor, Celia W. (National Institute of Arthritis and Metabolic Diseases, Bethesda, Md.). Stabilization of protoplasts and spheroplasts by spermine and other polyamines. J. Bacteriol. 83:1101–1111. 1962.—Spermine (10−3m) or spermidine prevents lysis of lysozyme-produced protoplasts of Escherichia coli W, E. coli B, and Micrococcus lysodeikticus in hypotonic media. Spheroplasts prepared by the action of penicillin are also stabilized by these concentrations of spermine and spermidine, but the protection is not as complete. Streptomycin, polylysine, and Ca++ are also effective or partially effective stabilizers, but 1,4-diaminobutane, 1,5-diaminopentane, ornithine, Mg++, and monovalent cations have no protective action at 10−3m concentration, and only a slight effect at higher concentrations. The osmotic stability conferred on protoplasts by spermine is irreversible. However, the protective effect of polyamines against lysis is not accompanied by restoration of viability to lysozyme protoplasts. There is a marked reduction in the loss of ultra-violet-absorbing material from the protoplasts to the medium when 10−3m spermine is present. PMID:16561942

  1. Electroantennogram and behavioral responses of Anastrepha suspensa (Diptera: Tephritidae) to putrescine and ammonium bicarbonate lures.

    PubMed

    Kendra, Paul E; Montgomery, Wayne S; Epsky, Nancy D; Heath, Robert R

    2009-08-01

    At present, the most effective synthetic lures for pest Anastrepha fruit flies are multicomponent blends that include ammonia and the diamine synergist putrescine (1,4-diaminobutane). Both chemicals generally have been regarded as protein cues that result in female-biased attraction. Using electroantennography (EAG) and flight tunnel bioassays, this study evaluated response of the Caribbean fruit fly, Anastrepha suspensa (Loew) to vapors released from commercial lure formulations of ammonium bicarbonate and putrescine. Over a range of doses tested, EAG response to ammonium bicarbonate was equivalent for both sexes, but female response was significantly greater than male response to putrescine and to a 1:1 mixture of ammonium bicarbonate and putrescine. Amplitude of EAG response to the mixture was approximately equal to the summation of responses to the individual substrates. Using a fixed dose of substrate, EAG measurements from females 1-14 d old indicated that antennal sensitivity to both lures varied according to physiological state of the fly. Peak response to ammonium bicarbonate was recorded from immature females, peak response to putrescine from sexually mature females. In bioassays, more females were captured with ammonium bicarbonate plus putrescine than with ammonium bicarbonate alone. This difference was not observed in males, resulting in a higher female to male ratio in captures with ammonium bicarbonate plus putreseine (3:1) versus ammonium bicarbonate alone (1:1). Results suggest that separate olfactory receptors are involved in detection of the two semiochemicals, and that the putrescine component is primarily responsible for the female-biased attraction.

  2. Interaction of polyamines with proteins of photosystem II: Cation binding and photosynthetic oxygen evolution

    NASA Astrophysics Data System (ADS)

    Beauchemin, R.; Harnois, J.; Rouillon, R.; Tajmir-Riahi, H. A.; Carpentier, R.

    2007-05-01

    Polyamines are organic cations that function in diverse physiological processes that share as a common thread a close relationship to cell proliferation and growth. Polyamines also affect photosynthetic oxygen evolution and therefore, this study was designed to investigate the interaction of 1,3-diaminopropane, 1,4-diaminobutane (putrescine), and 1,5-diaminopentane (cadaverine) cations with proteins of photosystem II (PSII) using PSII-enriched submembrane fractions with diamine concentrations between 0.01 and 20 mM. Fourier transformed infrared (FTIR) difference spectroscopy with its self-deconvolution and second derivative resolution enhancement, as well as curve-fitting procedures were applied in order to determine the diamine binding mode, the protein conformational changes, and the structural properties of diamine-protein complexes. Spectroscopic evidence showed that diamines interact with proteins (H-bonding) through polypeptide C dbnd O groups with no major perturbations of protein secondary structure. At very low diamine concentration (0.01 mM), no inhibition of oxygen-evolution occurred, while at higher diamine content (5-10 mM), 100% inhibition was observed. Chorophyll fluorescence measurements demonstrated that the inhibition mainly affects the oxygen evolving complex of PSII. Comparisons of the effects of these dipositive organic cations with divalent metal cations on one hand and with polyvalent spermine and spermidine on the other hand, show major alterations of the protein secondary structure as positive charge increases.

