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Sample records for substituted acetophenone thiosemicarbazones

  1. Biotransformations of Substituted Phenylethanols and Acetophenones by Environmental Bacteria

    Edna Kagohara

    2008-01-01

    Full Text Available Whole cells of hydrocarbon-degrading bacteria, isolated from polluted sediments in the Santos Estuary (Baixada Santista, São Paulo, Brazil, were able to catalyse oxidoreduction reactions with various substituted phenylethanols and acetophenones as substrates. A number of substituted phenylethanols were formed with high (>99 % enantiomeric excess. The results of microbial oxidation of phenylethanols 2, 3, 5–7 by Acinetobacter sp. 6.4T and the reduction of acetophenones 1a–6a by Serratia marcescens 5.4T showed that the bacteria used as biocatalysts in this study present significant potential for exploitation in biotechnological processes. The reduction of prochiral acetophenones by Serratia marcescens 3.5T yielded optically active alcohols with 90–99 % enantiomeric excess, and Acinetobacter sp. 6.4T is a potential biocatalyst for the oxidation of alcohols.

  2. Spectral, thermal, electrochemical and analytical studies on Cd(II) and Hg(II) thiosemicarbazone complexes

    El-Asmy, A. A.; El-Gammal, O. A.; Saleh, H. S.

    2008-11-01

    The coordination characteristic of the investigated thiosemicarbazones towards hazard pollutants, Cd(II) and Hg(II), becomes the first goal. Their complexes have been studied by microanalysis, thermal, electrochemical and spectral (electronic, IR and MS) studies. The substitutent (salicylaldehyde, acetophenone, benzophenone, o-hydroxy- p-methoxybenzophenone or diacetylmonoxime) plays an important role in the complex formation. The coordination sites were the S for thiosemicarbazide (HTS); NN for benzophenone thiosemicarbazone (HBTS); NS for acetophenone thiosemicarbazone (HATS) and salicylaldehyde thiosemicarbazone (H 2STS); NNS or NSO for diacetylmonoxime thiosemicarbazone (H 2DMTS). The stability constants of Hg(II) complexes were higher than Cd(II). The kinetic and thermodynamic parameters for the different thermal decomposition steps in the complexes have been evaluated. The activation energy values of the first step ordered the complexes as: [Cd(H 2STS)Cl 2]H 2O > [Cd(H 2DAMTS)Cl 2] > [Cd(HBTS) 2Cl 2]2H 2O > [Cd(HATS) 2Cl 2]. The CV of [Cd(H 2STS)Cl 2]H 2O and [Hg(HBTS)Cl 2] were recorded. The use of H 2DMTS as a new reagent for the separation and determination of Cd(II) ions from water and some synthetic samples using flotation technique is aimed to be discussed.

  3. [Synthesis and biological activity of 1,4-benzoquinone-guanylhydrazone-thiosemicarbazone analogs. 1. Substitution at the S atom].

    Schulze, W; Gutsche, W; Wohlrabe, K; Fleck, W; Tresselt, D

    1985-08-01

    The synthesis of S-substituted derivatives of 1,4-benzoquinone-guanylhydrazone-thiosemicarbazone is described. The obtained 1,4-benzoquinone-guanylhydrazone-S-alkyl (resp. aralkyl)-isothiosemicarbazones, in comparison with the unsubstituted standard compound, showed a significantly decreased biological activity against the murine leukemias L 1210 and P 388 as well as against the growth of several kinds of bacteria. Therefore the S-substitution seems not to be useful for reaching a maximum activity.

  4. ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS

    Manzur, Carolina; Millán, Lorena; Figueroa, Walter; Hamon, Jean-René; Mata, Jose A.; Carrillo, David

    2002-01-01

    A series of twelve new organometallic acetophenone-hydrazone complexes of general formula [(h 5-Cp)Fe(h 6-o-RC6H4)-NHN=CMe-C6H4-p-R’]+PF6- (Cp= C5H5; R,R’=H,Me, [5]+PF6-; H,MeO, [6]+PF6-; H,NMe2, [7]+PF6-; Me,Me, [8]+PF6-; Me,MeO, [9]+PF6-; Me,NMe2, [10]+PF6-; MeO,Me, [11]+PF6-; MeO,MeO, [12]+PF6-; MeO,NMe2, [13]+PF6-; Cl,Me, [14]+PF6-; Cl,MeO, [15]+PF6-; Cl,NMe2, [16]+PF6-) has been prepared by reaction between their corresponding organometallic hydrazine precursors [(h 5-Cp)Fe(h 6-o-RC6H4)-...

  5. Conformational analysis of some 4‧-substituted 2-(phenylselanyl)- 2-(methoxy)- acetophenones

    Traesel, Henrique J.; Olivato, Paulo R.; Valença, J.; Rodrigues, Daniel N. S.; Zukerman-Schpector, Julio; Colle, Maurizio Dal

    2018-04-01

    A conformational study of some 4‧-substituited 2-(phenylselanyl)-2-(methoxy)-acetophenones (OMe 1, H 2, and Cl 3) was performed using IR carbonyl stretching band analysis supported by NBO and PCM calculations at the B3LYP/6-31 + G (d,p) level for 1-3 and using X-ray diffraction for 1 and 2. The computational results indicated the existence of three stable conformers for the series (c2, c3, and c1 in order of decreasing stability), whose relative abundance changes with solvent permittivity. The experimental trend observed for the components of the triplet carbonyl band in all solvents matches well with computational results and thus allows for their assignment to distinct conformers. The relative population of the c1 conformer increases in more polar solvents, becoming the most stable conformer in the highest permittivity solvent, acetonitrile, as indicated by IR spectra and PCM calculations. These findings are related to the quasi parallel geometry assumed by the Cδ+ = Oδ- and Cδ+-Oδ- dipoles, which favour stronger solvation. NBO analysis shows that the sum of the energies (ΣE) of the relevant orbital interactions stabilizes the c3 conformer of 1-3 slightly, likely due to the minor contribution of the LPO5→σ*C3sbnd Se10 interaction. However, only the c1 conformer is significantly destabilized by the Oδ-(1)CO … Oδ-(5)OMe short contact electrostatic repulsion, which is also responsible for its highest νCO frequency. In addition, the LPO5→ σ*C2sbnd C3 orbital interaction accounts for the lowest νCO frequency of c3 conformer. X-ray single crystal analysis of compounds 1 and 2 indicates that in the solid state they assume the least stable c1 conformation found in the gas phase. Molecules of these compounds are stabilized in the crystal through a series of Csbnd H⋯O and Csbnd H … π intermolecular interactions.

  6. 13C and 1H nuclear magnetic resonance of methyl-substituted acetophenones and methyl benzoates: steric hindrance and inhibited conjugation.

    Budesínský, Milos; Kulhánek, Jirí; Böhm, Stanislav; Cigler, Petr; Exner, Otto

    2004-10-01

    The 1H and 13C NMR spectra of 14 methyl-substituted acetophenones and 14 methyl-substituted methyl benzoates were assigned and interpreted with respect to the conformation of the C(ar)-C(O) bond. The substituent effects are proportional in the two series and can be divided into polar and steric: each has different effects on the 13C SCS of the individual atoms. In the case of C atoms C(O), C(1) and CH3(CO), the steric effects were quantitatively separated by comparing SCS in the ortho and para positions. The steric effects are proportional for the individual C atoms and also to steric effects estimated from other physical quantities. However, they do not depend simply on the angle of torsion phi of the functional group as anticipated hitherto. A better description distinguishes two classes of compounds: sterically not hindered or slightly hindered planar molecules and strongly sterically hindered, markedly non-planar. In order to confirm this reasoning without empirical correlations, the J(C,C) coupling constants were measured for three acetophenone derivatives labeled with 13C in the acetyl methyl group. The constants confirm unambiguously the conformation of 2-methylacetophenone; their zero values are in accord with the conformation of 2,6-dimethylacetophenone. The zero values in the unsubstituted acetophenone are at variance with previous erroneous report but all J(C,C) values are in accord with calculations at the B3LYP/6-311++G(2d,2p)//B3LYP/6-311+G(d,p) level. Copyright 2004 John Wiley & Sons, Ltd.

  7. Synthesis, antiviral evaluation and molecular docking studies of N4-aryl substituted/unsubstituted thiosemicarbazones derived from 1-indanones as potent anti-bovine viral diarrhea virus agents.

    Soraires Santacruz, María C; Fabiani, Matías; Castro, Eliana F; Cavallaro, Lucía V; Finkielsztein, Liliana M

    2017-08-01

    A series of N 4 -arylsubstituted thiosemicarbazones derived from 1-indanones and a set of compounds lacking such substitution in the N 4 position of the thiosemicarbazone moiety were synthesized and evaluated for their anti-bovine viral diarrhea virus (BVDV) activity. Among these, derivatives 2 and 15 displayed high activity (EC 50 =2.7±0.4 and 0.7±0.1µM, respectively) as inhibitors of BVDV replication. Novel key structural features related to the anti-BVDV activity were identified by structure-activity relationship (SAR) analysis. In a previous study, the thiosemicarbazone of 5,6-dimethoxy-1-indanone (5,6-TSC) was characterized as a non-nucleoside inhibitor (NNI) of the BVDV RNA-dependent RNA polymerase. In the present work, cross-resistance assays were performed with the most active compounds. Such studies were carried out on 5,6-TSC resistant BVDV (BVDV-TSC r T1) carrying mutations in the viral polymerase. This BVDV mutant was also resistant to compound 15. Molecular docking studies and MM/PBSA calculations were performed to assess the most active derivatives at the 5,6-TSC viral polymerase binding site. The differences in the interaction pattern and the binding affinity of derivative 15 either to the wild type or BVDV-TSC r T1 polymerase were key factors to define the mode of action of this compound. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Synthesis, Characterization, and Biological Evaluation of certain 6-methyl-2(3H)-benzo-1, 3-thiazolyl-1'-ethylidene-2-(o, p- Substituted Acetophenones) Hydrazine Analogs.

    Alang, G; Kaur, G; Kaur, R; Singh, A; Tiwari, R

    2010-10-01

    In the present study, five new derivatives (GG4 to GG8) of benzothiazoles were synthesized and evaluated against Staphylococcus aureus (MTCC 737), Pseudomonas aeruginosa (MTCC 424), Escherichia coli (MTCC 1687), and yeast-like fungi Candida tropicalis. p-Toluidine on treatment with ammonium thiocynate formed 2-benzothiazolamines (II), which on reaction with hydrazine hydrate formed a hydrazino derivative (III). Compounds GG4 to GG8 were synthesized by reacting the hydrazine derivative with different acetophenones. All the synthesized compounds were identified by IR and (1)H-NMR, and antimicrobial activity was performed on the synthesized compounds. Presence of NO(2), Br, OCH(3), and Cl groups to the substituted benzothiazole enhanced the antibacterial and antifungal activities.

  9. Synthesis, structures, spectroscopy and antimicrobial properties of complexes of copper(II) with salicylaldehyde N-substituted thiosemicarbazones and 2,2'-bipyridine or 1,10-phenanthroline.

    Lobana, Tarlok S; Indoria, Shikha; Jassal, Amanpreet Kaur; Kaur, Harpreet; Arora, Daljit S; Jasinski, Jerry P

    2014-04-09

    Among the biometals (Cu, Co, Ni-cofactors in many enzymes), copper derivatives of O, N, S-donor salicylaldehyde thiosemicarbazones have received considerable attention owing to their potential biological applications. Eight new complexes of salicylaldehyde-N-substituted thiosemicarbazones [5-MeO-2-HO-C₆H₄-C(2)(H)N(3)-N(2)H-C(1)(S)-N(1)HR; R = Me, H2L(1); Et, H₂L(1), Ph, H₂L(3), H, H₂L(4)] with copper(II), namely, [Cu(κ(3)-O,N,S-L)( κ(2)-N,N-L')] {(L)(2-) = (L(1))(2-), L' = bipy, 1, phen, 2; (L)(2-) = (L(2))(2-), L' = bipy, 3, phen, 4; (L)(2-) = (L(3))(2-), L' = bipy, 5, phen, 6; (L)(2-) = (L(4))(2-), L' = bipy, 7, phen, 8} have been isolated. Complexes have slightly distorted square pyramidal geometry around the metal center (τ parameter = 0.243-0.357) and display weak to intense fluorescence in the region, 375-475 nm. These copper complexes have shown significant growth inhibitory activity (antimicrobial activity) against Staphylococcus aureus (MTCC740), methicillin resistant Staphylococcus aureus (MRSA), Klebsiella pneumoniae 1 (MTCC109), Shigella flexneri (MTCC1457), Pseudomonas aeruginosa (MTCC741) and Candida albicans (MTCC227). The activity against MRSA is an interesting observation as the commercially available gentamycin is found to be inactive against this bacterial strain. Specifically complex 5 formed by 5-methoxysalicylaldehyde-N-phenylthiosemicatbazone has shown novel antimicrobial activity against various bacteria and yeast investigated. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  10. Synthesis, Characterization, and Biological Evaluation of certain 6-methyl-2(3H)-benzo-1, 3-thiazolyl-1’-ethylidene-2-(o, p- Substituted Acetophenones) Hydrazine Analogs

    Alang, G; Kaur, G; Kaur, R; Singh, A; Tiwari, R

    2010-01-01

    In the present study, five new derivatives (GG4 to GG8) of benzothiazoles were synthesized and evaluated against Staphylococcus aureus (MTCC 737), Pseudomonas aeruginosa (MTCC 424), Escherichia coli (MTCC 1687), and yeast-like fungi Candida tropicalis. p-Toluidine on treatment with ammonium thiocynate formed 2-benzothiazolamines (II), which on reaction with hydrazine hydrate formed a hydrazino derivative (III). Compounds GG4 to GG8 were synthesized by reacting the hydrazine derivative with different acetophenones. All the synthesized compounds were identified by IR and 1H-NMR, and antimicrobial activity was performed on the synthesized compounds. Presence of NO2, Br, OCH3, and Cl groups to the substituted benzothiazole enhanced the antibacterial and antifungal activities. PMID:21264101

  11. CHARACTERIZATION AND ANTIPARASITIC ACTIVITY OF BENZOPHENONE THIOSEMICARBAZONES ON Trypanosoma brucei brucei

    Georges C. Accrombessi

    2011-02-01

    Full Text Available The structure of four synthesized thiosemicarbazones, substituted or not, of benzophenone has been confirmed by spectrometrical analysis IR, NMR 1H and 13C. Their anti-trypanosomal activities were evaluated on Trypanosoma brucei brucei. Among these compounds, benzophenone 4 phenyl-3-thiosemicarbazone 4 has the highest activity with the half-inhibitory concentration (IC50 = 8.48 micromolar (µM. Benzophenone 4-methyl-3-thiosemicarbazone 3 and benzophenone thiosemicarbazone 1 showed moderate anti-trypanosomal activity with IC50 values equal to 23.27 µM and 67.17 µM respectively. Benzophenone 2 methyl-3-thiosemicarbazone 2 showed no activity up to IC50 = 371.74 µM.

  12. Tween® 20-Enhanced Bioreduction of Acetophenones Promoted by Daucus carota Root

    Monique Rodrigues da Costa

    2017-01-01

    Full Text Available The effect of surfactants on the bioreduction of acetophenones mediated by carrot (Daucus carota root was investigated. Among the tested surfactants, Tween® 20 slightly improved the conversion. The amount of surfactant was optimised, and the presented methodology was applied to other substituted acetophenones, which led to the preparation of their respective optically enriched 1-phenylethanols with high conversion levels and high enantioselectivities.

  13. Evidence for side-chain π-delocalization in a planar substituted benzene: an experimental and theoretical charge density study on 2,5-dimethoxybenzaldehyde thiosemicarbazone.

    Farrugia, Louis J; Khalaji, Aliakbar Dehno

    2011-11-17

    The charge density in 2,5-dimethoxybenzaldehyde thiosemicarbazone (1) has been studied experimentally using Mo-K(α) X-ray diffraction at 100 K, and by theory using DFT calculations at the B3LYP/6-311++G(2d,2p) level. The quantum theory of atoms in molecules (QTAIM) was used to investigate the extent of π-delocalization in the thioamide side-chain, which is virtually coplanar with the benzene ring. The experimental and theoretical ellipticity profiles along the bond paths were in excellent agreement, and showed that some of the formal single bonds in the side-chain have significant π-bond character. This view was supported by the magnitudes of the topological bond orders and by the delocalization indices δ(Ω(A), Ω(B)). An orbital decomposition of δ(Ω(A), Ω(B)) demonstrated that there was significant π-character in all the interchain non-H chemical bonds. On the other hand, the source function referenced at the interchain bond critical points could not provide any evidence for π-delocalization, showing instead only limited σ-delocalization between nearest neighbors. Overall, the topological evidence and the atomic graphs of the oxygen atoms did not provide convincing evidence for π-delocalization involving the methoxy substituents.

  14. In vitro antioxidant, antiinflammatory and in silico molecular docking studies of thiosemicarbazones

    Subhashree, G. R.; Haribabu, J.; Saranya, S.; Yuvaraj, P.; Anantha Krishnan, D.; Karvembu, R.; Gayathri, D.