  3. Hyperbranched-dendrimer architectural copolymer gene delivery using hyperbranched PEI conjugated to poly(propyleneimine) dendrimers: synthesis, characterization, and evaluation of transfection efficiency

    NASA Astrophysics Data System (ADS)

    Alavi, Seyyed Jamal; Gholami, Leila; Askarian, Saeedeh; Darroudi, Majid; Massoudi, Abdolhossein; Rezaee, Mehdi; Kazemi Oskuee, Reza

    2017-02-01

    The applications of dendrimer-based vectors seem to be promising in non-viral gene delivery because of their potential for addressing the problems with viral vectors. In this study, generation 3 poly(propyleneimine) (G3-PPI) dendrimers with 1, 4-diaminobutane as a core initiator was synthesized using a divergent growth approach. To increase the hydrophobicity and reduce toxicity, 10% of primary amines of G3-PPI dendrimers were replaced with bromoalkylcarboxylates with different chain lengths (6-bromohexanoic and 10-bromodecanoic). Then, to retain the overall buffering capacity and enhance transfection, the alkylcarboxylate-PPIs were conjugated to 10 kDa branched polyethylenimine (PEI). The results showed that the modified PPI was able to form complexes with the diameter of less than 60 nm with net-positive surface charge around 20 mV. No significant toxicity was observed in modified PPIs; however, the hexanoate conjugated PPI-PEI (PPI-HEX-10% PEI) and the decanoate conjugated PPI-PEI (PPI-DEC-10%-PEI) showed the best transfection efficiency in murine neuroblastoma (Neuro-2a) cell line, even PPI-HEX-10%-PEI showed transfection efficiency equal to standard PEI 25 kDa with reduced toxicity. This study suggested a new series of hyperbranched (PEI)-dendrimer (PPI) architectural copolymers as non-viral gene delivery vectors with high transfection efficiency and low toxicity.

  4. Studies on DNA binding behaviour of biologically active transition metal complexes of new tetradentate N2O2 donor Schiff bases: inhibitory activity against bacteria.

    PubMed

    Sobha, S; Mahalakshmi, R; Raman, N

    2012-06-15

    A series of Cu(II), Ni(II) and Zn(II) complexes of the type ML have been synthesized with Schiff bases derived from o-acetoacetotoluidide, 2-hydroxybenzaldehyde and o-phenylenediamine/1,4-diaminobutane. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytic in nature. All the six metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The analytical data helped to elucidate the structure of the metal complexes. The Schiff bases are found to act as tetradentate ligands using N(2)O(2) donor set of atoms leading to a square-planar geometry for the complexes around all the metal ions. The binding properties of metal complexes with DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. Detailed analysis reveals that the metal complexes intercalate into the DNA base stack as intercalators. All the metal complexes cleave the pUC19 DNA in presence of H(2)O(2.) The Schiff bases and their complexes have been screened for their antibacterial activity against five bacterial strains (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, Klebsiella pneumoniae) by disk diffusion method. All the metal complexes have potent biocidal activity than the free ligands.

  5. Synthesis and characterization of (H2dab)2Cu8Ge4S14·2H2O: An expanded framework based on icosahedral Cu8S12 cluster

    NASA Astrophysics Data System (ADS)

    Zhang, Ren-Chun; Zhang, Chi; Ji, Shou-Hua; Ji, Min; An, Yong-Lin

    2012-02-01

    A new three-dimensional framework copper-thiogermanate, (H2dab)2Cu8Ge4S14·2H2O (1), was prepared under solvothermal condition and characterized by elemental analysis, single-crystal and powder X-ray diffraction, thermogravimetric analysis and UV-vis diffuse reflectance spectroscopy. Compound 1 crystallizes in the monoclinic space group P2(1)/c, a=11.444(4) Å, b=12.984(4) Å, c=12.455(6) Å, β=91.527(1)°, V=1850.2(3) Å3, Z=2. It contains a new three-dimensional Cu-Ge-S framework constructed from icosahedral [Cu8S12]16- clusters linked by [GeS4]4- and dimeric [Ge2S6]4- units, with diprotonated 1,4-dab (1,4-diaminobutane) and H2O molecules located in the intersecting channels. UV-vis reflectance spectroscopy reveals the band gap of compound 1 is 2.5 eV.

  6. Effect of dietary putrescine on whole body growth and polyamine metabolism.

    PubMed

    Smith, T K

    1990-09-01

    Putrescine (1,4-diaminobutane) is the simplest of the mammalian polyamines. These are small, positively charged molecules which are essential for cell growth and are thought to play a role in regulation of anabolic events such as synthesis of DNA, RNA, and protein. Recent reports have indicated the potential for dietary precursor amino acids of putrescine to alter tissue putrescine concentrations. The current study was conducted to determine the physiologic significance of these effects by feeding up to flooding doses of putrescine to determine any influence on whole body growth and polyamine metabolism. A total of 96 chicks were fed purified crystalline amino acid diets containing 0.0, 0.2, 0.4, 0.6, 0.8, or 1.0% purified putrescine (four birds per pen, four pens per diet) for 14 days. The feeding of 0.2% putrescine increased growth rate beyond that of controls while further supplements reduced growth and were toxic when 0.8 and 1.0% putrescine were fed. Hepatic and muscle concentrations of ornithine increased with dietary putrescine while the effect in kidney was much less. Putrescine concentrations in liver, kidney, and muscle rose when 0.4% putrescine or more was fed. This effect was particularly obvious in muscle in which there were also increases in the concentrations of spermidine and spermine. In a subsequent similar experiment, putrescine was fed at 0.0, 0.1, 0.2, 0.3, 0.4, or 0.5% to determine the effect on the activities of the key enzymes regulating polyamine synthesis. The feeding of putrescine at even 0.1% caused a rapid reduction in hepatic ornithine decarboxylase activity while S-adenosylmethionine decarboxylase and arginase activities were not influenced by diet. It was concluded that excess tissue putrescine can be toxic to whole organisms but small, orally administered doses of this metabolite can promote growth.

  7. Differential effect of alpha-difluoromethylornithine on the in vivo uptake of 14C-labeled polyamines and methylglyoxal bis(guanylhydrazone) by a rat prostate-derived tumor

    SciTech Connect

    Heston, W.D.; Kadmon, D.; Covey, D.F.; Fair, W.R.

    1984-03-01

    The uptake of exogenously administered radiolabeled polyamines by a rat prostate-derived tumor line, the Dunning R3327 MAT-Lu, and various normal tissues was studied. Pretreatment of tumor cells in vitro with alpha-difluoromethylornithine (DFMO), a polyamine synthesis inhibitor, resulted in a markedly enhanced uptake of both (/sup 14/C)putrescine and (14 C)spermidine. The in vitro uptake of (/sup 14/C)putrescine by these cells was effectively inhibited by unlabeled spermine, spermidine, 1,8-diaminooctane, 1,7-diaminoheptane, 1,6-diaminohexane, 1,5-diaminopentane, 1,4-diaminopentane, and 1,4-diaminobutane, but less effectively by 1,4-diamino-2,3-butene and 1,4-diamino-2,3-butyne. The diamines, 1,3-diaminopropane and 1,2-diaminoethane, were ineffective in inhibiting (/sup 14/C)putrescine uptake in vitro into the R3327 MAT-Lu cell line. When tumor-bearing animals were pretreated with DFMO or with DFMO and 5-alpha-dihydrotestosterone propionate, the tumor and prostate uptake of (/sup 14/C)putrescine and (/sup 14/C)-cadaverine was enhanced but not substantially increased in other tissues. In contrast to the in vitro results, spermidine and spermine were not enhanced substantially by DFMO pretreatment into any tissue, and their uptake into the tumor actually decreased. Ethylenediamine, which does not utilize the polyamine transport system, did not have its uptake increased into any tissue following DFMO pretreatment. The chemotherapeutic agent, methylglyoxal bis(guanylhydrazone), which utilizes the polyamine transport system for uptake into cells, exhibited uptake behavior different from that of the polyamines.

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

    PubMed Central

    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

  9. Purification and structural characterization of siderophore (corynebactin) from Corynebacterium diphtheriae.

    PubMed

    Zajdowicz, Sheryl; Haller, Jon C; Krafft, Amy E; Hunsucker, Steve W; Mant, Colin T; Duncan, Mark W; Hodges, Robert S; Jones, David N M; Holmes, Randall K

    2012-01-01

    During infection, Corynebacterium diphtheriae must compete with host iron-sequestering mechanisms for iron. C. diphtheriae can acquire iron by a siderophore-dependent iron-uptake pathway, by uptake and degradation of heme, or both. Previous studies showed that production of siderophore (corynebactin) by C. diphtheriae is repressed under high-iron growth conditions by the iron-activated diphtheria toxin repressor (DtxR) and that partially purified corynebactin fails to react in chemical assays for catecholate or hydroxamate compounds. In this study, we purified corynebactin from supernatants of low-iron cultures of the siderophore-overproducing, DtxR-negative mutant strain C. diphtheriae C7(β) ΔdtxR by sequential anion-exchange chromatography on AG1-X2 and Source 15Q resins, followed by reverse-phase high-performance liquid chromatography (RP-HPLC) on Zorbax C8 resin. The Chrome Azurol S (CAS) chemical assay for siderophores was used to detect and measure corynebactin during purification, and the biological activity of purified corynebactin was shown by its ability to promote growth and iron uptake in siderophore-deficient mutant strains of C. diphtheriae under iron-limiting conditions. Mass spectrometry and NMR analysis demonstrated that corynebactin has a novel structure, consisting of a central lysine residue linked through its α- and ε- amino groups by amide bonds to the terminal carboxyl groups of two different citrate residues. Corynebactin from C. diphtheriae is structurally related to staphyloferrin A from Staphylococcus aureus and rhizoferrin from Rhizopus microsporus in which d-ornithine or 1,4-diaminobutane, respectively, replaces the central lysine residue that is present in corynebactin.