    2017-10-01

    A series of 5-methoxysalicylaldehyde appended thiosemicarbazones (1-4) and 2-hydroxy-1-naphthaldehyde appended thiosemicarbazones (5-8) was obtained from the reactions between 5-methoxysalicylaldehyde/2-hydroxy-1-naphthaldehyde and (un)substituted thiosemicarbazides with the view to ascertain their biological properties brought about by the change in substitution at N-terminal position of the thiosemicarbazide derivatives. The compounds were fully characterized by elemental analyses, and various spectroscopic techniques (UV-Visible, FT-IR, NMR and mass). The solid-state structure of three compounds (1, 2 and 7) was determined by single crystal X-ray diffraction method. The compounds (1, 2 and 7) have adopted a monoclinic crystal system with P21/c (1 and 2) or C2/c (7) space group. Antioxidant and non-haemolysis activities of the compounds (1-8) were analyzed by in vitro DPPH and haemolysis assays, respectively. Antiinflammatory potential was verified by in vitro PLA2 inhibition assay and in silico molecular docking study. In vitro and in silico studies revealed promising antiinflammatory potential of the thiosemicarbazone derivatives. Compounds 2, 4, 6, 7 and 8 showed significant antiinflammatory activity.

  15. Antifouling efficacy of a controlled depletion paint formulation with acetophenone

    Sangmok Jung

    2017-12-01

    Full Text Available Biofouling is an inevitable problem that occurs continually on marine fishing vessels and other small crafts. The nature of the antifouling (AF coatings used to prevent biofouling on these small vessels is of great environmental concern. Therefore, the efficacy of a non-toxic AF candidate, acetophenone, was evaluated in preliminary laboratory assays using marine bacteria, diatom and Ulva spores. At a low concentration of 100 μg cm–2 of acetophenone, spore attachment of a green fouling alga was significantly reduced (p < 0.01. Similarly, 40% acetophenone coatings significantly inhibited diatom attachment. This new non-toxic AF agent was incorporated into controlled depletion paint (CDP. Fouling coverage (%, biomass, and fouling resistance (% were estimated. On CDP coatings made with acetophenone (40%, a significant decrease in fouling biomass was estimated (p < 0.01.

  16. Coumarin or benzoxazinone bearing benzimidazolium and bis(benzimidazolium salts; involvement in transfer hydrogenation of acetophenone derivatives and hCA inhibition

    Mert Olgun Karataş

    2015-10-01

    Full Text Available Four new salts of benzimidazolium and bis(benzimidazolium which include coumarin or benzoxazinone moieties were synthesized and the structures of the newly synthesized compounds were elucidated on the basis of spectral analyses such as 1H-NMR, 13C-NMR, HSQC, IR, LC-MS and elemental analysis. Benzimidazolium salts were used intensively as N-heterocyclic carbene (NHC precursors in the various catalytic reactions such as transfer hydrogenation (TH, C-H bond activation, Heck, Suzuki reaction etc. With the prospect of potential NHC precursor properties of the synthesized compounds, they were employed in the (TH reaction of p-substitute acetophenones (acetophenone, p-methyl acetophenone, p-chloro acetophenone and good yields were observed. Coumarin compounds are known as inhibitor of carbonic anhydrase and inhibition effects of the synthesized compounds on human carbonic anhydrases (hCA were investigated as in vitro. The in vitro results demonstrated that all compounds inhibited hCA I and hCA II activity. Among the synthesized compounds 1,4-bis(1-((6,8-dimethyl-2H-chromen-2-one-4-ylmethylbenzimidazolium-3-ylbutane dichloride was found to be the most active IC50= 5.55 mM and 6.06 mM for hCA I and hCA II, respectively.

  17. Thiosemicarbazone complexes of the platinum metals. A story of ...

    Unknown

    Thiosemicarbazone complexes; platinum metals; variable coordination; ... carbonylic carbon via one or two intervening atoms, D,N,S tricoordination usually takes .... modelling studies show that in this coordination mode, the phenyl ring of the.

  18. [Anti-arrhythmic action of some amidinohydrazone substituted benzophenones. 1. Synthesis of new amidinohydrazone and N-phenylamidinohydrazone substituted benzophenones].

    Richter, P H; Kasbohm, K; Besch, A; Hagen, A

    1992-10-01

    The title compounds are synthesized as a rule by condensation of substituted benzophenones and derivatives of aminoguanidine in the presence of up to 2.5 moles of an anorganic acid. They can be obtained alternatively via corresponding hydrazones, thiosemicarbazones or methylthiothiocarbonylhydrazones.

  19. A fluorescent bioreporter for acetophenone and 1-phenylethanol derived from a specifically induced catabolic operon

    Enrico eMuhr

    2016-01-01

    Full Text Available The β-proteobacterium Aromatoleum aromaticum degrades the aromatic ketone acetophenone, a key intermediate of anaerobic ethylbenzene metabolism, either aerobically or anaerobically via a complex ATP-dependent acetophenone carboxylase and a benzoylacetate-CoA ligase. The genes coding for these enzymes (apcABCDE and bal are organized in an apparent operon and are expressed in the presence of the substrate acetophenone. To study the conditions under which this operon is expressed in more detail, we constructed a reporter strain by inserting a gene fusion of apcA, the first gene of the apc-bal operon, with the gene for the fluorescent protein mCherry into the chromosomal DNA of A. aromaticum. The mCherry fusion protein indeed responded consistently with the expression pattern of the acetophenone-metabolic enzymes under various growth conditions. After evaluating and quantifying the data by fluorescence microscopy, fluorescence based flow cytometry and immunoblot analysis, the recorded amounts of mCherry production were found to be proportional to the applied acetophenone concentrations. The reporter strain allowed quantification of acetophenone within a concentration range of 50 µM (detection limit to 250 µM after 12 and 24 hours. Moreover, production of the Apc-mCherry fusion protein in the reporter strain was highly specific and responded to acetophenone and both enantiomers of 1-phenylethanol, which are easily converted to acetophenone. Other analogous substrates showed either a significantly weaker response or none at all. Therefore, the reporter strain provides a basis for the development of a specific bioreporter system for acetophenone with application potentials reaching from environmental monitoring to petroleum prospecting.

  20. A Fluorescent Bioreporter for Acetophenone and 1-Phenylethanol derived from a Specifically Induced Catabolic Operon.

    Muhr, Enrico; Leicht, Oliver; González Sierra, Silvia; Thanbichler, Martin; Heider, Johann

    2015-01-01

    The β-proteobacterium Aromatoleum aromaticum degrades the aromatic ketone acetophenone, a key intermediate of anaerobic ethylbenzene metabolism, either aerobically or anaerobically via a complex ATP-dependent acetophenone carboxylase and a benzoylacetate-CoA ligase. The genes coding for these enzymes (apcABCDE and bal) are organized in an apparent operon and are expressed in the presence of the substrate acetophenone. To study the conditions under which this operon is expressed in more detail, we constructed a reporter strain by inserting a gene fusion of apcA, the first gene of the apc-bal operon, with the gene for the fluorescent protein mCherry into the chromosome of A. aromaticum. The fusion protein indeed accumulated consistently with the expression pattern of the acetophenone-metabolic enzymes under various growth conditions. After evaluating and quantifying the data by fluorescence microscopy, fluorescence-based flow cytometry and immunoblot analysis, mCherry production was found to be proportional to the applied acetophenone concentrations. The reporter strain allowed quantification of acetophenone within a concentration range of 50 μM (detection limit) to 250 μM after 12 and 24 h. Moreover, production of the Apc-mCherry fusion protein in the reporter strain was highly specific and responded to acetophenone and both enantiomers of 1-phenylethanol, which are easily converted to acetophenone. Other analogous substrates showed either a significantly weaker response or none at all. Therefore, the reporter strain provides a basis for the development of a specific bioreporter system for acetophenone with an application potential reaching from environmental monitoring to petroleum prospecting.

  1. Casbane diterpenes and acetophenones of Croton nepetaefolius (Euphorbiaceae)

    Santos, Helcio Silva; Mesquita, Francisca Maria Rodrigues; Lemos, Telma Leda G.; Monte, Francisco Jose Queiroz; Braz-Filho, Raimundo

    2008-01-01

    Croton nepetaefolius is an aromatic plant native to the northeast of Brazil where it is extensively used in folk medicine as a sedative, orexigen and antispasmodic agent. The present work deals with the chromatographic analysis of the ethanolic extract of Croton nepetaefolius stalk. It allowed the isolation and characterization of two diterpenoids named 1,4-dihydroxy-2E,6E,12E-trien-5-one-casbane and 4-hydroxy- 2E,6E,12E-5-one-casbane, two acetophenones named 2-hydroxy-4,6-dimethoxyacetophenone and 2-hydroxy-3,4,6- trimethoxyacetophenone and the steroids 3-O-beta-D-glucopiranosylsitosterol and a mixture of beta-sitosterol and stigmasterol. Structural elucidation was done on the basis of spectral data, mainly high field NMR and EIMS. (author)

  2. Synthesis of complex compounds in the system [ReOG5]2--thiosemicarbazone acetone-Hg-acetone

    Amindzhanov, A.A.; Kurbanov, N.M.

    1993-01-01

    Present article is devoted to synthesis of complex compounds in the system [ReOG 5 ] 2- -thiosemicarbazone acetone-Hg-acetone. The literature data on complex compounds of various metals with thiosemicarbazone was summarized. The synthesis of complex compounds in the system [ReOG 5 ] 2- -thiosemicarbazone acetone-Hg-acetone was conducted. The complex compounds of rhenium with methyl ident thiosemicarbazone were synthesized.

  3. Synergistic extraction of Th(IV) by 2-hydroxy-1-naphthaldehyde thiosemicarbazone and neutral donors

    Banerjee, S.; Basu, S.

    2003-01-01

    The extraction behaviour of Th(IV) from aqueous nitric acid medium employing 2-hydroxy-1-naphthaldehyde thiosemicarbazone has been studied in the presence of various donors, like trioctyl phosphine oxide (TOPO), calix[3]OH[3]OMe[6]arene, trioctyl amine (TOA), dimethyl sulphoxide (DMSO) in ethylacetate solvent. The constants (log k ex ) for the binary complex in organic phase [Th(A)(NO 3 ) 3 ], where A is the ligand, was found to be 3.99, which was by far the largest amongst the corresponding values known for the other thiosemicarbazones. The overall equilibrium constants (log K) for the ternary species [Th(A)TOPO(NO 3 ) 3 ], [Th(A)TOA(NO 3 ) 3 ], [Th(A)Calix[3]OH[3]OMe[6]arene(NO 3 ) 3 ], [Th(A)DMSO(NO 3 ) 3 ] were estimated to be 8.287, 8.862, 8.415, 6.921 respectively. The trend in equilibrium constants were in accordance with the substitution of the donor. The extraction of Th 4+ by the ligand-donor combination was maximum at pH = 1 and extraction decreases with increase in pH. It has been found that the extent of extraction of Th 4+ in the organic phase as the binary as well as ternary complex [Th(A)(NO 3 ) 3 ] and [Th(A)(NO 3 ) 3 S], where S is the donor, increases with increase in the concentration of the ligand. Similar trend is obtained in the extraction by donors in absence of ligand. In case of ternary extraction, using different donors, amines are found to perform best compared to the other donors. The trend is as follows: TOA > calix[3]OH[3]OMe[6]arene > TOPO > DMSO. In addition, the effect of different diluents on extraction was also studied and the observed trend was methyl salicylate > ethyl acetate > methyl isobutyl ketone > ethyl benzoate. (orig.)

  4. Microbial conversion of ethylbenzene to 1-phenethanol and acetophenone by Nocardia tartaricans ATCC 31190.

    Cox, D P; Goldsmith, C D

    1979-09-01

    A culture of Nocardia tartaricans ATCC 31190 was capable of catalyzing the conversion of ethylbenzene to 1-phenethanol and acetophenone while growing in a shake flask culture with hexadecane as the source of carbon and energy. This subterminal oxidative reaction with ethylbenzene appears not to have been previously reported for Nocardia species. When N. tartaricans was grown on glucose as its source of carbon and energy and ethylbenzene was added, no subsequent production of 1-phenethanol or acetophenone was observed. The mechanisms of 1-phenethanol and acetophenone production from ethylbenzene are thought to involve a subterminal oxidation of the alpha-carbon of the alkyl group to 1-phenethanol followed by biological oxidation of the latter to acetophenone.

  5. DNA-binding, catalytic oxidation, C—C coupling reactions and antibacterial activities of binuclear Ru(II thiosemicarbazone complexes: Synthesis and spectral characterization

    Arumugam Manimaran

    2012-07-01

    Full Text Available New hexa-coordinated binuclear Ru(II thiosemicarbazone complexes of the type {[(B(EPh3(COClRu]2L} (where, E = P or As; B = PPh3 or AsPh3 or pyridine; L = mononucleating NS donor of N-substituted thiosemicarbazones have been synthesized and characterized by elemental analysis, FT-IR, UV–vis and 31P{1H} NMR cyclic voltammetric studies. The DNA-binding studies of Ru(II complexes with calf thymus DNA (CT-DNA were investigated by UV–vis, viscosity measurements, gel-electrophoresis and fluorescence spectroscopy. The new complexes have been used as catalysts in C—C coupling reaction and in the oxidation of alcohols to their corresponding carbonyl compounds by using NMO as co-oxidant and molecular oxygen (O2 atmosphere at ambient temperature. Further, the new binucleating thiosemicarbazone ligands and their Ru(II complexes were also screened for their antibacterial activity against Klebsiella pneumoniae, Shigella sp., Micrococcus luteus, Escherichia coli and Salmonella typhi. From this study, it was found out that the activity of the complexes almost reaches the effectiveness of the conventional bacteriocide.

  6. Thiosemicarbazones: preparation methods, synthetic applications and biological importance

    Tenorio, Romulo P.; Goes, Alexandre J.S.; Lima, Jose G. de; Faria, Antonio R. de; Alves, Antonio J.; Aquino, Thiago M. de

    2005-01-01

    Thiosemicarbazones are a class of compounds known by their chemical and biological properties, such as antitumor, antibacterial, antiviral and antiprotozoal activity. Their ability to form chelates with metals has great importance in their biological activities. Their synthesis is very simple, versatile and clean, usually giving high yields. They are largely employed as intermediates, in the synthesis of others compounds. This article is a survey of some of these characteristics showing their great importance to organic and medicinal chemistry. (author)

  7. Titanium zirconium and hafnium coordination compounds with vanillin thiosemicarbazone

    Konunova, Ts.B.; Kudritskaya, S.A.

    1987-01-01

    Coordination compounds of titanium zirconium and hafnium tetrachlorides with vanillin thiosemicarbazone of MCl 4 x nLig composition, where n=1.5, 4 for titanium and 1, 2, 4 for zirconium and hafnium, are synthesized. Molar conductivity of ethanol solutions is measured; IR spectroscopic and thermochemical investigation are carried out. The supposition about ligand coordination via sulfur and azomethine nitrogen atoms is made. In all cases hafnium forms stable compounds than zirconium

  8. Cu(II) bis(thiosemicarbazone) radiopharmaceutical binding to serum albumin: further definition of species dependence and associated substituent effects

    Basken, Nathan E.; Green, Mark A.

    2009-01-01

    Introduction: The pyruvaldehyde bis(N 4 -methylthiosemicarbazonato)copper(II) (Cu-PTSM) and diacetyl bis(N 4 -methylthiosemicarbazonato)copper(II) (Cu-ATSM) radiopharmaceuticals exhibit strong, species-dependent binding to the IIA site of human serum albumin (HSA), while the related ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) radiopharmaceutical appears to exhibit only nonspecific binding to HSA and animal serum albumins. Methods: To further probe the structural basis for the species dependence of this albumin binding interaction, we examined protein binding of these three radiopharmaceuticals in solutions of albumin and/or serum from a broader array of mammalian species (rat, sheep, donkey, rabbit, cow, pig, dog, baboon, mouse, cat and elephant). We also evaluated the albumin binding of several copper(II) bis(thiosemicarbazone) chelates offering more diverse substitution of the ligand backbone. Results: Cu-PTSM and Cu-ATSM exhibit a strong interaction with HSA that is not apparent with the albumins of other species, while the binding of Cu-ETS to albumin is much less species dependent. The strong interaction of Cu-PTSM with HSA does not appear to simply correlate with variation, relative to the animal albumins, of a single amino acid lining HSA's IIA site. Those agents that selectively interact with HSA share the common feature of only methyl or hydrogen substitution at the carbon atoms of the diimine fragment of the ligand backbone. Conclusions: The interspecies variations in albumin binding of Cu-PTSM and Cu-ATSM are not simply explained by unique amino acid substitutions in the IIA binding pocket of the serum albumins. However, the specific affinity for this region of HSA is disrupted when substituents bulkier than a methyl group appear on the imine carbons of the copper bis(thiosemicarbazone) chelate.

  9. Cu(II) bis(thiosemicarbazone) radiopharmaceutical binding to serum albumin: further definition of species dependence and associated substituent effects

    Basken, Nathan E. [Division of Nuclear Pharmacy, Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette, IN 47907 (United States); Green, Mark A. [Division of Nuclear Pharmacy, Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette, IN 47907 (United States)], E-mail: magreen@purdue.edu

    2009-07-15

    Introduction: The pyruvaldehyde bis(N{sup 4}-methylthiosemicarbazonato)copper(II) (Cu-PTSM) and diacetyl bis(N{sup 4}-methylthiosemicarbazonato)copper(II) (Cu-ATSM) radiopharmaceuticals exhibit strong, species-dependent binding to the IIA site of human serum albumin (HSA), while the related ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) radiopharmaceutical appears to exhibit only nonspecific binding to HSA and animal serum albumins. Methods: To further probe the structural basis for the species dependence of this albumin binding interaction, we examined protein binding of these three radiopharmaceuticals in solutions of albumin and/or serum from a broader array of mammalian species (rat, sheep, donkey, rabbit, cow, pig, dog, baboon, mouse, cat and elephant). We also evaluated the albumin binding of several copper(II) bis(thiosemicarbazone) chelates offering more diverse substitution of the ligand backbone. Results: Cu-PTSM and Cu-ATSM exhibit a strong interaction with HSA that is not apparent with the albumins of other species, while the binding of Cu-ETS to albumin is much less species dependent. The strong interaction of Cu-PTSM with HSA does not appear to simply correlate with variation, relative to the animal albumins, of a single amino acid lining HSA's IIA site. Those agents that selectively interact with HSA share the common feature of only methyl or hydrogen substitution at the carbon atoms of the diimine fragment of the ligand backbone. Conclusions: The interspecies variations in albumin binding of Cu-PTSM and Cu-ATSM are not simply explained by unique amino acid substitutions in the IIA binding pocket of the serum albumins. However, the specific affinity for this region of HSA is disrupted when substituents bulkier than a methyl group appear on the imine carbons of the copper bis(thiosemicarbazone) chelate.