  10. Metabolic engineering of Escherichia coli for the production of putrescine: a four carbon diamine.

    PubMed

    Qian, Zhi-Gang; Xia, Xiao-Xia; Lee, Sang Yup

    2009-11-01

    A four carbon linear chain diamine, putrescine (1,4-diaminobutane), is an important platform chemical having a wide range of applications in chemical industry. Biotechnological production of putrescine from renewable feedstock is a promising alternative to the chemical synthesis that originates from non-renewable petroleum. Here we report development of a metabolically engineered strain of Escherichia coli that produces putrescine at high titer in glucose mineral salts medium. First, a base strain was constructed by inactivating the putrescine degradation and utilization pathways, and deleting the ornithine carbamoyltransferase chain I gene argI to make more precursors available for putrescine synthesis. Next, ornithine decarboxylase, which converts ornithine to putrescine, was amplified by a combination of plasmid-based and chromosome-based overexpression of the coding genes under the strong tac or trc promoter. Furthermore, the ornithine biosynthetic genes (argC-E) were overexpressed from the trc promoter, which replaced the native promoter in the genome, to increase the ornithine pool. Finally, strain performance was further improved by the deletion of the stress responsive RNA polymerase sigma factor RpoS, a well-known global transcription regulator that controls the expression of ca. 10% of the E. coli genes. The final engineered E. coli strain was able to produce 1.68 g L(-1) of putrescine with a yield of 0.168 g g(-1) glucose. Furthermore, high cell density cultivation allowed production of 24.2 g L(-1) of putrescine with a productivity of 0.75 g L(-1) h(-1). The strategy reported here should be useful for the bio-based production of putrescine from renewable resources, and also for the development of strains capable of producing other diamines, which are important as nitrogen-containing platform chemicals.

  11. Elimination of polyamine N-acetylation and regulatory engineering improved putrescine production by Corynebacterium glutamicum.

    PubMed

    Nguyen, Anh Q D; Schneider, Jens; Wendisch, Volker F

    2015-05-10

    Corynebacterium glutamicum has been engineered for production of the polyamide monomer putrescine or 1,4-diaminobutane. Here, N-acetylputrescine was shown to be a significant by-product of putrescine production by recombinant putrescine producing C. glutamicum strains. A systematic gene deletion approach of 18 (putative) N-acetyltransferase genes revealed that the cg1722 gene product was responsible for putrescine acetylation. The encoded enzyme was purified and characterized as polyamine N-acetyltransferase. The enzyme accepted acetyl-CoA and propionyl-CoA as donors for acetylation of putrescine and other diamines as acceptors, but showed highest catalytic efficiency with the triamine spermidine and the tetraamine spermine and, hence, was named SnaA. Upon deletion of snaA in the putrescine producing strain PUT21, no acteylputrescine accumulated, but about 41% more putrescine as compared to the parent strain. Moreover, a transcriptome approach identified increased expression of the cgmAR operon encoding a putative permease and a transcriptional TetR-family repressor upon induction of putrescine production in C. glutamicum PUT21. CgmR is known to bind to cgmO upstream of cgmAR and gel mobility shift experiments with purified CgmR revealed that putrescine and other diamines perturbed CgmR-cgmO complex formation, but not migration of free cgmO DNA. Deletion of the repressor gene cgmR resulted in expression changes of a number of genes and increased putrescine production of C. glutamicum PUT21 by 19% as compared to the parent strain. Overexpression of the putative transport gene cgmA increased putrescine production by 24% as compared to the control strain. However, cgmA overexpression in PUT21ΔsnaA did not further improve putrescine production, hence, the beneficial effects of both targets were not synergistic at the highest described yield of 0.21 g g(-1).

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

    PubMed

    Dago, Camille Déliko; Ambeu, Christelle N'ta; Coulibaly, Wacothon-Karime; Békro, Yves-Alain; Mamyrbékova, Janat; Defontaine, Audrey; Baratte, Blandine; Bach, Stéphane; Ruchaud, Sandrine; Guével, Rémy Le; Ravache, Myriam; Corlu, Anne; Bazureau, Jean-Pierre

    2015-07-08

    A new route to 3-(4-arylmethylamino)butyl-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-(arylmethyl)butane-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.

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

    PubMed Central

    Vargas-Straube, María José; Cámara, Beatriz; Tello, Mario; Montero-Silva, Francisco; Cárdenas, Franco; Seeger, Michael

    2016-01-01

    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. PMID:26963250

  14. 3D graphene preparation via covalent amide functionalization for efficient metal-free electrocatalysis in oxygen reduction

    PubMed Central

    Ahmed, Mohammad Shamsuddin; Kim, Young-Bae

    2017-01-01

    3D and porous reduced graphene oxide (rGO) catalysts have been prepared with sp3-hybridized 1,4-diaminobutane (sp3-DABu, rGO-sp3-rGO) and sp2-hybridized 1,4-diaminobenzene (sp2-DABe, rGO-sp2-rGO) through a covalent amidation and have employed as a metal-free electrocatalyst for oxygen reduction reaction (ORR) in alkaline media. Both compounds have used as a junction between functionalized rGO layers to improve electrical conductivity and impart electrocatalytic activity to the ORR resulting from the interlayer charge transfer. The successful amidation and the subsequent reduction in the process of catalyst preparation have confirmed by X-ray photoelectron spectroscopy. A hierarchical porous structure is also confirmed by surface morphological analysis. Specific surface area and thermal stability have increased after successful the amidation by sp3-DABu. The investigated ORR mechanism reveals that both functionalized rGO is better ORR active than nonfunctionalized rGO due to pyridinic-like N content and rGO-sp3-rGO is better ORR active than rGO-sp2-rGO due to higher pyridinic-like N content and π-electron interaction-free interlayer charge transfer. Thus, the rGO-sp3-rGO has proven as an efficient metal-free electrocatalyst with better electrocatalytic activity, stability, and tolerance to the crossover effect than the commercially available Pt/C for ORR. PMID:28240302