  10. The antimicrobial activity of lapachol and its thiosemicarbazone and semicarbazone derivatives

    Marina Azevedo Souza

    2013-05-01

    Full Text Available Lapachol was chemically modified to obtain its thiosemicarbazone and semicarbazone derivatives. These compounds were tested for antimicrobial activity against several bacteria and fungi by the broth microdilution method. The thiosemicarbazone and semicarbazone derivatives of lapachol exhibited antimicrobial activity against the bacteria Enterococcus faecalis and Staphylococcus aureus with minimal inhibitory concentrations (MICs of 0.05 and 0.10 µmol/mL, respectively. The thiosemicarbazone and semicarbazone derivatives were also active against the pathogenic yeast Cryptococcus gattii (MICs of 0.10 and 0.20 µmol/mL, respectively. In addition, the lapachol thiosemicarbazone derivative was active against 11 clinical isolates of Paracoccidioides brasiliensis, with MICs ranging from 0.01-0.10 µmol/mL. The lapachol-derived thiosemicarbazone was not cytotoxic to normal cells at the concentrations that were active against fungi and bacteria. We synthesised, for the first time, thiosemicarbazone and semicarbazone derivatives of lapachol. The MICs for the lapachol-derived thiosemicarbazone against S. aureus, E. faecalis, C. gattii and several isolates of P. brasiliensis indicated that this compound has the potential to be developed into novel drugs to treat infections caused these microbes.

  11. Eco-Friendly Synthesis of Some Thiosemicarbazones and Their Applications as Intermediates for 5-Arylazothiazole Disperse Dyes

    Hatem E. Gaffer

    2015-12-01

    Full Text Available The solid-solid reactions of thiosemicarbazide with 4-formylantipyrine, 2-acetylpyrrole and camphor were performed to afford the thiosemicarbazones 1–3 which underwent hetero-cyclization with phenacyl bromide to furnish the corresponding thiazole derivatives 4–6. The yields of the reactions are quantitative in all cases and the products do not require further purification. A series of 5-arylazo-2-(substituted ylidene-hydrazinyl-thiazole dyes 7–9 was then prepared by diazo coupling of thiazole derivatives 4–6 with several diazonium chlorides. The synthesized dyes were applied as disperse dyes for dyeing polyester fabric. The dyed fabrics exhibit good washing, perspiration, sublimation and light fastness properties, with little variation in their moderate to good rubbing fastness.

  12. Synergistic extraction of Th(IV) by 2-hydroxy-1-naphthaldehyde thiosemicarbazone and neutral donors

    Banerjee, S.; Basu, S. [Nuclear and Analytical Chemistry Lab., Dept. of Chemistry, The Univ. of Burdwan, Burdwan (India)

    2003-07-01

    The extraction behaviour of Th(IV) from aqueous nitric acid medium employing 2-hydroxy-1-naphthaldehyde thiosemicarbazone has been studied in the presence of various donors, like trioctyl phosphine oxide (TOPO), calix[3]OH[3]OMe[6]arene, trioctyl amine (TOA), dimethyl sulphoxide (DMSO) in ethylacetate solvent. The constants (log k{sub ex}) for the binary complex in organic phase [Th(A)(NO{sub 3}){sub 3}], where A is the ligand, was found to be 3.99, which was by far the largest amongst the corresponding values known for the other thiosemicarbazones. The overall equilibrium constants (log K) for the ternary species [Th(A)TOPO(NO{sub 3}){sub 3}], [Th(A)TOA(NO{sub 3}){sub 3}], [Th(A)Calix[3]OH[3]OMe[6]arene(NO{sub 3}){sub 3}], [Th(A)DMSO(NO{sub 3}){sub 3}] were estimated to be 8.287, 8.862, 8.415, 6.921 respectively. The trend in equilibrium constants were in accordance with the substitution of the donor. The extraction of Th{sup 4+} by the ligand-donor combination was maximum at pH = 1 and extraction decreases with increase in pH. It has been found that the extent of extraction of Th{sup 4+} in the organic phase as the binary as well as ternary complex [Th(A)(NO{sub 3}){sub 3}] and [Th(A)(NO{sub 3}){sub 3}S], where S is the donor, increases with increase in the concentration of the ligand. Similar trend is obtained in the extraction by donors in absence of ligand. In case of ternary extraction, using different donors, amines are found to perform best compared to the other donors. The trend is as follows: TOA > calix[3]OH[3]OMe[6]arene > TOPO > DMSO. In addition, the effect of different diluents on extraction was also studied and the observed trend was methyl salicylate > ethyl acetate > methyl isobutyl ketone > ethyl benzoate. (orig.)

  13. Synthesis and cytotoxicity evaluation of thiosemicarbazones and their thiazole derivatives

    Saulo Feheiberg Pinto Braga

    Full Text Available ABSTRACT The aims of this study were to synthesize a series of thiosemicarbazones and their thiazole derivatives, to investigate their cytotoxic activity against three human cancers and normal (Vero cells cell lines, and to evaluate the pro-apoptotic potential of the most active compounds. Materials and Methods: The thiosemicarbazones were obtained by reacting an aromatic aldehyde with thiosemicarbazide (yield 71-96%, which were subjected to a cyclization with α-bromoacetophenone to yield the required thiazole heterocycles (yield 63-100%. All the synthesized compounds were screened at 50 µM concentration against three cell lines representing HL60 (promyelocytic leukemia, Jurkat (acute lymphoblastic leukemia, and MCF-7 (breast cancer. The pro-apoptotic effect was measured by flow cytometry as the percentage of cells with hypodiploid DNA. Results: Three thiazole compounds showed activity against at least one tumor cell line (IC50 = 43-76 µM and low cytotoxicity against Vero cells (IC50 > 100 M. The most active compound of this series induced 91% and 51% DNA fragmentation in HL60 and MCF-7 cell lines, respectively, suggesting that this compound triggered apoptosis in these cells. Conclusion: Among the synthesized compounds, one in particular was found to exert antiproliferative and pro-apoptotic activity on tumor cells and can be considered promising as a lead molecule for the design of new analogues with improved activity.

  14. Cu-catalyzed aerobic oxidative esterification of acetophenones with alcohols to α-ketoesters.

    Xu, Xuezhao; Ding, Wen; Lin, Yuanguang; Song, Qiuling

    2015-02-06

    Copper-catalyzed aerobic oxidative esterification of acetophenones with alcohols using molecular oxygen has been developed to form a broad range of α-ketoesters in good yields. In addition to reporting scope and limitations of our new method, mechanism studies are reported that reveal that the carbonyl oxygen in the ester mainly originated from dioxygen.

  15. In vivo function of Pgβglu-1 in the release of acetophenones in white spruce

    Melissa H. Mageroy

    2017-07-01

    Full Text Available Eastern spruce budworm (Choristoneura fumiferiana Clemens (ESBW is a major forest pest which feeds on young shoots of white spruce (Picea glauca and can cause landscape level economic and ecological losses. Release of acetophenone metabolites, piceol and pungenol, from their corresponding glycosides, picein and pungenin, can confer natural resistance of spruce to ESBW. A beta-glucosidase gene, Pgβglu-1, was recently discovered and the encoded enzyme was characterized in vitro to function in the release of the defensive acetophenone aglycons. Here we describe overexpression of Pgβglu-1 in a white spruce genotype whose metabolome contains the glucosylated acetophenones, but no detectable amounts of the aglycons. Transgenic overexpression of Pgβglu-1 resulted in release of the acetophenone aglycons in planta. This work provides in vivo evidence for the function of Pgβglu-1.

  16. Investigation of the Biological Properties of (HeteroAromatic Thiosemicarbazones

    Jaroslaw Polanski

    2012-11-01

    Full Text Available Two series of thiosemicarbazone-based iron chelators (twenty-seven compounds were designed and synthesized using a microwave-assisted approach. Quinoline and halogenated phenyl were selected as parent scaffolds on the basis of a similarity search. The lipophilicity of the synthesized compounds was measured using HPLC and then calculated. Primary in vitro screening of the synthesized compounds was performed against eight pathogenic fungal strains. Only a few compounds showed moderate activity against fungi, and (E-2-(quinolin-2-ylvinyl-N,N-dimethylhydrazine-carbothioamide appeared to be more effective than fluconazole against most of the fungal strains tested. Antiproliferative activity was measured using a human colon cancer cell line (HCT-116. Several of the tested compounds showed submicromolar antiproliferative activity. Compounds were also tested for their activity related to the inhibition of photosynthetic electron transport (PET in spinach (Spinacia oleracea L. chloroplasts. The structure-activity relationships are discussed for all of the compounds.

  17. Thermal Decomposition Reaction of Acetophenone Cyclic Diperoxide in Solvents of Different Physicochemical Properties

    C. M. Mateo

    2000-03-01

    Full Text Available The thermal decomposition reaction of acetophenone cyclic diperoxide (trans-3,6-dimethyl-3,6-diphenyl-1,2,4,5-tetroxane; APDP at the initial concentration of c.a. 0.01 mol kg-1 and temperature ranges of 135.5 to 185.0° C has been investigated in dioxane and acetonitrile solutions, and in an 2-propanol/benzene mixture.

  18. Synthesis, EPR, Electronic and Magnetic Studies on Cobalt (II) Complexes of Semicarbazone and Thiosemicarbazone

    Chandra, S.; Gupta, L.K.; Sharma, K.K.

    2005-01-01

    Cobalt (II) complexes having the general composition Co(L2) X2 [where Lisopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and4-aminoacetophenone thiosemicarbazone (LLD) and X=Cl] have been synthesized. All the Co(II) complexes reported here have been characterized by elemental analyses, magnetic moments, IR, electronic and EPR spectral studies. All the complexes were found to have magnetic moments corresponding to three unpaired electrons. The possible geometries of the complexes were assigned on the basis of electronic infrared and EPR spectral studies. (author) = = = = = = = = = = = = = = =

  19. Intermolecular interaction of thiosemicarbazone derivatives to solvents and a potential Aedes aegypti target

    da Silva, João Bosco P.; Hallwass, Fernando; da Silva, Aluizio G.; Moreira, Diogo Rodrigo; Ramos, Mozart N.; Espíndola, José Wanderlan P.; de Oliveira, Ana Daura T.; Brondani, Dalci José; Leite, Ana Cristina L.; Merz, Kenneth M.

    2015-08-01

    DFT calculations were used to access information about structure, energy and electronic properties of series of phenyl- and phenoxymethyl-(thio)semicarbazone derivatives with demonstrated activity against the larvae of Aedes aegypti in stage L4. The way as the thiosemicarbazone derivatives can interact with solvents like DMSO and water were analyzed from the comparison between calculated and experimental 1H NMR chemical shifts. The evidences of thiosemicarbazone derivatives making H-bond interaction to solvent have provide us insights on how they can interact with a potential A. aegypti's biological target, the Sterol Carrier Protein-2.

  20. A novel class of thiosemicarbazones show multi-functional activity for the treatment of Alzheimer's disease.

    Palanimuthu, Duraippandi; Poon, Rachal; Sahni, Sumit; Anjum, Rukhsana; Hibbs, David; Lin, Hsuan-Yu; Bernhardt, Paul V; Kalinowski, Danuta S; Richardson, Des R

    2017-10-20

    Over 44 million people live with Alzheimer's disease (AD) worldwide. Currently, only symptomatic treatments are available for AD and no cure exists. Considering the lack of effective treatments for AD due to its multi-factorial pathology, development of novel multi-target-directed drugs are desirable. Herein, we report the development of a novel series of thiosemicarbazones derived from 1-benzylpiperidine, a pharmacophore within the acetylcholinesterase inhibitor, Donepezil. These thiosemicarbazones were designed to target five major AD hallmarks, including: low acetylcholine levels, dysfunctional autophagy, metal dys-homeostasis, protein aggregation and oxidative stress. Of these thiosemicarbazones, pyridoxal 4-N-(1-benzylpiperidin-4-yl)thiosemicarbazone (PBPT) emerged as the lead compound. This agent demonstrated the most promising multi-functional activity by exhibiting very low anti-proliferative activity, substantial iron chelation efficacy, inhibition of copper-mediated amyloid-β aggregation, inhibition of oxidative stress, moderate acetylcholinesterase inhibitory activity and autophagic induction. These diverse properties highlight the potential of the lead ligand, PBPT, as a promising multi-functional agent for AD treatment. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  1. An Expedient Method for the Synthesis of Thiosemicarbazones under Microwave Irradiation in Solvent-free Medium

    LI, Jian-Ping; ZHENG, Peng-Zhi; ZHU, Jun-Ge; LIU, Rui-Jie; QU, Gui-Rong

    2006-01-01

    A simple, efficient and eco-friendly method for the synthesis of thiosemicarbazones from thiosemicarbazides and aldehyde under microwave irradiation has been reported, and no solvent and catalyst were used. And the technique of microwave irradiation coupled with solvent-free condition proved to be a quite valuable method in the organic synthesis.

  2. A new acetophenone derivative from flowers of Helichrysum italicum (Roth) Don ssp. italicum.

    Rigano, Daniela; Formisano, Carmen; Pagano, Ester; Senatore, Felice; Piacente, Sonia; Masullo, Milena; Capasso, Raffaele; Izzo, Angelo A; Borrelli, Francesca

    2014-12-01

    A new acetophenone derivative named gnaphaliol 9-O-propanoate (1) was isolated from the chloroform fraction of EtOH extract of Helichrysum italicum ssp. italicum flowers along with the five known acetophenones 12-acetoxytremetone (2), 13-(2-methylpropanoyloxy)toxol (3), [2,3-dihydro-2-[1-(hydroxymethyl)ethenyl]-5-benzofuranyl]-ethanone (4), 1-[2-[1-[(acetyloxy)methyl]ethenyl]-2,3-dihydro-3-hydroxy-5-benzofuranyl]-ethanone (5) and gnaphaliol (6). The structures of compounds 1-6 were elucidated by extensive spectroscopic methods including 1D- ((1)H and (13)C) and 2D-NMR (DQF-COSY, HSQC, HMBC, TOCSY and ROESY) experiments as well as ESIMS analysis. The isolated compounds were investigated for their cytotoxicity, anti-inflammatory and antioxidant properties. Biological assays on human colonic epithelial cells showed that compound 2 possessed antioxidant effects reducing reactive oxygen species (ROS) production. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Synthesis and prospective study of the use of thiophene thiosemicarbazones as signalling scaffolding for the recognition of anions

    Raposo, M. Manuela M.; García-Acosta, Beatriz; Ábalos, Tatiana; Calero, P.; Martínez-Máñez, Ramón; Ros-Lis, José Vicente; Soto, Juan

    2010-01-01

    A family of phenyl-thiosemicarbazone dyes have been prepared and their interactions with anions monitorized via UV-Vis, fluorescence and 1H NMR titrations. Additionally quantum chemical calculations and electrochemical studies completed the studies carried out. The phenyl-thiosemicarbazone dyes show a modulation of their hydrogen-bonding and electron-donating capabilities as a function of the chemical groups attached and display two different chromo-fluorogenic responses towards anions in ace...

  4. Tuning of the charge in octahedral ferric complexes based on pyridoxal-N-substituted thiosemicarbazone ligands

    Tido, Eddy W. Yemeli; Faulmann, Christophe; Roswanda, Robby; Meetsma, Auke; van Koningsbruggen, Petra J.

    2010-01-01

    Four novel mononuclear coordination compounds namely: [Fe(Hthpy)(2)](SO(4))(1/2)center dot 3.5H(2)O 1, [Fe(Hthpy)(2)]NO(3)center dot 3H(2)O 2, [Fe(H(2)mthpy)(2)](CH(3)C(6)H(4)SO(3))(3)center dot CH(3)CH(2)OH 3 and [Fe(Hethpy)(ethpy)]center dot 8H(2)O 4, (H(2)thpy = pyridoxalthiosemicarbazone,

  5. SYNTHESIS AND ANTITUMOR ACTIVITY OF COPPER, NICKEL AND COBALT COORDINATION COMPOUNDS WITH 1-(2-HYDROXYPHENYLETHANONE N(4-ALLYL-3-THIOSEMICARBAZONE

    Vasilii GRAUR

    2015-12-01

    Full Text Available The paper presents the synthesis of the ligand 1-(2-hydroxyphenylethanone N(4-allyl-3-thiosemicarbazone (H2L and six coordination compounds of copper, nickel and cobalt with this ligand. The structure of thiosemicarbazone H2L was studied using 1H and 13С NMR spectroscopy. The synthesized coordination compounds were studied using elemental analysis, gravimetric analysis of water content, molar conductivity, and magnetochemistry. For H2L the antitumor activity towards human leukemia HL-60 cells and cervical cancer HeLa cells was determined. It was established that the substitution of hydrogen atom with methyl group in the azomethinic fragment leads to the growth of antitumor activity.SINTEZA ŞI ACTIVITATEA ANTITUMORALĂ A COMPUŞILOR COMPLECŞI AI CUPRULUI, NICHELULUI ŞI COBALTULUI CU N(4-ALIL-3-TIOSEMICARBAZONA 1-(2-HIDROXIFENILETANONEILucrarea conţine descrierea sintezei N(4-alil-3-tiosemicarbazonei 1-(2-hidroxifeniletanonei (H2L şi a şase compuşi coordinativi ai cuprului, nichelului şi cobaltului cu acest ligand. Structura tiosemicarbazonei H2L a fost stabilită în baza datelor spectroscopiei RMN 1H şi 13C. Compuşi coordinativi au fost studiaţi cu ajutorul analizei elementale, analizei gravimetrice a conţinutului de apă, conductivitaţii molare şi magnetochimiei. Pentru H2L a fost determinată activitatea antitumorală faţă de celulele leucemiei umane HL-60 şi ale cancerului cervical HeLa. S-a stabilit că înlocuirea atomului de hidrogen cu o grupare metil în fragmentul azomethinic conduce la creşterea activitaţii antitumorale.

  6. Study on the reactive transient α-λ3-iodanyl-acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed α-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry.

    Wang, Hao-Yang; Zhou, Juan; Guo, Yin-Long

    2012-03-30

    Hypervalent iodine compounds are important and widely used oxidants in organic chemistry. In 2005, Ochiai reported the PhI-catalyzed α-acetoxylation reaction of acetophenone by the oxidation of PhI with m-chloroperbenzoic acid (m-CPBA) in acetic acid. However, until now, the most critical reactive α-λ(3)-iodine alkyl acetophenone intermediate (3) had not been isolated or directly detected. Electrospray ionization tandem mass spectrometry (ESI-MS/MS) was used to intercept and characterize the transient reactive α-λ(3)-iodine alkyl acetophenone intermediate in the reaction solution. The trivalent iodine species was detected when PhI and m-CPBA in acetic acid were mixed, which indicated the facile oxidation of a catalytic amount of PhI(I) to the iodine(III) species by m-CPBA. Most importantly, 3·H(+) was observed at m/z 383 from the reaction solution and this ion gave the protonated α-acetoxylation product 4·H(+) at m/z 179 in MS/MS by an intramolecular reductive elimination of PhI. These ESI-MS/MS studies showed the existence of the reactive α-λ(3)-iodine alkyl acetophenone intermediate 3 in the catalytic cycle. Moreover, the gas-phase reactivity of 3·H(+) was consistent with the proposed solution-phase reactivity of the α-λ(3)-iodine alkyl acetophenone intermediate 3, thus confirming the reaction mechanism proposed by Ochiai. Copyright © 2012 John Wiley & Sons, Ltd.

  7. Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone

    List, Nanna Holmgaard; Beerepoot, Maarten; Olsen, Jógvan Magnus Haugaard

    2015-01-01

    for the quantum region, covering (multiconfigurational) self-consistent-field and Kohn–Sham density functional theory. As the first application of the implementation, we consider the internal vibrational Stark effect of the C=O group of acetophenone in different solvents and derive its vibrational linear Stark...

  8. Extractive spectrophotometric determination of molybdenum using p-chloroisonitroso acetophenone hydrazone

    Lokhande, R.S.; Agashe, A.P.; Hundiwale, D.G.

    2001-01-01

    Separation technique like solvent extraction can be advantageously employed for the determination of metals at low concentration in micrograms using spectrophotometric methods. Hydrazoxine has been used for the extraction and spectrophotometric determination of metals at trace level as well as for the studies of transition metals in complex form. In the present paper, solvent extraction technique has been used to develop methods for the separation and spectrophotometric determination of Mo(VI) with p-chloroisonitroso acetophenone hydrazone was extracted into chloroform from aqueous solution in the pH range 8 to 8.5. The absorption maxima was also tried for the extracted species and Beer's law was also studied for its applicability. In this, interference from the foreign ion has also been examined. (author)

  9. Phase transition and intramolecular hydrogen bonding in nitro derivatives of ortho-hydroxy acetophenones

    Filarowski, A.; Kochel, A.; Koll, A.; Bator, G.; Mukherjee, S.

    2006-03-01

    The crystal structures of two ortho-hydroxy aryl ketones (5-chloro-3-nitro-2-hydroxyacetophenone, 5-methyl-3-nitro-2-hydroxyacetophenone and the complex 5-chloro-3-nitro-2-hydroxyacetophenone with 2-aminobenzoic acid (anthranilic acid)) were determined by X-ray diffraction. The existence of an intramolecular hydrogen bond of enol character between the hydroxyl and acetyl groups was found by the X-ray method. The enol character was also confirmed by DFT (B3LYP/6-31+G(d,p)) calculations. A phase transition was found at 138 K in 5-chloro-3-nitro-2-hydroxyacetophenone. This phase transition was investigated by differential scanning calorimetry (DSC), dilatometry, and the dielectric method. A study of the nitro-group dynamics in the ortho-hydroxy acetophenones was carried out with DFT (B3LYP/6-31+G(d,p)) calculations.

  10. Synthesis and biochemical evaluation of benzoylbenzophenone thiosemicarbazone analogues as potent and selective inhibitors of cathepsin L

    Parker, Erica N; Song, Jiangli; Kishore Kumar, G D

    2015-01-01

    selective in their inhibition of cathepsin L compared to cathepsin B. Thiosemicarbazone analogue 32 inhibited invasion through Matrigel of MDA-MB-231 breast cancer cells by 70% at 10μM. Thiosemicarbazone analogue 8 significantly inhibited the invasive potential of PC-3ML prostate cancer cells by 92% at 5μ......Upregulation of cathepsin L in a variety of tumors and its ability to promote cancer cell invasion and migration through degradation of the extracellular matrix suggest that cathepsin L is a promising biological target for the development of anti-metastatic agents. Based on encouraging results from......) was well-tolerated in a CDF1 mouse model bearing an implanted C3H mammary carcinoma, and showed efficacy in tumor growth delay. Low cytotoxicity, inhibition of cell invasion, and in vivo tolerability are desirable characteristics for anti-metastatic agents functioning through an inhibition of cathepsin L...

  11. Vibrational spectroscopy (FT-IR and Laser-Raman) investigation, and computational (M06-2X and B3LYP) analysis on the structure of 4-(3-fluorophenyl)-1-(propan-2-ylidene)-thiosemicarbazone.

    Sert, Yusuf; Miroslaw, Barbara; Çırak, Çağrı; Doğan, Hatice; Szulczyk, Daniel; Struga, Marta

    2014-07-15

    In this study, the experimental and theoretical vibrational spectral analysis of 4-(3-fluorophenyl)-1-(propan-2-ylidene)-thiosemicarbazone have been carried out. The experimental FT-IR (4000-400 cm(-1)) and Laser-Raman spectra (4000-100 cm(-1)) have been recorded for the solid state samples. The theoretical vibrational frequencies and the optimized geometric parameters (bond lengths and angles) have been calculated for gas phase using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr) and M06-2X (the highly parametrized, empirical exchange correlation function) quantum chemical methods with 6-311++G(d,p) basis set. The diversity in molecular geometry of fluorophenyl substituted thiosemicarbazones has been discussed based on the X-ray crystal structure reports and theoretical calculation results from the literature. The assignments of the vibrational frequencies have been done on the basis of potential energy distribution (PED) analysis by using VEDA4 software. A good correlation was found between the computed and experimental geometric and vibrational data. In addition, the highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbital energy levels and other related molecular energy values of the compound have been determined using the same level of theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Gold(III) bis(thiosemicarbazonate) compounds in breast cancer cells: Cytotoxicity and thioredoxin reductase targeting.

    Rodríguez-Fanjul, Vanessa; López-Torres, Elena; Mendiola, M Antonia; Pizarro, Ana María

    2018-03-25

    Gold(III) compounds have received increasing attention in cancer research. Three gold complexes of general formula [Au III L]Cl, where L is benzil bis(thiosemicarbazonate), compound 1, benzil bis(4-methyl-3-thiosemicarbazonate), compound 2, or benzil bis(4-cyclohexyl-3-thiosemicarbazonate), compound 3, have been synthesized and fully characterized, including the X-ray crystal structure of compound 3, confirming square-planar geometry around the gold(III) centre. Compound 1 showed moderate cytotoxicity and accumulation in MCF7 breast cancer cells but did not inhibit thioredoxin reductase (TrxR) activity and did not induce reactive oxygen species (ROS) production. Compound 2, the least cytotoxic, was found to be capable of modestly inhibiting TrxR activity and produced low levels of ROS in the MCF7 cell line. The most cytotoxic compound, 3, had the highest cellular accumulation and its distribution pattern showed a clear preference for the cytosol and mitochondria of MCF7 cells. It readily hampered intracellular TrxR activity leading to a dramatic alteration of the cellular redox state and to the induction of cell death. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

  13. Optimization of Pressurized Liquid Extraction of Three Major Acetophenones from Cynanchum bungei Using a Box-Behnken Design

    Li, Wei; Zhao, Li-Chun; Sun, Yin-Shi; Lei, Feng-Jie; Wang, Zi; Gui, Xiong-Bin; Wang, Hui

    2012-01-01

    In this work, pressurized liquid extraction (PLE) of three acetophenones (4-hydroxyacetophenone, baishouwubenzophenone, and 2,4-dihydroxyacetophenone) from Cynanchum bungei (ACB) were investigated. The optimal conditions for extraction of ACB were obtained using a Box-Behnken design, consisting of 17 experimental points, as follows: Ethanol (100%) as the extraction solvent at a temperature of 120 °C and an extraction pressure of 1500 psi, using one extraction cycle with a static extraction time of 17 min. The extracted samples were analyzed by high-performance liquid chromatography using an UV detector. Under this optimal condition, the experimental values agreed with the predicted values by analysis of variance. The ACB extraction yield with optimal PLE was higher than that obtained by soxhlet extraction and heat-reflux extraction methods. The results suggest that the PLE method provides a good alternative for acetophenone extraction. PMID:23203079

  14. Optimization of Pressurized Liquid Extraction of Three Major Acetophenones from Cynanchum bungei Using a Box-Behnken Design

    Hui Wang

    2012-11-01

    Full Text Available In this work, pressurized liquid extraction (PLE of three acetophenones (4-hydroxyacetophenone, baishouwubenzophenone, and 2,4-dihydroxyacetophenone from Cynanchum bungei (ACB were investigated. The optimal conditions for extraction of ACB were obtained using a Box-Behnken design, consisting of 17 experimental points, as follows: Ethanol (100% as the extraction solvent at a temperature of 120 °C and an extraction pressure of 1500 psi, using one extraction cycle with a static extraction time of 17 min. The extracted samples were analyzed by high-performance liquid chromatography using an UV detector. Under this optimal condition, the experimental values agreed with the predicted values by analysis of variance. The ACB extraction yield with optimal PLE was higher than that obtained by soxhlet extraction and heat-reflux extraction methods. The results suggest that the PLE method provides a good alternative for acetophenone extraction.

  15. Concise Access to 2-Aroylbenzothiazoles by Redox Condensation Reaction between o-Halonitrobenzenes, Acetophenones, and Elemental Sulfur.

    Nguyen, Thanh Binh; Pasturaud, Karine; Ermolenko, Ludmila; Al-Mourabit, Ali

    2015-05-15

    A wide range of 2-aroylbenzothiazoles 3 including some pharmacologically relevant derivatives can be obtained in high yields by simply heating o-halonitrobenzenes 1, acetophenones 2, elemental sulfur, and N-methylmorpholine. This three-component nitro methyl coupling was found to occur in an excellent atom-, step-, and redox-efficient manner in which elemental sulfur played the role of nucleophile building block and redox moderating agent to fulfill electronic requirements of the global reaction.

  16. Dynamic Combinatorial Chemistry and Organocatalysis with Thiosemicarbazones and Organocatalysts for Hydrazone and Oxime Bioconjugations

    Larsen, Dennis

    new types of catalysts were discovered: The 2-aminophenols and the 2-(aminomethyl)benzimidazoles. With aldehyde substrates none of the newly discovered catalysts were as effective as a previously discovered benzenephosphonic acid, but with aromatic ketones, an otherwise challenging class of substrates......, the 2-(aminomethyl)benzimidazoles showed promising efficacies, reaching an hitherto unseen 5-fold rate enhancement for hydrazone formation on model acetophenone at pH 7.4....

  17. The novel thiosemicarbazone, di-2-pyridylketone 4-cyclohexyl-4-methyl-3-thiosemicarbazone (DpC, inhibits neuroblastoma growth in vitro and in vivo via multiple mechanisms

    Zhu-Ling Guo

    2016-09-01

    Full Text Available Abstract Background Neuroblastoma is a relatively common and highly belligerent childhood tumor with poor prognosis by current therapeutic approaches. A novel anti-cancer agent of the di-2-pyridylketone thiosemicarbazone series, namely di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT, demonstrates promising anti-tumor activity. Recently, a second-generation analogue, namely di-2-pyridylketone 4-cyclohexyl-4-methyl-3-thiosemicarbazone (DpC, has entered multi-center clinical trials for the treatment of advanced and resistant tumors. The current aim was to examine if these novel agents were effective against aggressive neuroblastoma in vitro and in vivo and to assess their mechanism of action. Methods Neuroblastoma cancer cells as well as immortalized normal cells were used to assess the efficacy and selectivity of DpC in vitro. An orthotopic SK-N-LP/Luciferase xenograft model was used in nude mice to assess the efficacy of DpC in vivo. Apoptosis in tumors was confirmed by Annexin V/PI flow cytometry and H&E staining. Results DpC demonstrated more potent cytotoxicity than Dp44mT against neuroblastoma cells in a dose- and time-dependent manner. DpC significantly increased levels of phosphorylated JNK, neuroglobin, cytoglobin, and cleaved caspase 3 and 9, while decreasing IkBα levels in vitro. The contribution of JNK, NF-ĸB, and caspase signaling/activity to the anti-tumor activity of DpC was verified by selective inhibitors of these pathways. After 3 weeks of treatment, tumor growth in mice was significantly (p < 0.05 reduced by DpC (4 mg/kg/day given intravenously and the agent was well tolerated. Xenograft tissues showed significantly higher expression of neuroglobin, cytoglobin, caspase 3, and tumor necrosis factor-α (TNFα levels and a slight decrease in interleukin-10 (IL-10. Conclusions DpC was found to be highly potent against neuroblastoma, demonstrating its potential as a novel therapeutic for this disease. The ability

  18. Preparation of Pd-Loaded Hierarchical FAU Membranes and Testing in Acetophenone Hydrogenation.

    Molinari, Raffaele; Lavorato, Cristina; Mastropietro, Teresa F; Argurio, Pietro; Drioli, Enrico; Poerio, Teresa

    2016-03-22

    Pd-loaded hierarchical FAU (Pd-FAU) membranes, containing an intrinsic secondary non-zeolitic (meso)porosity, were prepared and tested in the catalytic transfer hydrogenation of acetophenone (AP) to produce phenylethanol (PE), an industrially relevant product. The best operating conditions were preliminarily identified by testing different solvents and organic hydrogen donors in a batch hydrogenation process where micron-sized FAU seeds were employed as catalyst support. Water as solvent and formic acid as hydrogen source resulted to be the best choice in terms of conversion for the catalytic hydrogenation of AP, providing the basis for the design of a green and sustainable process. The best experimental conditions were selected and applied to the Pd-loaded FAU membrane finding enhanced catalytic performance such as a five-fold higher productivity than with the unsupported Pd-FAU crystals (11.0 vs. 2.2 mgproduct gcat(-1)·h(-1)). The catalytic performance of the membrane on the alumina support was also tested in a tangential flow system obtaining a productivity higher than that of the batch system (22.0 vs. 11.0 mgproduct gcat(-1)·h(-1)).

  19. KINETICS AND MECHANISM OF PHOTOINDUCED POLYMERIZATION BY α,α-DIMETHOXY-α-PHENYL ACETOPHENONE

    WANG Xiuzhi; LI Miaozhen; CHANG Zhiying; WANG Erjian

    1993-01-01

    α,α- dimethoxy- α-phenyl acetophenone (DMPA) is an efficient and thermally stable photoinitiator.Here its spectral characteristics in the transient state were shown. The transient species were identified as a benzoyl radical and a dimethoxyl benzyl radical that played a primary initiation role in polymerization. The kinetics and mechanism of the bulk polymerization of MMA were investigated. The exponent of DMPA concentration and κp/κt1/2 value were found to be 0.5 and 0.066 mol-1/2l1/2 s-1/2 , respectively. The existence of oxygen led to obtain the polymer with higher molecular weight, which can be attributed to the occurrence of the subsequent polymerization induced by active polymer end group. In the photocrosslinking reaction, the dependence of DMPA content on initial rate has been found. A principal reason is that the sample contained higher percentage of DMPA has higher light-absorbed efficiency. In solid film, higher concentration of DMPA is permitted to be used because there is little excited state self-quenching effect in the rigid medium.