  15. Biodegradable polyurethane ureas with variable polyester or polycarbonate soft segments: effects of crystallinity, molecular weight and composition on mechanical properties

    PubMed Central

    Ma, Zuwei; Hong, Yi; Nelson, Devin M.; Pichamuthu, Joseph E.; Leeson, Cory E.; Wagner, William R.

    2011-01-01

    Biodegradable polyurethane urea (PUU) elastomers are ideal candidates for fabricating tissue engineering scaffolds with mechanical properties akin to strong and resilient soft tissues. PUU with a crystalline poly(ε-caprolactone) (PCL) macrodiol soft segment (SS) showed good elasticity and resilience at small strains (<50%), but showed poor resilience under large strains due to stress-induced crystallization of the PCL segments, with a permanent set of 677±30% after tensile failure. To obtain softer and more resilient PUUs, noncrystalline poly(trimethylene carbonate) (PTMC) or poly(δ-valerolactone-co-ε-caprolactone) (PVLCL) macrodiols of different molecular weights were used as SSs that were reacted with 1, 4-diisocyanatobutane and chain extended with 1, 4-diaminobutane. Mechanical properties of the PUUs were characterized by tensile testing with static or cyclic loading and dynamic mechanical analysis. All the PUUs synthesized showed large elongations at break (800–1400%) and high tensile strength (30–60 MPa). PUUs with non-crystalline SSs all showed improved elasticity and resilience relative to the crystalline PCL-based PUU, especially for the PUUs with high molecular weight SSs (PTMC 5400 Mn and PVLCL 6000 Mn), of which the permanent deformation after tensile failure was only 12±7% and 39±4%, respectively. The SS molecular weight also influenced the tensile modulus in an inverse fashion. Accelerated degradation studies in PBS containing 100 U/mL lipase showed significantly greater mass loss for the two polyester-based PUUs versus the polycarbonate-based PUU, and for PVLCL versus PCL polyester PUUs. Basic cytocompatibility was demonstrated with primary vascular smooth muscle cell culture. The synthesized families of PUUs showed variable elastomeric behavior that could be explained in terms of the underlying molecular design and crystalline behavior. Depending upon the application target of interest, these materials may provide options or guidance for

  16. Purification and Structural Characterization of Siderophore (Corynebactin) from Corynebacterium diphtheriae

    PubMed Central

    Zajdowicz, Sheryl; Haller, Jon C.; Krafft, Amy E.; Hunsucker, Steve W.; Mant, Colin T.; Duncan, Mark W.; Hodges, Robert S.; Jones, David N. M.; Holmes, Randall K.

    2012-01-01

    During infection, Corynebacterium diphtheriae must compete with host iron-sequestering mechanisms for iron. C. diphtheriae can acquire iron by a siderophore-dependent iron-uptake pathway, by uptake and degradation of heme, or both. Previous studies showed that production of siderophore (corynebactin) by C. diphtheriae is repressed under high-iron growth conditions by the iron-activated diphtheria toxin repressor (DtxR) and that partially purified corynebactin fails to react in chemical assays for catecholate or hydroxamate compounds. In this study, we purified corynebactin from supernatants of low-iron cultures of the siderophore-overproducing, DtxR-negative mutant strain C. diphtheriae C7(β) ΔdtxR by sequential anion-exchange chromatography on AG1-X2 and Source 15Q resins, followed by reverse-phase high-performance liquid chromatography (RP-HPLC) on Zorbax C8 resin. The Chrome Azurol S (CAS) chemical assay for siderophores was used to detect and measure corynebactin during purification, and the biological activity of purified corynebactin was shown by its ability to promote growth and iron uptake in siderophore-deficient mutant strains of C. diphtheriae under iron-limiting conditions. Mass spectrometry and NMR analysis demonstrated that corynebactin has a novel structure, consisting of a central lysine residue linked through its α- and ε- amino groups by amide bonds to the terminal carboxyl groups of two different citrate residues. Corynebactin from C. diphtheriae is structurally related to staphyloferrin A from Staphylococcus aureus and rhizoferrin from Rhizopus microsporus in which d-ornithine or 1,4-diaminobutane, respectively, replaces the central lysine residue that is present in corynebactin. PMID:22514641

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

    PubMed

    Vargas-Straube, María José; Cámara, Beatriz; Tello, Mario; Montero-Silva, Francisco; Cárdenas, Franco; Seeger, Michael

    2016-01-01

    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.

  18. Nuclease activity and interaction studies of unsymmetrical binuclear Ni(II) complexes with CT-DNA and BSA.

    PubMed

    Poornima, S; Gunasekaran, K; Kandaswamy, M

    2015-10-07

    New unsymmetrical binuclear nickel(II) complexes [Ni2L(1-5)] (ClO4)2 (1-5) were synthesized by using [NiL] [(3-((9E)-(2-((E)-(3-formyl-2-olato-5-methylbenzylideneamino)methyl) phenylimino)methyl)-3-formyl-5-methyl-2-olato)nickel(II)] with various diamines like 1,2-diaminoethane (L(1)), 1,3-diaminopropane (L(2)), 1,4-diaminobutane (L(3)), 1,2-diaminobenzene (L(4)) and 1,8-diaminonaphthalene (L(5)) and characterized by elemental analysis and spectroscopic methods. The molecular structure of binuclear nickel(II) complex 1 is determined by a single crystal X-ray diffraction method. Cyclic voltammograms of binuclear Ni(II) complexes exhibit two quasi-reversible reduction waves in the cathodic region and two oxidation waves in the anodic region. DNA binding, protein binding and DNA cleavage studies were investigated. The interactions of complexes (1-5) with calf thymus DNA were studied by spectroscopic techniques, including absorption and fluorescence methods. The binding affinities of complexes (1-5) with CT-DNA and nuclease activities are in the following order: 5> 4>3 >2>1 . Binuclear Ni(II) complex 1 cleaved the plasmid DNA by a hydrolytic pathway. The hydrolytic cleavage of DNA by the complexes is supported by evidence from free radical quenching and T4 ligase ligation. Binuclear Ni(II) complexes (1-5) displayed significant protein (bovine serum albumin) interactions. The experimental results showed that the interaction between binuclear Ni(II) complexes and BSA was mainly a static quenching process.

  19. Sequestering ability of some chelating agents towards methylmercury(II).

    PubMed

    Falcone, Gabriella; Foti, Claudia; Gianguzza, Antonio; Giuffrè, Ottavia; Napoli, Anna; Pettignano, Alberto; Piazzese, Daniela

    2013-01-01

    A study on the interactions between CH(3)Hg(+) and some S, N and O donor ligands (2-mercaptopropanoic acid (thiolactic acid (H(2)TLA)), 3-mercaptopropanoic acid (H(2)MPA), 2-mercaptosuccinic acid (thiomalic acid (H(3)TMA)), D,L-penicillamine (H(2)PSH), L-cysteine (H(2)CYS), glutathione (H(3)GSH), N,N'-bis(3-aminopropyl)-1-4-diaminobutane (spermine (SPER)), 1,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid (H(6)MLT)) and ethylenediaminetetraacetic acid (H(4)EDTA)) is reported. The speciation models in aqueous solution and the possible structures of the complexes formed are discussed on the basis of potentiometric, calorimetric, UV spectrophotometric and electrospray mass spectrometric results. For the CH(3)Hg(+)-S donor ligand systems, the formation of ML(1-z) and MLH(2-z) complex species is observed, together with a diprotonated MLH(2)(3-z) species for CYS(2-), PSH(2-) and GSH(3-) and the mixed hydrolytic one ML(OH)(-z) for TLA(2-) and MPA(2-). The dependence of the stability on ionic strength and on temperature is also analysed. In the other CH(3)Hg(+)-L systems (L = MLT(6-), SPER and EDTA(4-)), ML(1-z), MLH(2-z) and MLH(2)(3-z) complex species are formed, together with the MLH(3)(4-z) species for SPER, the mixed hydrolytic ML(OH)(-z) one for SPER and EDTA, and the M(2)L(2-z) for EDTA only. On the basis of the speciation models proposed, the sequestering ability of the ligands towards methylmercury(II) cation is evaluated. All S donor ligands show a good sequestering power (at 10(-11) mol L(-1) level, in the pH range 4 to 8) following the trend MPA(2-) < PSH(2-) < GSH(3-) < TLA(2-) < CYS(2-) < TMA(3-), while significantly lower is the sequestering ability of MLT, SPER and EDTA (at 10(-3)-10(-5) mol L(-1) level, in the pH range 4 to 8).

  20. Improving putrescine production by Corynebacterium glutamicum by fine-tuning ornithine transcarbamoylase activity using a plasmid addiction system.