  20. Preparation of Pd-Loaded Hierarchical FAU Membranes and Testing in Acetophenone Hydrogenation

    Raffaele Molinari

    2016-03-01

    Full Text Available Pd-loaded hierarchical FAU (Pd-FAU membranes, containing an intrinsic secondary non-zeolitic (mesoporosity, were prepared and tested in the catalytic transfer hydrogenation of acetophenone (AP to produce phenylethanol (PE, an industrially relevant product. The best operating conditions were preliminarily identified by testing different solvents and organic hydrogen donors in a batch hydrogenation process where micron-sized FAU seeds were employed as catalyst support. Water as solvent and formic acid as hydrogen source resulted to be the best choice in terms of conversion for the catalytic hydrogenation of AP, providing the basis for the design of a green and sustainable process. The best experimental conditions were selected and applied to the Pd-loaded FAU membrane finding enhanced catalytic performance such as a five-fold higher productivity than with the unsupported Pd-FAU crystals (11.0 vs. 2.2 mgproduct gcat−1·h−1. The catalytic performance of the membrane on the alumina support was also tested in a tangential flow system obtaining a productivity higher than that of the batch system (22.0 vs. 11.0 mgproduct gcat−1·h−1.

  1. Deuteration of acetanilides and other substituted aromatics using [Ir(COD)(Cy3P)(Py)]PF6 as catalyst

    Hesk, D.; Das, P.R.; Evans, B.

    1995-01-01

    Deuterium exchange labelling using [Ir(COD)(Cy 3 P)(Py)]PF 6 as catalyst and deuterium gas was studied on a number of substituted acetanilides. In most cases products containing deuterium ortho to the anilide group were obtained with a high degree of enrichment. With one exception no evidence for meta, para or anilide methyl labelling was seen. The catalyst was also effective in the ortho deuteration of acetophenone, benzophenone and the β-lactam containing compound Sch 48461. (Author)

  2. Solvent extraction of silver(I) from dilute cyanide solutions with 2,4-dihydroxyacetophenone thiosemicarbazone

    Reddy, A.V.; Reddy, Y.K.; Reddy, G.S.

    1986-01-01

    The solvent extraction of silver(I) was carried out in 0.5M nitric acid in the presence of cyanide by 2,4-dihydroxyacetophenone thiosemicarbazone (DATS). Ethyl acetate was used as a solvent and quantitative recovery was possible with 12.5-fold excess of the reagent in a single extraction. In this medium silver(I) forms a 2:2 complex (metal:ligand) with DATS. The effect of diverse ions on the extraction of silver(I) was investigated. (author)

  3. Guanylation of thiosemicarbazones: a new synthetic route to polysubstituted guanylhydrazones with antimicrobial activity

    Cunha, Silvio; Macedo Junior, Fernando Cesar de; Costa, Giselle A.N.; Neves, Daniela C.; Souza Neta, Lourdes Cardoso de

    2009-01-01

    Thiosemicarbazones were employed for the first time as electrophiles in the guanylation reaction promoted by HgCl 2 , affording polysubstituted guanylhydrazones, with regioselective introduction of each nitrogen substituent. The antibacterial and antifungal activities of guanylhydrazones were evaluated by determination of minimal inhibitory concentrations. Some of them exhibited very low minimal inhibitory concentrations (MIC) and broad-spectrum activities. The configurations of two guanylhydrazones were assigned by X-ray analysis that also revealed intramolecular interactions of the type N-H...N and C-H...N. (author)

  4. Spectral studies of coordination compounds of cobalt(II) with thiosemicarbazone of heterocyclic ketone

    Chandra, Sulekh; Kumar, Umendra

    2005-12-01

    The paper presents the spectral analysis of cobalt(II) complexes with indoxyl thiosemicarbazone (ITSC) of general composition [CoL 2X 2] (where L = ITSC, X = Cl -, NO 3-, (1/2)SO 42-, NCS -). The geometry of the complexes have been characterized by elemental analysis, molar conductance, magnetic susceptibility measurements and spectral (electronic, IR, EPR, 1H NMR, mass) studies. The various physico-chemical techniques suggested a coordination number of six (octahedral) for chloro, nitrato and thiocyanato complexes. Whereas sulfato complex was found to have five coordinate trigonal-bipyramidal geometry. All the complexes are of high spin type showing magnetic moment corresponding to three unpaired electrons.

  5. Electron-topological investigation of the structure-antitumor activity relationship of thiosemicarbazone derivatives.

    Dimoglo, A S; Chumakov, Y M; Dobrova, B N; Saracoglu, M

    1997-04-01

    In the frameworks of the electron-topological method (ETM) the structure-antitumor activity relationship was investigated for a series of thiosemicarbazone derivatives. The series included 70 compounds. Conformational analysis and quantum-chemical calculations were carried out for each compound. The revealed activity feature showed a satisfactory description of the class of active compounds according to two different parameters P and alpha estimating the probabilities of the feature realization in the class of active compounds (they are equal to 0.94 and 0.86, correspondingly). The results of testing demonstrated the high ability of ETM in predicting the activity investigated.

  6. Synthesis and antimicrobial activities of new 4-thiazolidones derived from formipyridine thiosemicarbazones

    Vercoza, George Leonardo; Feitoza, Danniel Delmondes; Alves, Antonio Jose; Aquino, Thiago Mendonca de; Lima, Jose Gildo de; Araujo, Janete Magali; Cunha, Ivana Glaucia B.; Goes, Alexandre Jose da Silva

    2009-01-01

    Twelve novel 4-thiazolidinone derivatives (2a-l) have been synthesized by reacting formylpyridine thiosemicarbazones (1a-l) and anhydride maleic in toluene. Their chemical structures were confirmed by IR, 1 H and 13 C NMR. The new compounds were submitted to in vitro evaluation against pathogenic Gram-positive, Gram-negative bacteria and yeasts. The findings obtained showed that the compounds 2a, 2d, 2e and 2g were effective against some of the bacterial strains used, whereas the compounds 2d, 2e and 2i exhibited a moderate antifungal activity against the yeast strains evaluated. An initial structure activity relationship (SAR) was established. (author)

  7. Synthesis and Characterization of New Palladium(II) Thiosemicarbazone Complexes and Their Cytotoxic Activity against Various Human Tumor Cell Lines

    Hernández, Wilfredo; Paz, Juan; Carrasco, Fernando; Spodine, Evgenia; Manzur, Jorge; Sieler, Joachim; Blaurock, Steffen; Beyer, Lothar

    2013-01-01

    The palladium(II) bis-chelate complexes of the type [Pd(TSC1-5)2] (6–10), with their corresponding ligands 4-phenyl-1-(acetone)-thiosemicarbazone, HTSC1 (1), 4-phenyl-1-(2′-chloro-benzaldehyde)-thiosemicarbazone, HTSC2 (2), 4-phenyl-1-(3′-hydroxy-benzaldehyde)-thiosemicarbazone, HTSC3 (3), 4-phenyl-1-(2′-naphthaldehyde)-thiosemicarbazone, HTSC4 (4), and 4-phenyl-1-(1′-nitro-2′-naphthaldehyde)-thiosemicarbazone, HTSC5 (5), were synthesized and characterized by elemental analysis and spectroscopic techniques (IR and 1H- and 13C-NMR). The molecular structure of HTSC3, HTSC4, and [Pd(TSC1)2] (6) have been determined by single crystal X-ray crystallography. Complex 6 shows a square planar geometry with two deprotonated ligands coordinated to PdII through the azomethine nitrogen and thione sulfur atoms in a cis arrangement. The in vitro cytotoxic activity measurements indicate that the palladium(II) complexes (IC50 = 0.01–9.87 μM) exhibited higher antiproliferative activity than their free ligands (IC50 = 23.48–70.86 and >250 μM) against different types of human tumor cell lines. Among all the studied palladium(II) complexes, the [Pd(TSC3)2] (8) complex exhibited high antitumor activity on the DU145 prostate carcinoma and K562 chronic myelogenous leukemia cells, with low values of the inhibitory concentration (0.01 and 0.02 μM, resp.). PMID:24391528

  8. Synthesis, biological evaluation and molecular docking of N-phenyl thiosemicarbazones as urease inhibitors.

    Hameed, Abdul; Khan, Khalid Mohammed; Zehra, Syeda Tazeen; Ahmed, Ramasa; Shafiq, Zahid; Bakht, Syeda Mahwish; Yaqub, Muhammad; Hussain, Mazhar; de la Vega de León, Antonio; Furtmann, Norbert; Bajorath, Jürgen; Shad, Hazoor Ahmad; Tahir, Muhammad Nawaz; Iqbal, Jamshed

    2015-08-01

    Urease is an important enzyme which breaks urea into ammonia and carbon dioxide during metabolic processes. However, an elevated activity of urease causes various complications of clinical importance. The inhibition of urease activity with small molecules as inhibitors is an effective strategy for therapeutic intervention. Herein, we have synthesized a series of 19 benzofurane linked N-phenyl semithiocarbazones (3a-3s). All the compounds were screened for enzyme inhibitor activity against Jack bean urease. The synthesized N-phenyl thiosemicarbazones had varying activity levels with IC50 values between 0.077 ± 0.001 and 24.04 ± 0.14 μM compared to standard inhibitor, thiourea (IC50 = 21 ± 0.11 μM). The activities of these compounds may be due to their close resemblance of thiourea. A docking study with Jack bean urease (PDB ID: 4H9M) revealed possible binding modes of N-phenyl thiosemicarbazones. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. Generating nanoparticles containing a new 4-nitrobenzaldehyde thiosemicarbazone compound with antileishmanial activity

    Aparecida Britta, Elizandra [Programa de Pós-Graduação em Ciências Farmacêuticas, Universidade Estadual de Maringá (Brazil); Conceição da Silva, Cleuza; Forti Rubira, Adley [Departamento de Química, Universidade Estadual de Maringá (Brazil); Vataru Nakamura, Celso, E-mail: cvnakamura@uem.br [Programa de Pós-Graduação em Ciências Farmacêuticas, Universidade Estadual de Maringá (Brazil); Borsali, Redouane, E-mail: borsali@cermav.cnrs.fr [Centro de Pesquisas em Macromoléculas Vegetais, CERMAV, Grenoble (France)

    2016-12-01

    Thiosemicarbazones are an important class of compounds that have been extensively studied in recent years, mainly because of their broad profile of pharmacological activity. A new 4-nitrobenzaldehyde thiosemicarbazone compound (BZTS) that was derived from S-limonene has been demonstrated to have significant antiprotozoan activity. However, the hydrophobic characteristic of BZTS limits its administration and results in low oral bioavailability. In the present study, we proposed the synthesis of nanoparticle-based block copolymers that can encapsulate BZTS, with morphological evaluation of the nanoparticle suspensions being performed by transmission and cryo-transmission electronic microscopy. The mean particle sizes of the nanoparticle suspensions were determined by static light and dynamic light scattering (SLS/DLS), and the hydrodynamic radius (Rh) was determined using the Stokes-Einstein equation. The zeta potential (ζ) and polydispersity index (PDI) were also determined. The entrapment encapsulation efficiency of the BZTS nanoparticles was measured by ultraviolet spectrophotometry. In vitro activity of BZTS nanoparticle suspensions against intracellular amastigotes of Leishmania amazonensis and cytotoxic activity were also evaluated. The results showed the production of spherical nanoparticles with varied sizes depending on the hydrophobic portion of the amphiphilic diblock copolymers used. Significant concentration-dependent inhibitory activity against intracellular amastigotes was observed, and low cytotoxic activity was demonstrated against macrophages. - Highlights: • The spherical nanoparticles were obtained using distinct diblock copolymers. • BZTS was successfully encapsulated in the nanoparticles. • BZTS nanoparticle suspensions presented activity in Leishmania amazonensis.

  10. Generating nanoparticles containing a new 4-nitrobenzaldehyde thiosemicarbazone compound with antileishmanial activity

    Aparecida Britta, Elizandra; Conceição da Silva, Cleuza; Forti Rubira, Adley; Vataru Nakamura, Celso; Borsali, Redouane

    2016-01-01

    Thiosemicarbazones are an important class of compounds that have been extensively studied in recent years, mainly because of their broad profile of pharmacological activity. A new 4-nitrobenzaldehyde thiosemicarbazone compound (BZTS) that was derived from S-limonene has been demonstrated to have significant antiprotozoan activity. However, the hydrophobic characteristic of BZTS limits its administration and results in low oral bioavailability. In the present study, we proposed the synthesis of nanoparticle-based block copolymers that can encapsulate BZTS, with morphological evaluation of the nanoparticle suspensions being performed by transmission and cryo-transmission electronic microscopy. The mean particle sizes of the nanoparticle suspensions were determined by static light and dynamic light scattering (SLS/DLS), and the hydrodynamic radius (Rh) was determined using the Stokes-Einstein equation. The zeta potential (ζ) and polydispersity index (PDI) were also determined. The entrapment encapsulation efficiency of the BZTS nanoparticles was measured by ultraviolet spectrophotometry. In vitro activity of BZTS nanoparticle suspensions against intracellular amastigotes of Leishmania amazonensis and cytotoxic activity were also evaluated. The results showed the production of spherical nanoparticles with varied sizes depending on the hydrophobic portion of the amphiphilic diblock copolymers used. Significant concentration-dependent inhibitory activity against intracellular amastigotes was observed, and low cytotoxic activity was demonstrated against macrophages. - Highlights: • The spherical nanoparticles were obtained using distinct diblock copolymers. • BZTS was successfully encapsulated in the nanoparticles. • BZTS nanoparticle suspensions presented activity in Leishmania amazonensis.

  11. Electrochemical Studies of Monoterpenic Thiosemicarbazones as Corrosion Inhibitor for Steel in 1 M HCl

    R. Idouhli

    2018-01-01

    Full Text Available We have studied the inhibitory effect of some Monoterpenic Thiosemicarbazones on steel corrosion in 1 M HCl solution. The potentiodynamic polarization and electrochemical impedance spectroscopy were used. The Monoterpenic Thiosemicarbazones have inhibited significantly the dissolution of steel. The inhibition efficiency increased with increasing inhibitor concentration and also with the increase in temperature (293–323 K. Furthermore, the results obtained revealed that the adsorption of inhibitor on steel surface obeys Langmuir adsorption model and the thermodynamic parameters such as enthalpy and activation energy were determined. The scanning electron microscopy combined with dispersive X-ray spectroscopy examinations were used to see the shape of the surface morphology and to determine the elemental composition. Scanning electron microscope (SEM images show that the surface damage decreases when the inhibitor is added. The quantum chemical calculations using density functional theory (DFT were performed in order to provide some insights into the electronic density distribution as well as the nature of inhibitor-steel interaction.

  12. Selecting ethanol as an ideal organic solvent probe in radiation chemistry γ-radiolysis of acetone-ethanol system and acetophenone-ethanol system

    Jin Haofang; Wu Jilan; Fang Xingwang; Zhang Xujia

    1995-01-01

    Radiolysis of acetone-ethanol solution and acetophenone-ethanol solution has been studied in this work. The dependences of G values of the final γ radiolysis products such as H 2 . 2,3-butanediol and acetaldehyde on additive concentration in liquid ethanol have been obtained. There are two kinds of new final products, isopropanol and 2-methyl-2,3-butanediol are detected in irradiated acetone-ethanol solution. As for acetophenone-ethanol system, more new final products are found. In addition, experiments of pulse radiolysis upon acetophenone-ethanol solution have also been performed. The absorption spectrum with λ max at 315nm and 440nm is observed, which is assigned to ketyl radical ion C 6 H 5 (CH 3 )CO - . And the reaction mechanism of the two systems is proposed respectively with a moderate success. (author)

  13. SYNTHESIS AND ANTITUMOR ACTIVITY OF COPPER, NICKEL AND COBALT COORDINATION COMPOUNDS WITH 1-(2-HYDROXYPHENYL)ETHANONE N(4)-ALLYL-3-THIOSEMICARBAZONE

    Vasilii GRAUR; Serghei SAVCIN; Victor TSAPKOV; Aurelian GULEA

    2015-01-01

    The paper presents the synthesis of the ligand 1-(2-hydroxyphenyl)ethanone N(4)-allyl-3-thiosemicarbazone (H2L) and six coordination compounds of copper, nickel and cobalt with this ligand. The structure of thiosemicarbazone H2L was studied using 1H and 13С NMR spectroscopy. The synthesized coordination compounds were studied using elemental analysis, gravimetric analysis of water content, molar conductivity, and magnetochemistry. For H2L the antitumor activity towards human leukemia HL-60 ce...

  14. Energy decomposition analysis of the interactions in adduct ions of acetophenone and Na+, NH4+ and H+ in the gas phase

    Sugimura, Natsuhiko; Igarashi, Yoko; Aoyama, Reiko; Shibue, Toshimichi

    2017-09-01

    The physical origins of the interactions in the acetophenone cation adducts [M+Na]+, [M+NH4]+, and [M+H]+ were explored by localized molecular orbital-energy decomposition analysis and density functional theory. The analyses highlighted the differences in the interactions in the three adduct ions. Electrostatic energy was important in [M+Na]+ and there was little change in the acetophenone orbital shape. Both electrostatic and polarization energy were important in [M+NH4]+, and a considerable change in the orbital shape occurred to maximize the strength of the hydrogen bond. Polarization energy was the major attractive force in [M+H]+.