    PubMed

    Schneider, Jens; Eberhardt, Dorit; Wendisch, Volker F

    2012-07-01

    Corynebacterium glutamicum shows a great potential for the production of the polyamide monomer putrescine (1,4-diaminobutane). Previously, we constructed the putrescine-producing strain PUT1 by deletion of argF, the gene for ornithine transcarbamoylase (OTC), and argR, encoding the L-arginine repressor, combined with heterologous expression of the Escherichia coli gene for L-ornithine decarboxylase SpeC. As a consequence of argF deletion, this strain requires supplementation of L-arginine and shows growth-decoupled putrescine production. To avoid costly supplementation with L-arginine and the strong feedback inhibition of the key enzyme N-acetylglutamate kinase (ArgB) by L-arginine, a plasmid addiction system for low-level argF expression was developed. By fine-tuning argF expression through modifications of the promoter, the translational start codon and/or the ribosome binding site, high productivity and titer could be obtained. OTC activity varied almost thousandfold between 960 and 1 mU mg⁻¹ resulting in putrescine yields on glucose from less than 0.001 up to 0.26 g g⁻¹, the highest yield in bacteria reported to date. The most promising strain, designated PUT21, was characterized comprehensively. PUT21 strain grew with a rate of 0.19 h⁻¹ in mineral salt medium without the need for L-arginine supplementation and produced putrescine with a yield of 0.16 g g⁻¹ glucose at a volumetric productivity of 0.57 g L⁻¹ h⁻¹ and a specific productivity of 0.042 g g⁻¹ h⁻¹. The carbon balance suggested that no major unidentified by-product was produced. Compared to the first-generation strain PUT1, the putrescine yield observed with PUT21 was increased by 60%. In fed-batch cultivation with C. glutamicum PUT21, a putrescine titer of 19 g L⁻¹ at a volumetric productivity of 0.55 g L⁻¹ h⁻¹ and a yield of 0.16 g g⁻¹ glucose could be achieved. Moreover, while plasmid segregation of the initial strain required antibiotic selection

  1. Amine templating effect absent in uranyl sulfates synthesized with 1,4-n-butyldiamine

    SciTech Connect

    Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

    2013-01-15

    Two new uranyl sulfates, (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS2) and (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2})(SO{sub 4}){sub 2}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS3), were synthesized and their crystal structures determined. NDUS2 was obtained in highly acidic media heat-treated at 373 K and subsequently maintained at 278 K until crystals formed after two months. NDUS3 results from the degradation of NDUS2 over the course of a few days. NDUS2 and NDUS3 crystallize in the monoclinic space group P2{sub 1}/n, a=10.9075(4) A, b=10.4513(4) A, c=17.7881(7) A, {beta}=97.908(2) Degree-Sign , V=2008.52(13) A{sup 3}, Z=4, at 140 K and a=8.8570(4) A, b=7.3299(3) A, c=20.4260(9) A, {beta}=95.140(2) Degree-Sign , V=1320.74(10) A{sup 3}, Z=4, at 140 K, respectively. The compounds contain interlayer 1,4-n-butyldiammonium cations that charge-balance the anionic structural units. - Graphical abstract: Amine templating effect absent in uranyl sulfates synthesized with 1,4-diaminobutane, as shown by the synthesis of two new uranyl sulfates, (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS2) and (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2})(SO{sub 4}){sub 2}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS3). Highlights: Black-Right-Pointing-Pointer Two layered uranyl sulfates were synthesized. Black-Right-Pointing-Pointer Amine molecules are located in the interlayers of the compounds. Black-Right-Pointing-Pointer No templating effect of the amine was observed. Black-Right-Pointing-Pointer Amine molecules are only charge balancing cations in the structures.

  2. Synthesis and characterization of zeolite-type materials: Germanates and zirconogermanates

    NASA Astrophysics Data System (ADS)

    Smith, Rebeca

    The great importance that zeolites have in the industry accounting for 40 billion US dollars a year to the petroleum cracking industry alone has attracted the interest of synthesizing and developing new crystalline microstructures. This work presents the unique structural properties of germanates, zeolite-type materials, by first reviewing five unique structure building units (SBUs) that include: 4=1 units, D4R units and large clusters with 7-, 9-, and 10-germanium atoms. Then, the work of the syntheses and characterization of different germanate structures is presented. The synthesis and characterization of four zirconogermanates constructed from the same cluster consisting of five tetrahedral germanium atoms and one zirconium atom in octahedral coordination is presented. The structures were prepared using different amines as structure directing agents (SDA); ASU-23 (using 1,4-bis(3-aminopropyl) consists of one layered structure, ASU-24 (using hexamethylenediamine) is a pillared layered structure with exceptionally low framework density (FD=8.48 metal atoms per nanometer cubed), ASU-25 and ASU-26 (using 1,3-diaminopropane and ethylenediamine respectively) have 3-dimensional (3D) frameworks. The layer germanate (ASU-22) is built from 7-germanium clusters. X-ray structural analysis [P6(3)cm, a =28.794(2), c=20.603(4), V=14793(3) (unit cell parameters are in angstroms, volume in angstroms cubed)] revealed that the framework exhibits the kagome (kgm) topology. The extensive series of syntheses demonstrated the key role played by HF in the condensation of the 7-germanium clusters (these clusters have not been synthesized without HF). The zirconogermanate, ASU-17, in the 1,4-diaminobutane-HF system, was synthesized as crystalline powder and identified in the cubic crystals system with space group Ia-3d and unit cell parameter a =51.3 (angstroms) and corresponds to the SU-M structure reported by a group in Sweden. Exploratory work leading to the discovery this 3D cubic

  3. Quantitation of 11 alkylamines in atmospheric samples: separating structural isomers by ion chromatography

    NASA Astrophysics Data System (ADS)

    Place, Bryan K.; Quilty, Aleya T.; Di Lorenzo, Robert A.; Ziegler, Susan E.; VandenBoer, Trevor C.

    2017-03-01

    Amines are important drivers in particle formation and growth, which have implications for Earth's climate. In this work, we developed an ion chromatographic (IC) method using sample cation-exchange preconcentration for separating and quantifying the nine most abundant atmospheric alkylamines (monomethylamine (MMAH+), dimethylamine (DMAH+), trimethylamine (TMAH+), monoethylamine (MEAH+), diethylamine (DEAH+), triethylamine (TEAH+), monopropylamine (MPAH+), isomonopropylamine (iMPAH+), and monobutylamine (MBAH+)) and two alkyl diamines (1, 4-diaminobutane (DABH+) and 1, 5-diaminopentane (DAPH+)). Further, the developed method separates the suite of amines from five common atmospheric inorganic cations (Na+, NH4+, K+, Mg2+, Ca2+). All 16 cations are greater than 95 % baseline resolved and elute in a runtime of 35 min. This paper describes the first successful separation of DEAH+ and TMAH+ by IC and achieves separation between three sets of structural isomers, providing specificity not possible by mass spectrometry. The method detection limits for the alkylamines are in the picogram per injection range and the method precision (±1σ) analyzed over 3 months was within 16 % for all the cations. The performance of the IC method for atmospheric application was tested with biomass-burning (BB) particle extracts collected from two forest fire plumes in Canada. In extracts of a size-resolved BB sample from an aged plume, we detected and quantified MMAH+, DMAH+, TMAH+, MEAH+, DEAH+, and TEAH+ in the presence of Na+, NH4+, and K+ at molar ratios of amine to inorganic cation ranging from 1 : 2 to 1 : 1000. Quantities of DEAH+ and DMAH+ of 0.2-200 and 3-1200 ng m-3, respectively, were present in the extracts and an unprecedented amine-to-ammonium molar ratio greater than 1 was observed in particles with diameters spanning 56-180 nm. Extracts of respirable fine-mode particles (PM2. 5) from a summer forest fire in British Columbia in 2015 were found to contain iMPAH+, TMAH+, DEAH

  4. A series of M(II)Cu(II)3 stars (M = Mn, Ni, Cu, Zn) exhibiting unusual magnetic properties.

    PubMed

    Mondal, Suraj; Mandal, Shuvankar; Carrella, Luca; Jana, Arpita; Fleck, Michel; Köhn, Andreas; Rentschler, Eva; Mohanta, Sasankasekhar

    2015-01-05

    The work in this report describes the syntheses, electrospray ionization mass spectromtery, structures, and experimental and density functional theoretical (DFT) magnetic properties of four tetrametallic stars of composition [M(II)(Cu(II)L)3](ClO4)2 (1, M = Mn; 2, M = Ni; 3, M = Cu; 4, M = Zn) derived from a single-compartment Schiff base ligand, N,N'-bis(salicylidene)-1,4-butanediamine (H2L), which is the [2 + 1] condensation product of salicylaldehyde and 1,4-diaminobutane. The central metal ion (Mn(II), Ni(II), Cu(II), or Zn(II)) is linked with two μ2-phenoxo bridges of each of the three [Cu(II)L] moieties, and thus the central metal ion is encapsulated in between three [Cu(II)L] units. The title compounds are rare or sole examples of stars having these metal-ion combinations. In the cases of 1, 3, and 4, the four metal ions form a centered isosceles triangle, while the four metal ions in 2 form a centered equilateral triangle. Both the variable-temperature magnetic susceptibility and variable-field magnetization (at 2-10 K) of 1-3 have been measured and simulated contemporaneously. While the Mn(II)Cu(II)3 compound 1 exhibits ferromagnetic interaction with J = 1.02 cm(-1), the Ni(II)Cu(II)3 compound 2 and Cu(II)Cu(II)3 compound 3 exhibit antiferromagnetic interaction with J = -3.53 and -35.5 cm(-1), respectively. Variable-temperature magnetic susceptibility data of the Zn(II)Cu(II)3 compound 4 indicate very weak antiferromagnetic interaction of -1.4 cm(-1), as expected. On the basis of known correlations, the magnetic properties of 1-3 are unusual; it seems that ferromagnetic interaction in 1 and weak/moderate antiferromagnetic interaction in 2 and 3 are possibly related to the distorted coordination environment of the peripheral copper(II) centers (intermediate between square-planar and tetrahedral). DFT calculations have been done to elucidate the magnetic properties. The DFT-computed J values are quantitatively (for 1) or qualitatively (for 2 and 3) matched