  15. Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone

    List, Nanna Holmgaard, E-mail: nhl@sdu.dk; Jensen, Hans Jørgen Aagaard; Kongsted, Jacob [Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, Odense M, Odense DK-5230 Denmark (Denmark); Beerepoot, Maarten T. P.; Gao, Bin; Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø–The Arctic University of Norway, N-9037 Tromsø (Norway); Olsen, Jógvan Magnus Haugaard [Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, Odense M, Odense DK-5230 Denmark (Denmark); Laboratory of Computational Chemistry and Biochemistry, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland)

    2015-01-21

    We present an implementation of analytical quantum mechanical molecular gradients within the polarizable embedding (PE) model to allow for efficient geometry optimizations and vibrational analysis of molecules embedded in large, geometrically frozen environments. We consider a variational ansatz for the quantum region, covering (multiconfigurational) self-consistent-field and Kohn–Sham density functional theory. As the first application of the implementation, we consider the internal vibrational Stark effect of the C=O group of acetophenone in different solvents and derive its vibrational linear Stark tuning rate using harmonic frequencies calculated from analytical gradients and computed local electric fields. Comparisons to PE calculations employing an enlarged quantum region as well as to a non-polarizable embedding scheme show that the inclusion of mutual polarization between acetophenone and water is essential in order to capture the structural modifications and the associated frequency shifts observed in water. For more apolar solvents, a proper description of dispersion and exchange–repulsion becomes increasingly important, and the quality of the optimized structures relies to a larger extent on the quality of the Lennard-Jones parameters.

  16. Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone

    List, Nanna Holmgaard; Jensen, Hans Jørgen Aagaard; Kongsted, Jacob; Beerepoot, Maarten T. P.; Gao, Bin; Ruud, Kenneth; Olsen, Jógvan Magnus Haugaard

    2015-01-01

    We present an implementation of analytical quantum mechanical molecular gradients within the polarizable embedding (PE) model to allow for efficient geometry optimizations and vibrational analysis of molecules embedded in large, geometrically frozen environments. We consider a variational ansatz for the quantum region, covering (multiconfigurational) self-consistent-field and Kohn–Sham density functional theory. As the first application of the implementation, we consider the internal vibrational Stark effect of the C=O group of acetophenone in different solvents and derive its vibrational linear Stark tuning rate using harmonic frequencies calculated from analytical gradients and computed local electric fields. Comparisons to PE calculations employing an enlarged quantum region as well as to a non-polarizable embedding scheme show that the inclusion of mutual polarization between acetophenone and water is essential in order to capture the structural modifications and the associated frequency shifts observed in water. For more apolar solvents, a proper description of dispersion and exchange–repulsion becomes increasingly important, and the quality of the optimized structures relies to a larger extent on the quality of the Lennard-Jones parameters

  17. Triplet state photochemistry and the three-state crossing of acetophenone within time-dependent density-functional theory

    Huix-Rotllant, Miquel, E-mail: miquel.huix@gmail.com; Ferré, Nicolas, E-mail: nicolas.ferre@univ-amu.fr [Institut de Chimie Radicalaire (UMR-7273), Aix-Marseille Université, CNRS, 13397 Marseille Cedex 20 (France)

    2014-04-07

    Even though time-dependent density-functional theory (TDDFT) works generally well for describing excited states energies and properties in the Franck-Condon region, it can dramatically fail in predicting photochemistry, notably when electronic state crossings occur. Here, we assess the ability of TDDFT to describe the photochemistry of an important class of triplet sensitizers, namely, aromatic ketones. We take acetophenone as a test molecule, for which accurate ab initio results exist in the literature. Triplet acetophenone is generated thanks to an exotic three-state crossing involving one singlet and two triplets states (i.e., a simultaneous intersystem crossing and triplet conical intersection), thus being a stringent test for approximate TDDFT. We show that most exchange-correlation functionals can only give a semi-qualitative picture of the overall photochemistry, in which the three-state crossing is rather represented as a triplet conical intersection separated from the intersystem crossing. The best result overall is given by the double hybrid functional mPW2PLYP, which is even able to reproduce quantitatively the three-state crossing region. We rationalize this results by noting that double hybrid functionals include a larger portion of double excitation character to the excited states.

  18. Solvent-free Hydrodeoxygenation of Bio-oil Model Compounds Cyclopentanone and Acetophenone over Flame-made Bimetallic Pt-Pd/ZrO2 Catalysts

    Jiang, Yijiao; Büchel, Robert; Huang, Jun; Krumeich, Frank; Pratsinis, Sotiris E.; Baiker, Alfons

    2013-01-01

    Bimetallic Pt-Pd/ZrO2 catalysts with different Pt/Pd atomic ratio and homogeneous dispersion of the metal nanoparticles were prepared in a single step by flame-spray pyrolysis. The catalysts show high activity and tuneable product selectivity for the solvent-free hydrodeoxygenation of the bio-oil model compounds cyclopentanone and acetophenone. PMID:22674738

  19. Synthesis, physicochemical and optical properties of bis-thiosemicarbazone functionalized graphene oxide

    Kumar, Santosh; Wani, Mohmmad Y.; Arranja, Claudia T.; Castro, Ricardo A. E.; Paixão, José A.; Sobral, Abilio J. F. N.

    2018-01-01

    Fluorescent materials are important for low-cost opto-electronic and biomedical sensor devices. In this study we present the synthesis and characterization of graphene modified with bis-thiosemicarbazone (BTS). This new material was characterized using Fourier transform infrared spectroscopy (FT-IR), Ultraviolet-visible (UV-Vis) and Raman spectroscopy techniques. Further evaluation by X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and atomic-force microscopy (AFM) allowed us to fully characterize the morphology of the fabricated material. The average height of the BTSGO sheet is around 10 nm. Optical properties of BTSGO evaluated by photoluminescence (PL) spectroscopy showed red shift at different excitation wavelength compared to graphene oxide or bisthiosemicarbazide alone. These results strongly suggest that BTSGO material could find potential applications in graphene based optoelectronic devices.

  20. Ruthenium (II) complexes of thiosemicarbazone: Synthesis, biosensor applications and evaluation as antimicrobial agents

    Yildirim, Hatice [Dokuz Eylul University, The Graduate School of Natural and Applied Sciences, Department of Chemistry, 35160 Buca, Izmir (Turkey); Guler, Emine [Ege University, Faculty of Science, Department of Biochemistry, 35100 Bornova, Izmir (Turkey); Yavuz, Murat, E-mail: myavuz@dicle.edu.tr [Ege University, Faculty of Science, Department of Biochemistry, 35100 Bornova, Izmir (Turkey); Dicle University, Faculty of Science, Department of Chemistry, 21280 Diyarbakir (Turkey); Ozturk, Nurdan; Kose Yaman, Pelin [Dokuz Eylul University, The Graduate School of Natural and Applied Sciences, Department of Chemistry, 35160 Buca, Izmir (Turkey); Subasi, Elif; Sahin, Elif [Dokuz Eylul University, Faculty of Science, Department of Chemistry, 35160 Buca, Izmir (Turkey); Timur, Suna [Ege University, Faculty of Science, Department of Biochemistry, 35100 Bornova, Izmir (Turkey); Ege University, Institute on Drug Abuse, Toxicology and Pharmaceutical Science (BATI), 35100 Bornova, Izmir (Turkey)

    2014-11-01

    A conformationally rigid half-sandwich organoruthenium (II) complex [(η{sup 6}-p-cymene)RuClTSC{sup N–S}]Cl, (1) and carbonyl complex [Ru(CO)Cl(PPh{sub 3}){sub 2}TSC{sup N–S}] (2) have been synthesized from the reaction of [{(η"6-p-cymene)RuCl}{sub 2}(μ-Cl){sub 2}] and [Ru(H)(Cl)(CO)(PPh{sub 3}){sub 3}] with thiophene-2-carboxaldehyde thiosemicarbazon (TSC) respectively and both novel ruthenium (II) complexes have been characterized by elemental analysis, FT-IR and NMR spectroscopy. The peripheral TSC in the complexes acts as an electrochemical coupling unit providing the ability to carry out electrochemical deposition (ED) and to form an electro-deposited film on a graphite electrode surface. The biosensing applicability of complexes 1 and 2 was investigated by using glucose oxidase (GOx) as a model enzyme. Electrochemical measurements at − 0.9 V versus Ag/AgCl electrode by following the ED Ru(II) reduction/oxidation due to from the enzyme activity, in the presence of glucose substrate. The designed biosensor showed a very good linearity for 0.01–0.5 mM glucose. The in vitro antimicrobial activities of complexes 1 and 2 were also investigated against nine bacterial strains and one fungus by the disc diffusion test method. No activity was observed against the Gram-negative strains and fungus, whereas complex 1 showed moderate antibacterial activities against Gram-positive bacterial strains. - Highlights: • Novel Ru (II) thiosemicarbazone complexes were synthesized and characterized. • Electrochemical depositions were performed. • Rigid half-sandwich Ru (II) complex showed enhanced antibacterial activity.

  1. Ruthenium (II) complexes of thiosemicarbazone: Synthesis, biosensor applications and evaluation as antimicrobial agents

    Yildirim, Hatice; Guler, Emine; Yavuz, Murat; Ozturk, Nurdan; Kose Yaman, Pelin; Subasi, Elif; Sahin, Elif; Timur, Suna

    2014-01-01

    A conformationally rigid half-sandwich organoruthenium (II) complex [(η 6 -p-cymene)RuClTSC N–S ]Cl, (1) and carbonyl complex [Ru(CO)Cl(PPh 3 ) 2 TSC N–S ] (2) have been synthesized from the reaction of [{(η 6 -p-cymene)RuCl} 2 (μ-Cl) 2 ] and [Ru(H)(Cl)(CO)(PPh 3 ) 3 ] with thiophene-2-carboxaldehyde thiosemicarbazon (TSC) respectively and both novel ruthenium (II) complexes have been characterized by elemental analysis, FT-IR and NMR spectroscopy. The peripheral TSC in the complexes acts as an electrochemical coupling unit providing the ability to carry out electrochemical deposition (ED) and to form an electro-deposited film on a graphite electrode surface. The biosensing applicability of complexes 1 and 2 was investigated by using glucose oxidase (GOx) as a model enzyme. Electrochemical measurements at − 0.9 V versus Ag/AgCl electrode by following the ED Ru(II) reduction/oxidation due to from the enzyme activity, in the presence of glucose substrate. The designed biosensor showed a very good linearity for 0.01–0.5 mM glucose. The in vitro antimicrobial activities of complexes 1 and 2 were also investigated against nine bacterial strains and one fungus by the disc diffusion test method. No activity was observed against the Gram-negative strains and fungus, whereas complex 1 showed moderate antibacterial activities against Gram-positive bacterial strains. - Highlights: • Novel Ru (II) thiosemicarbazone complexes were synthesized and characterized. • Electrochemical depositions were performed. • Rigid half-sandwich Ru (II) complex showed enhanced antibacterial activity

  2. Radioactive Indium(114mIn) complexes derived thiosemicarbazones for development of glioma radionuclide therapy tools

    Ribeiro, Thais S.; Menezes, Maria Ângela B.C.; Belo, Luiz Cláudio M.; Santos, Raquel G. dos; Franco, Lucas L.; Oliveira, Alexandre A.; Beraldo, Heloisa O.

    2017-01-01

    Chemotherapy is widely used as the main course of treatment for various types of cancer. However, the side effects derived from the prolonged use of highly cytotoxic drugs in association with chemotherapy induced resistance are important challenges for effective therapy. In this context, radionuclide therapy (RNT) can be an alternative way to decrease the toxicity and improve the specificity of anti tumoral drugs. Our group has recently demonstrated that Indium (III) coordination to N(4)-Tolyl-2-acetylpyridine-derived thiosemicarbazones improves cytotoxic effects on leukemia cell lines. Once 114m In is a prolific Auger electron emitter, in this study In (III) complexes and their radioactive analogs were produced by neutron activation and their potential for RNT was further studied. Native and radioactive complexes were tested in different concentrations in U87 and T98 glioblastoma multiform (GBM) cell lines, as well as in MRC5 fibroblast cell line. All drugs presented a dose dependent cytotoxicity against cancer cells at submicromolar concentrations. The treatment with 1 μM of the radioactive analogs containing 114m In proved to be at least 1.5 times more potent than non-radioactive complexes in GBM cell lines. Due to the innate resistance of glioblastomas to chemotherapy and radiotherapy, the potentiation factor showed by the test radioactive complexes may be interesting in the course of treatment against these tumors. Therefore, the presented data suggests a synergistic effect of the radionuclide therapy conducted in this study, which might be due to the combinations of pharmacological and radiotherapeutic activities of the 114m In - thiosemicarbazone compounds. (author)

  3. Synthesis of biological active thiosemicarbazone and characterization of the interaction with human serum albumin

    Yu, Wangshu; Shi, Lei; Hui, Guangquan [College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China); Cui, Fengling, E-mail: fenglingcui@hotmail.com [College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China)

    2013-02-15

    The synthesis of a new biological active reagent, 2-((1,4-dihydroxy)-9,10-anthraquinone) aldehyde thiosemicarbazone (DHAQTS), was designed. The interaction between DHAQTS and HSA was studied by fluorescence spectroscopy in combination with molecular modeling under simulation of physiological conditions. According to the results of fluorescence measurements, the quenching mechanism was suggested to be static. The thermodynamic parameters are calculated by van't Hoff equation, which demonstrated that hydrophobic interactions are the predominant intermolecular forces stabilizing the complex. The number of binding sites (n) was calculated. Through the site marker competitive experiment, DHAQTS was confirmed to be located in site I of HSA. The binding distance r=2.83 nm between the donor HSA and acceptor DHAQTS was obtained according to Foerster's non-radiative energy transfer theory. The three-dimensional fluorescence spectral results showed the conformation and microenvironment of HSA changed in the presence of DHAQTS. The effects of common ions on the binding of DHAQTS to HSA were also evaluated. The experimental results were in agreement with the results obtained via a molecular docking study. - Highlights: Black-Right-Pointing-Pointer 2-((1,4-dihydroxy)-9,10-anthraquinone)aldehyde thiosemicarbazone (DHAQTS) was synthesized. Black-Right-Pointing-Pointer DHAQTS can quench the fluorescence of human serum albumin (HSA) by static quenching mechanism. Black-Right-Pointing-Pointer Hydrophobic interactions were the predominant intermolecular forces. Black-Right-Pointing-Pointer The competitive experiment was carried out to identify the DHAQTS binding site on HSA. Black-Right-Pointing-Pointer Three-dimensional spectra confirmed DHAQTS caused the conformational change of HSA.

  4. Synthesis of biological active thiosemicarbazone and characterization of the interaction with human serum albumin

    Yu, Wangshu; Shi, Lei; Hui, Guangquan; Cui, Fengling

    2013-01-01

    The synthesis of a new biological active reagent, 2-((1,4-dihydroxy)-9,10-anthraquinone) aldehyde thiosemicarbazone (DHAQTS), was designed. The interaction between DHAQTS and HSA was studied by fluorescence spectroscopy in combination with molecular modeling under simulation of physiological conditions. According to the results of fluorescence measurements, the quenching mechanism was suggested to be static. The thermodynamic parameters are calculated by van't Hoff equation, which demonstrated that hydrophobic interactions are the predominant intermolecular forces stabilizing the complex. The number of binding sites (n) was calculated. Through the site marker competitive experiment, DHAQTS was confirmed to be located in site I of HSA. The binding distance r=2.83 nm between the donor HSA and acceptor DHAQTS was obtained according to Förster's non-radiative energy transfer theory. The three-dimensional fluorescence spectral results showed the conformation and microenvironment of HSA changed in the presence of DHAQTS. The effects of common ions on the binding of DHAQTS to HSA were also evaluated. The experimental results were in agreement with the results obtained via a molecular docking study. - Highlights: ► 2-((1,4-dihydroxy)-9,10-anthraquinone)aldehyde thiosemicarbazone (DHAQTS) was synthesized. ► DHAQTS can quench the fluorescence of human serum albumin (HSA) by static quenching mechanism. ► Hydrophobic interactions were the predominant intermolecular forces. ► The competitive experiment was carried out to identify the DHAQTS binding site on HSA. ► Three-dimensional spectra confirmed DHAQTS caused the conformational change of HSA.

  5. Thiosemicarbazones: preparation methods, synthetic applications and biological importance; Tiossemicarbazonas: metodos de obtencao, aplicacoes sinteticas e importancia biologica

    Tenorio, Romulo P.; Goes, Alexandre J.S. [Universidade Federal de Pernambuco, Recife, PE (Brazil). Dept. de Antibioticos]. E-mail: ajsg@ufpe.br; Lima, Jose G. de; Faria, Antonio R. de; Alves, Antonio J.; Aquino, Thiago M. de [Universidade Federal de Pernambuco, Recife, PE (Brazil). Dept. de Ciencias Farmaceuticas

    2005-11-15

    Thiosemicarbazones are a class of compounds known by their chemical and biological properties, such as antitumor, antibacterial, antiviral and antiprotozoal activity. Their ability to form chelates with metals has great importance in their biological activities. Their synthesis is very simple, versatile and clean, usually giving high yields. They are largely employed as intermediates, in the synthesis of others compounds. This article is a survey of some of these characteristics showing their great importance to organic and medicinal chemistry. (author)

  6. Copper(II) Thiosemicarbazone Complexes and Their Proligands upon UVA Irradiation: An EPR and Spectrophotometric Steady-State Study.

    Hricovíni, Michal; Mazúr, Milan; Sîrbu, Angela; Palamarciuc, Oleg; Arion, Vladimir B; Brezová, Vlasta

    2018-03-21

    X- and Q-band electron paramagnetic resonance (EPR) spectroscopy was used to characterize polycrystalline Cu(II) complexes that contained sodium 5-sulfonate salicylaldehyde thiosemicarbazones possessing a hydrogen, methyl, ethyl, or phenyl substituent at the terminal nitrogen. The ability of thiosemicarbazone proligands to generate superoxide radical anions and hydroxyl radicals upon their exposure to UVA irradiation in aerated aqueous solutions was evidenced by the EPR spin trapping technique. The UVA irradiation of proligands in neutral or alkaline solutions and dimethylsulfoxide (DMSO) caused a significant decrease in the absorption bands of aldimine and phenolic chromophores. Mixing of proligand solutions with the equimolar amount of copper(II) ions resulted in the formation of 1:1 Cu(II)-to-ligand complex, with the EPR and UV-Vis spectra fully compatible with those obtained for the dissolved Cu(II) thiosemicarbazone complexes. The formation of the complexes fully inhibited the photoinduced generation of reactive oxygen species, and only subtle changes were found in the electronic absorption spectra of the complexes in aqueous and DMSO solutions upon UVA steady-state irradiation. The dark redox activity of copper(II) complexes and proligand/Cu(II) aqueous solutions towards hydrogen peroxide which resulted in the generation of hydroxyl radicals, was confirmed by spin trapping experiments.

  7. Kinetic studies on the oxidation of oxyhemoglobin by biologically active iron thiosemicarbazone complexes: relevance to iron-chelator-induced methemoglobinemia.

    Basha, Maram T; Rodríguez, Carlos; Richardson, Des R; Martínez, Manuel; Bernhardt, Paul V

    2014-03-01

    The oxidation of oxyhemoglobin to methemoglobin has been found to be facilitated by low molecular weight iron(III) thiosemicarbazone complexes. This deleterious reaction, which produces hemoglobin protein units unable to bind dioxygen and occurs during the administration of iron chelators such as the well-known 3-aminopyridine-2-pyridinecarbaldehyde thiosemicarbazone (3-AP; Triapine), has been observed in the reaction with Fe(III) complexes of some members of the 3-AP structurally-related thiosemicarbazone ligands derived from di-2-pyridyl ketone (HDpxxT series). We have studied the kinetics of this oxidation reaction in vitro using human hemoglobin and found that the reaction proceeds with two distinct time-resolved steps. These have been associated with sequential oxidation of the two different oxyheme cofactors in the α and β protein chains. Unexpected steric and hydrogen-bonding effects on the Fe(III) complexes appear to be the responsible for the observed differences in the reaction rate across the series of HDpxxT ligand complexes used in this study.

  8. Synthesis, structural, antibacterial and spectral studies of Co (II) complexes with salicylaldehyde and p-chloro-benzaldehyde 4-phenyl thiosemicarbazone

    Nur Nadia Dzulkifli; Yang Farina; Ibrahim Baba; Nazlina Ibrahim

    2012-01-01

    The Co(II) complexes derived from salicylaldehyde 4-phenyl thiosemicarbazone; SaOHtsc, p-chlorobenzaldehyde 4-phenyl thiosemicarbazone; ph-HClbtsc is reported and characterized based on elemental analysis, IR, magnetic susceptibility measurement, 1 H and 13 C NMR spectra. The Co(II) complexes have the molecular formula CoL 2 where the ligand corresponding to SaOHtsc and ph-HClbtsc. The elemental analysis for the ligands and complexes were in a good agreement with the theoretical values. The ligands coordinate to metal ions in different ways which is through mono negative bidentate or di negative tridentate. The magnetic susceptibility measurements showed that the CoL 2 complexes with ligand SaOHtsc are diamagnetic thus making this complexes suitable for NMR studies. The signals at the 10.04 ppm were assigned to N 2 H in the 1 H-NMR spectra of the free ligands was absent in the spectra of the complexes due to the deprotonation of the N 2 H and coordination to the metal centres. The absence of the band in IR spectrum which is assigned to v(N 2 -H) in the spectra of CoL 2 complexes is due to the deprotonation of the ligands upon complexation through azomethine nitrogen and thionic sulphur atom to metal ion. The thiosemicarbazones and its Co(II) complexes showed moderate inhibitory against bacteria Bacillus Subtilis, Staphylococcus Epidermis, Escherichia Coli and Proteus Mirabilis in 10 μg/ disc. (author)

  9. Synthesis, structural characterization, and pro-apoptotic activity of 1-indanone thiosemicarbazone platinum(II) and palladium(II) complexes: potential as antileukemic agents.

    Gómez, Natalia; Santos, Diego; Vázquez, Ramiro; Suescun, Leopoldo; Mombrú, Alvaro; Vermeulen, Monica; Finkielsztein, Liliana; Shayo, Carina; Moglioni, Albertina; Gambino, Dinorah; Davio, Carlos

    2011-08-01

    In the search for alternative chemotherapeutic strategies against leukemia, various 1-indanone thiosemicarbazones, as well as eight novel platinum(II) and palladium(II) complexes, with the formula [MCl₂(HL)] and [M(HL)(L)]Cl, derived from two 1-indanone thiosemicarbazones were synthesized and tested for antiproliferative activity against the human leukemia U937 cell line. The crystal structure of [Pt(HL1)(L1)]Cl·2MeOH, where L1=1-indanone thiosemicarbazone, was solved by X-ray diffraction. Free thiosemicarbazone ligands showed no antiproliferative effect, but the corresponding platinum(II) and palladium(II) complexes inhibited cell proliferation and induced apoptosis. Platinum(II) complexes also displayed selective apoptotic activity in U937 cells but not in peripheral blood monocytes or the human hepatocellular carcinoma HepG2 cell line used to screen for potential hepatotoxicity. Present findings show that, in U937 cells, 1-indanone thiosemicarbazones coordinated to palladium(II) were more cytotoxic than those complexed with platinum(II), although the latter were found to be more selective for leukemic cells suggesting that they are promising compounds with potential therapeutic application against hematological malignancies. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Substitutional analysis

    Rutherford, Daniel Edwin

    2013-01-01

    Classic monograph, suitable for advanced undergraduates and graduate students. Topics include calculus of permutations and tableaux, semi-normal representation, orthogonal and natural representations, group characters, and substitutional equations. 1968 edition.

  11. (Pressure + volume + temperature) properties for binary oligomeric solutions of poly(ethylene glycol mono-4-octylphenyl ether) with 1-octanol or acetophenone at pressures up to 50 MPa

    Lee, M.-J.; Ku, T.-J.; Lin Homu

    2009-01-01

    Densities were measured with a high-pressure densitometer for two binary oligomeric systems of poly(ethylene glycol mono-4-octylphenyl ether) (PEGOPE) with 1-octanol or acetophenone at temperatures from 298.15 K to 348.15 K and pressures up to 50 MPa. While the excess volumes are negative in (acetophenone + PEGOPE) over the entire composition range, those are found to change from positive to negative with increasing mole fraction of the solvent in (1-octanol + PEGOPE). The pressure-effect on the liquid densities can be represented accurately by the Tait equation. Moreover, an empirical equation with two characteristic parameters correlates well the PVT data over the entire experimental conditions for each binary system. The experimental specific volumes were also correlated with the Flory-Orwoll-Vrij (FOV) and the Schotte equations of state to within the experimental uncertainty.

  12. Identification of semicarbazones, thiosemicarbazones and triazine nitriles as inhibitors of Leishmania mexicana cysteine protease CPB.

    Jörg Schröder

    Full Text Available Cysteine proteases of the papain superfamily are present in nearly all eukaryotes. They play pivotal roles in the biology of parasites and inhibition of cysteine proteases is emerging as an important strategy to combat parasitic diseases such as sleeping sickness, Chagas' disease and leishmaniasis. Homology modeling of the mature Leishmania mexicana cysteine protease CPB2.8 suggested that it differs significantly from bovine cathepsin B and thus could be a good drug target. High throughput screening of a compound library against this enzyme and bovine cathepsin B in a counter assay identified four novel inhibitors, containing the warhead-types semicarbazone, thiosemicarbazone and triazine nitrile, that can be used as leads for antiparasite drug design. Covalent docking experiments confirmed the SARs of these lead compounds in an effort to understand the structural elements required for specific inhibition of CPB2.8. This study has provided starting points for the design of selective and highly potent inhibitors of L. mexicana cysteine protease CPB that may also have useful efficacy against other important cysteine proteases.

  13. Structural and biological evaluation of some metal complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone

    Yousef, T. A.; Abu El-Reash, G. M.; Al-Jahdali, M.; El-Rakhawy, El-Bastawesy R.

    2013-12-01

    The synthesis and characterization of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and U(VI)O2 complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone (H2PVT) are reported. Theoretical calculations have been performed to obtain IR spectra of ligand and its complexes using AM1, Zindo/1, MM+ and PM3, methods. The Schiff base and its metal complexes have been screened for antibacterial Pseudomonas aeruginosa, Escherichia coli, Bacillus subtilis and Staphylococcus saprophyticus. H2VPT shows no apparent digestion effect on the egg albumin while Mn(II), Hg(II) and Cu(II) complexes exhibited a considerable digestion effect following the order Cu(II) > Mn(II) > Hg(II). Moreover, Ni(II) and Co(II) complexes revealed strong digestion effect. Fe(II), Mn(II), Cu(II), Zn(II) and Ni(II) acted as metal co- SOD enzyme factors, which are located in different compartments of the cell.

  14. 2-Acetylpyridine N4-Phenyl- Thiosemicarbazone as a new tool for tumour diagnosis

    Soares, Marcella Araugio; Pesquero, Jorge Luiz

    2009-01-01

    The aim of this work was to determine in vivo biodistribution of radiolabelled 2-acetylpyridine N4 phenyl thiosemicarbazone (Ph) and to evaluate its applicability for tumour diagnosis. Ph was labelled with 125 I using lactoperoxidase method and radiochemical analysis was performed by chromatography. 125 I-Ph production was successful with 86 ± 9.2% of radiochemical purity and high specific activity (17.6 TBq /mmol). 125 I-Ph was used for biodistribution and pharmacokinetics studies on Swiss mice bearing Ehrlich solid tumour. 125 I-Ph presented a rapid blood clearance (T 1/2 = 97.2 min.) and the kidneys were the main excretion pathway (CL0.01 mL/min). 125 I-Ph uptake was significant in tumour (2.5%ID/g) and tumour-to-normal tissue uptake was more than 20-fold higher depending on the organ. The uptake by the organs like heart, lungs, stomach and liver followed the blood perfusion. Our results suggest that 125 I-Ph possess indispensable characteristics for an efficient radiopharmaceutical for tumour diagnosis. The next step will be to evaluate the quality of tumour SPECT images provided by 131 I-Ph. (author)

  15. Synthesis and In Vitro Evaluation of New Thiosemicarbazone Derivatives as Potential Antimicrobial Agents

    Zafer Asım Kaplancıklı

    2016-01-01

    Full Text Available In an effort to develop potent antimicrobial agents, new thiosemicarbazone derivatives were synthesized via the reaction of 4-[4-(trifluoromethylphenyl]thiosemicarbazide with aromatic aldehydes. The compounds were evaluated for their inhibitory effects on pathogenic bacteria and yeasts using the CLSI broth microdilution method. Microplate Alamar Blue Assay was also carried out to determine the antimycobacterial activities of the compounds against Mycobacterium tuberculosis H37Rv. Among these derivatives, compounds 5 and 11 were more effective against Enterococcus faecalis (ATCC 29212 than chloramphenicol, whereas compounds 1, 2, and 12 and chloramphenicol showed the same level of antibacterial activity against E. faecalis. Moreover, compound 2 and chloramphenicol exhibited the same level of antibacterial activity against Staphylococcus aureus. On the other hand, the most potent anticandidal derivatives were found as compounds 2 and 5. These derivatives and ketoconazole exhibited the same level of antifungal activity against Candida glabrata. According to the Microplate Alamar Blue Assay, the tested compounds showed weak to moderate antitubercular activity.

  16. Copper complexes containing thiosemicarbazones derived from 6-nitropiperonal: Antimicrobial and biophysical properties

    Beckford, Floyd A.; Webb, Kelsey R.

    2017-08-01

    A series of four thiosemicarbazones from 6-nitropiperonal along with the corresponding copper complexes were synthesized. The biophysical characteristics of the complexes were investigated by the binding to DNA and human serum albumin. The binding to DNA is moderate; the binding constants run from (0.49-7.50) × 104 M- 1. In relation to HSA, the complexes interact strongly with binding constants on the order of 105 M- 1. The complexes also display antioxidant behavior as determined by the ability to scavenge diphenylpicrylhydrazyl (dpph) and nitric oxide radicals. The antimicrobial profiles of the compounds, tested against a panel of microbes including five of the ESKAPE pathogens (Staphylococcus aureus, MRSA, Escherichia coli, Klebsiella pneumoniae, MDR, Acinetobacter baumannii, Pseudomonas aeruginosa) and two yeasts (Candida albicans and Cryptococcus neoformans var. grubii), are also described. The compounds contain a core moiety that is similar to oxolinic acid, a quinolone antibiotic that targets DNA gyrase and topoisomerase (IV). The binding interaction between the complexes and these important antibacterial targets were studied by computational methods, chiefly docking studies. The calculated dissociation constants for the interaction with DNA gyrase B (from Staphylococcus aureus) range from 4.32 to 24.65 μM; the binding was much stronger to topoisomerase IV, with dissociation constants ranging from 0.37 to 1.27 μM.

  17. β-Cyclodextrin hydrogels for the ocular release of antibacterial thiosemicarbazones.

    Glisoni, Romina J; García-Fernández, María J; Pino, Marylú; Gutkind, Gabriel; Moglioni, Albertina G; Alvarez-Lorenzo, Carmen; Concheiro, Angel; Sosnik, Alejandro

    2013-04-02

    Two types of hydrophilic networks with conjugated beta-cyclodextrin (β-CD) were developed with the aim of engineering useful platforms for the localized release of an antimicrobial 5,6-dimethoxy-1-indanone N4-allyl thiosemicarbazone (TSC) in the eye and its potential application in ophthalmic diseases. Poly(2-hydroxyethyl methacrylate) soft contact lenses (SCLs) displaying β-CD, namely pHEMA-co-β-CD, and super-hydrophilic hydrogels (SHHs) of directly cross-linked hydroxypropyl-β-CD were synthesized and characterized regarding their structure (ATR/FT-IR), drug loading capacity, swelling and in vitro release in artificial lacrimal fluid. Incorporation of TSC to the networks was carried out both during polymerization (DP method) and after synthesis (PP method). The first method led to similar drug loads in all the hydrogels, with minor drug loss during the washing steps to remove unreacted monomers, while the second method evidenced the influence of structural parameters on the loading efficiency (proportion of CD units, mesh size, swelling degree). Both systems provided a controlled TSC release for at least two weeks, TSC concentrations (up to 4000μg/g dry hydrogel) being within an optimal therapeutic window for the antimicrobial ocular treatment. Microbiological tests against P. aeruginosa and S. aureus confirmed the ability of TSC-loaded pHEMA-co-β-CD network to inhibit bacterial growth. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. 2-Acetylpyridine N4-Phenyl- Thiosemicarbazone as a new tool for tumour diagnosis

    Soares, Marcella Araugio; Pesquero, Jorge Luiz [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisiologia e Biofisica], e-mail: marcellaaraugio@yahoo.com.br; Costa, Pryscila R. da; Mendes, Isolda M.C.; Beraldo, Heloisa; Santos, Raquel Gouvea dos [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)], e-mail: santosr@cdtn.br

    2009-07-01

    The aim of this work was to determine in vivo biodistribution of radiolabelled 2-acetylpyridine N4 phenyl thiosemicarbazone (Ph) and to evaluate its applicability for tumour diagnosis. Ph was labelled with {sup 125}I using lactoperoxidase method and radiochemical analysis was performed by chromatography. {sup 125}I-Ph production was successful with 86 {+-} 9.2% of radiochemical purity and high specific activity (17.6 TBq /mmol). {sup 125}I-Ph was used for biodistribution and pharmacokinetics studies on Swiss mice bearing Ehrlich solid tumour. {sup 125}I-Ph presented a rapid blood clearance (T{sub 1/2}= 97.2 min.) and the kidneys were the main excretion pathway (CL0.01 mL/min). {sup 125}I-Ph uptake was significant in tumour (2.5%ID/g) and tumour-to-normal tissue uptake was more than 20-fold higher depending on the organ. The uptake by the organs like heart, lungs, stomach and liver followed the blood perfusion. Our results suggest that {sup 125}I-Ph possess indispensable characteristics for an efficient radiopharmaceutical for tumour diagnosis. The next step will be to evaluate the quality of tumour SPECT images provided by {sup 131}I-Ph. (author)

  19. Species dependence of [64Cu]Cu-Bis(thiosemicarbazone) radiopharmaceutical binding to serum albumins

    Basken, Nathan E.; Mathias, Carla J.; Lipka, Alexander E.; Green, Mark A.

    2008-01-01

    Introduction: Interactions of three copper(II) bis(thiosemicarbazone) positron emission tomography radiopharmaceuticals with human serum albumin, and the serum albumins of four additional mammalian species, were evaluated. Methods: 64 Cu-labeled diacetyl bis(N 4 -methylthiosemicarbazonato)copper(II) (Cu-ATSM), pyruvaldehyde bis(N 4 -methylthiosemicarbazonato)copper(II) (Cu-PTSM) and ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) were synthesized and their binding to human, canine, rat, baboon and porcine serum albumins quantified by ultrafiltration. Protein binding was also measured for each tracer in human, porcine, rat and mouse serum. Results: The interaction of these neutral, lipophilic copper chelates with serum albumin is highly compound- and species-dependent. Cu-PTSM and Cu-ATSM exhibit particularly high affinity for human serum albumin (HSA), while the albumin binding of Cu-ETS is relatively insensitive to species. At HSA concentrations of 40 mg/ml, '% free' (non-albumin-bound) levels of radiopharmaceutical were 4.0±0.1%, 5.3±0.2% and 38.6±0.8% for Cu-PTSM, Cu-ATSM and Cu-ETS, respectively. Conclusions: Species-dependent variations in radiopharmaceutical binding to serum albumin may need to be considered when using animal models to predict the distribution and kinetics of these compounds in humans

  20. Synthesis of isatin thiosemicarbazones derivatives: in vitro anti-cancer, DNA binding and cleavage activities.

    Ali, Amna Qasem; Teoh, Siang Guan; Salhin, Abdussalam; Eltayeb, Naser Eltaher; Khadeer Ahamed, Mohamed B; Abdul Majid, A M S

    2014-05-05

    New derivatives of thiosemicarbazone Schiff base with isatin moiety were synthesized L1-L6. The structures of these compounds were characterized based on the spectroscopic techniques. Compound L6 was further characterized by XRD single crystal. The interaction of these compounds with calf thymus (CT-DNA) exhibited high intrinsic binding constant (k(b)=5.03-33.00×10(5) M(-1)) for L1-L3 and L5 and (6.14-9.47×10(4) M(-1)) for L4 and L6 which reflect intercalative activity of these compounds toward CT-DNA. This result was also confirmed by the viscosity data. The electrophoresis studies reveal the higher cleavage activity of L1-L3 than L4-L6. The in vitro anti-proliferative activity of these compounds against human colon cancer cell line (HCT 116) revealed that the synthesized compounds (L3, L6 and L2) exhibited good anticancer potency. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Benzaldehyde thiosemicarbazone derived from limonene complexed with copper induced mitochondrial dysfunction in Leishmania amazonensis.

    Elizandra Aparecida Britta

    Full Text Available BACKGROUND: Leishmaniasis is a major health problem that affects more than 12 million people. Treatment presents several problems, including high toxicity and many adverse effects, leading to the discontinuation of treatment and emergence of resistant strains. METHODOLOGY/PRINCIPAL FINDINGS: We evaluated the in vitro antileishmanial activity of benzaldehyde thiosemicarbazone derived from limonene complexed with copper, termed BenzCo, against Leishmania amazonensis. BenzCo inhibited the growth of the promastigote and axenic amastigote forms, with IC(50 concentrations of 3.8 and 9.5 µM, respectively, with 72 h of incubation. Intracellular amastigotes were inhibited by the compound, with an IC(50 of 10.7 µM. BenzCo altered the shape, size, and ultrastructure of the parasites. Mitochondrial membrane depolarization was observed in protozoa treated with BenzCo but caused no alterations in the plasma membrane. Additionally, BenzCo induced lipoperoxidation and the production of mitochondrial superoxide anion radicals in promastigotes and axenic amastigotes of Leishmania amazonensis. CONCLUSION/SIGNIFICANCE: Our studies indicated that the antileishmania activity of BenzCo might be associated with mitochondrial dysfunction and oxidative damage, leading to parasite death.

  2. Species dependence of [{sup 64}Cu]Cu-Bis(thiosemicarbazone) radiopharmaceutical binding to serum albumins

    Basken, Nathan E. [Division of Nuclear Pharmacy, Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette, IN 47907 (United States)], E-mail: nbasken@purdue.edu; Mathias, Carla J. [Division of Nuclear Pharmacy, Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette, IN 47907 (United States); Lipka, Alexander E. [Department of Statistics, Purdue University, West Lafayette, IN 47907 (United States); Green, Mark A. [Division of Nuclear Pharmacy, Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette, IN 47907 (United States)], E-mail: magreen@purdue.edu

    2008-04-15

    Introduction: Interactions of three copper(II) bis(thiosemicarbazone) positron emission tomography radiopharmaceuticals with human serum albumin, and the serum albumins of four additional mammalian species, were evaluated. Methods: {sup 64}Cu-labeled diacetyl bis(N{sup 4}-methylthiosemicarbazonato)copper(II) (Cu-ATSM), pyruvaldehyde bis(N{sup 4}-methylthiosemicarbazonato)copper(II) (Cu-PTSM) and ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) were synthesized and their binding to human, canine, rat, baboon and porcine serum albumins quantified by ultrafiltration. Protein binding was also measured for each tracer in human, porcine, rat and mouse serum. Results: The interaction of these neutral, lipophilic copper chelates with serum albumin is highly compound- and species-dependent. Cu-PTSM and Cu-ATSM exhibit particularly high affinity for human serum albumin (HSA), while the albumin binding of Cu-ETS is relatively insensitive to species. At HSA concentrations of 40 mg/ml, '% free' (non-albumin-bound) levels of radiopharmaceutical were 4.0{+-}0.1%, 5.3{+-}0.2% and 38.6{+-}0.8% for Cu-PTSM, Cu-ATSM and Cu-ETS, respectively. Conclusions: Species-dependent variations in radiopharmaceutical binding to serum albumin may need to be considered when using animal models to predict the distribution and kinetics of these compounds in humans.

  3. A laser photofragmentation time-of-flight mass spectrometric study of acetophenone at 193 and 248 nm

    Zhao, H.-Q.; Cheung, Y.-S.; Liao, C.-L.; Liao, C.-X.; Ng, C. Y.; Li, Wai-Kee

    1997-11-01

    The photodissociation of acetophenone (C6H5COCH3) at 193 and 248 nm has been studied using the time-of-flight mass spectrometric technique. For hν=193 nm, two major primary channels, C6H5COCH3+hν→C6H5CO+CH3 [channel (1)] and C6H5+CH3CO [channel (2)], are observed with comparable cross sections. Data analysis shows that ≈30%-50% of primary C6H5CO and CH3CO radicals further decomposes, yielding secondary products C6H5+CO and CH3+CO, respectively. The translational energy release measurements indicate that for both channels (1) and (2) at 193 nm, ≈25%-30% of the available energy is channeled into kinetic energies of the primary photofragments. Measurements at hν=248 nm reveal that the branching ratio of channel (2) to channel (1) is ≈0.01. For channel (1) at hν=248 nm, ≈42% of the available energy is directed as the kinetic energy of the photofragments. The observed maximum kinetic energy release for channel (1) at 248 nm yields a value of 85.0±2.2 kcal/mol for the C6H5CO-CH3 bond dissociation energy at 0 K (D0). The photofragment angular distributions are found to be isotropic for both channels (1) and (2) at hν=193 nm and for channel (1) at hν=248 nm. A minor photodissociation channel C6H5COCH3+hν→C6H5CH3+CO is identified at both hν=193 and 248 nm. The energetics for the dissociation reactions of acetophenone have also been investigated using ab initio Gaussian-2-type procedures. The heats of formation at 0 K (ΔfH°0) for C6H5CO and C6H5 calculated using the isodesmic reaction scheme are 33.9±1.3 and 87.6±1.0 kcal/mol, respectively. These results suggest that the literature ΔfH°0 values for C6H5CO and C6H5 are likely to be low by 3-4 kcal/mol. These theoretical ΔfH° values for C6H5CO and C6H5 yield a theoretical D0(C6H5CO-CH3) value of 85.1±1.4 kcal/mol, which is in excellent accord with the experimental results obtained in the present study.

  4. Ultrasonic-bath-assisted preparation of mononuclear copper(I) thiosemicarbazone complex particles: crystal structure, characterization and antimicrobial activity

    Khalaji, A.D.; Shahsavani, E.; Feizi, N.; Kučeráková, Monika; Dušek, Michal; Mazandarani, R.; Amiri, A.

    2017-01-01

    Roč. 20, č. 2 (2017), s. 125-131 ISSN 1631-0748 R&D Projects: GA MŠk LO1603; GA ČR(CZ) GA15-12653S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : thiosemicarbazone * copper(I) complex * spectroscopy * X-ray crystallography Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.879, year: 2016

  5. Copper, nickel and zinc complexes of a new water-soluble thiosemicarbazone ligand: Synthesis, characterization, stability and biological evaluation

    Hosseini-Yazdi, S.A.; Mirzaahmadi, A.; Khandar, A.A.; Mahdavi, M.; Rahimian, A.; Eigner, Václav; Dušek, Michal; Zarrini, G.

    2017-01-01

    Roč. 248, Dec (2017), s. 658-667 ISSN 0167-7322 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk(CZ) LO1603 EU Projects: European Commission(CZ) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : cytotoxicity * thiosemicarbazone * water-soluble Schiff base * stability * antioxidant * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.648, year: 2016

  6. CNDO/2 calculations for α-oximino-acetoacetanilide thiosemicarbazone and synthesis and characterization of some metal chelates derived from it

    Patel, P.S.; Ray, A.; Patel, M.M.

    1992-01-01

    Solid complexes of α-oximinoacetoacetanilide thiosemicarbazone (OAATS) with Ni(II), Co(II), Zn(II), Mn(II), Cd(II), Hg(II) and UO 2 (II) have been prepared and characterized on the basis of their elemental analyses, conductivity, differential scanning calorimetry, thermogravimetric analysis, infrared and electronic spectral measurements, in conjunction with magnetic susceptibility measurements. Molecular orbital calculations employing the CNDO/2 method have been made for a number of conformations of the ligand molecule to ascertain the most stable one. (author). 24 refs., 3 figs., 2 tabs

  7. Operator substitution

    Hautus, M.L.J.

    1994-01-01

    Substitution of an operator into an operator-valued map is defined and studied. A Bezout-type remainder theorem is used to derive a number of results. The tensor map is used to formulate solvability conditions for linear matrix equations. Some applications to system theory are given, in particular

  8. Solvent substitution

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general ''Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated

  9. Tonemic Substitution

    Ezenwafor

    grammatical constructions. The choice of substitutable tonemes as observed from the analyzed data is highly. Ezenwafordependent on the intuitive judgement of the native speaker. This work shows with adequate data, that regular tonemic changes are not always meaningful in Ekwulobia lect. Such tonemic alternations are ...

  10. Solvent substitution

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  11. Thermophysical Properties of Acetophenone with Ethylchloroacetate at Temperatures of 303.15, 313.15 and 323.15 K

    Saravanakumar, K. [Sathyabama Univ., Chennai (India); Baskaran, R. [St.Joseph' s College of Engineering, Chennai (India); Kubendran, T. R. [Anna Univ., Chennai (India)

    2012-08-15

    Densities, viscosities, refractive indices and speed of sounds of the binary mixtures of Acetophenone with Ethylchloroacetate were measured over the entire mole fractions at (303.15, 313.15 and 323.15) K. From these experimental results, excess molar volume V{sup E}, viscosity deviation Δη, refractive index deviation Δn{sub D}, deviations in speed of sound Δu, deviations in isentropic compressibility Δk{sub s} and excess intermolecular free length ΔL{sub f} were calculated. The viscosity data have been correlated with the equations of Grunberg and Nissan, Hind et al., Tamura and Kurata, Katti and Chaudri, Sedgwick, Krishnan-Laddha and McAllister. The thermo physical properties under study were fit to the Jouyban-Acree model. The excess values were correlated using Redlich-Kister polynomial equation to obtain their coefficients and standard deviations. It was found that in all cases, the data obtained fitted with the values correlated by the corresponding models very well. The results are interpreted in terms of molecular interactions occurring in the solution.

  12. Thermophysical Properties of Acetophenone with Ethylchloroacetate at Temperatures of 303.15, 313.15 and 323.15 K

    Saravanakumar, K.; Baskaran, R.; Kubendran, T. R.

    2012-01-01

    Densities, viscosities, refractive indices and speed of sounds of the binary mixtures of Acetophenone with Ethylchloroacetate were measured over the entire mole fractions at (303.15, 313.15 and 323.15) K. From these experimental results, excess molar volume V E , viscosity deviation Δη, refractive index deviation Δn D , deviations in speed of sound Δu, deviations in isentropic compressibility Δk s and excess intermolecular free length ΔL f were calculated. The viscosity data have been correlated with the equations of Grunberg and Nissan, Hind et al., Tamura and Kurata, Katti and Chaudri, Sedgwick, Krishnan-Laddha and McAllister. The thermo physical properties under study were fit to the Jouyban-Acree model. The excess values were correlated using Redlich-Kister polynomial equation to obtain their coefficients and standard deviations. It was found that in all cases, the data obtained fitted with the values correlated by the corresponding models very well. The results are interpreted in terms of molecular interactions occurring in the solution

  13. Vibrational, NMR and UV-visible spectroscopic investigation and NLO studies on benzaldehyde thiosemicarbazone using computational calculations

    Moorthy, N.; Prabakar, P. C. Jobe; Ramalingam, S.; Pandian, G. V.; Anbusrinivasan, P.

    2016-04-01

    In order to investigate the vibrational, electronic and NLO characteristics of the compound; benzaldehyde thiosemicarbazone (BTSC), the XRD, FT-IR, FT-Raman, NMR and UV-visible spectra were recorded and were analysed with the calculated spectra by using HF and B3LYP methods with 6-311++G(d,p) basis set. The XRD results revealed that the stabilized molecular systems were confined in orthorhombic unit cell system. The cause for the change of chemical and physical properties behind the compound has been discussed makes use of Mulliken charge levels and NBO in detail. The shift of molecular vibrational pattern by the fusing of ligand; thiosemicarbazone group with benzaldehyde has been keenly observed. The occurrence of in phase and out of phase molecular interaction over the frontier molecular orbitals was determined to evaluate the degeneracy of the electronic energy levels. The thermodynamical studies of the temperature region 100-1000 K to detect the thermal stabilization of the crystal phase of the compound were investigated. The NLO properties were evaluated by the determination of the polarizability and hyperpolarizability of the compound in crystal phase. The physical stabilization of the geometry of the compound has been explained by geometry deformation analysis.

  14. Comparative evaluation of Bis(thiosemicarbazone)- Biotin and Met-ac-TE3A for tumor imaging

    Singh, Sweta; Tiwari, Anjani K.; Varshney, Raunak; Mathur, R.; Shukla, Gauri; Bag, N.; Singh, B.; Mishra, Anil K.

    2016-01-01

    2,2‧,2″-(11-(2-((4-mercapto-1-methoxy-1-oxobutan-2-yl)amino)-2-oxoethyl)-1,4,8,11-tetraaza cyclotetradecane-1,4,8-triyl)triacetic acid, Met-ac-TE3A and (E)-N-methyl-2-((E)-3-(2-(2-(5-((3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl)pentanoyl)hydrazinecarbono-thioyl)hydrazonobutan-2-ylidene)hydrazinecarbothioamide, Bis(thiosemicarbazone)- Biotin were synthesized and evaluated for imaging application. The pharmacokinetics of these ligands were determined by tracer methods. In vitro human serum stability of 99mTc Met-ac-TE3A/99mTc Bis(thiosemicarbazone)-Biotin after 24 h was found to be 96.5% and 97.0% respectively. Blood kinetics of both ligands in normal rabbits showed biphasic clearance pattern. Ex vivo biodistribution study revealed significant initial tumor uptake and high tumor/muscles ratio which is a pre-requisite condition for a ligand to work as SPECT-radiopharmaceutical for tumor imaging.

  15. Study of antioxidant, anti-protease and anti-urease potential of schiff bases of acetophenone with different amines

    Ahmed, D.; Mir, H.

    2014-01-01

    Seven acetophenone-derived Schiff bases were synthesized with different amines including 2-aminobenzoic acid (HL1), 4-aminobenzoic acid (HL2), 2-naphthylamine (HL3), phenylhydrazine (HL4), 1,2-ethanediamine (HL5), 1,2-diaminobenzene (HL6) and 1,4-diaminobenzene (HL7), and were subjected to various assays including FRAP (ferric reducing antioxidant power), DPPH (1,1-diphenyl-2-picrylhydrazyl), phosphomolybdate, reducing power, and lipid peroxidation inhibition. They were also evaluated for protease and urease inhibitory activities. Based on the results, structure-activity relationship (SAR) was determined. Only two bases, HL1 and HL4, exhibited antioxidant or free radical scavenging activity in DPPH assay. HL4 was most potent (IC50 15 micro g/mL), while HL1 was only slightly active. As HL4 was the only base with hydrogen bonded to nitrogen, most probably it involves hydrogen transfer (HT) mechanism. All the bases exhibited a range of antioxidant activity in assays involving electron transfer (ET). In the reducing power assay, HL5, HL6 and HL7 showed considerable potential while in FRAP assay, HL7 was most active followed by HL3. In phosphomolybdate assay, HL6 had the highest potency followed by HL7, while HL4 and HL3 also displayed good activity. All the bases showed moderate to high lipid peroxidation inhibitory activity. HL7 exhibited highest protease inhibitory activity (EC50 43.9 mu g/mL) followed by HL6 (EC/sub 50/ 52 mu g/mL). HL4 and HL5 did not show protease inhibitory activity at all. HL2 was most potent in inhibiting urease activity (EC50 29.91 mu g/mL). HL5 and HL6 showed moderate activity. The study showed how variation in structures of Schiff bases alters their antioxidant and anti-enzymatic activities. (author)

  16. Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone

    Chandra, Sulekh; Kumar, Anil

    2007-12-01

    Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L) 2(SO 4) and Cu(L) 2(SO 4) [where L = L 1 and L 2] which are of five coordinated square pyramidal geometry.

  17. Determination of mercury by liquid chromatography in fresh water fishes using 2-thiophenealdehyde-4-phenyl-3-thiosemicarbazone

    Khuhawar, M.Y.; Languani, S.N.

    2001-01-01

    Co (II), Ag (I) and Hg (II) or Co (II), Ni (II), Fe (II), Cu (II) and Hg (II) are simultaneously extracted as metal chelates compounds of 2-thiophenealdehyde-4-phenyl-3-thiosemicarbazone (TAPT) in chloroform. The complexes were separated from microsorb C-18, 5 mue m column when eluted with methanol/acetonitrile/water/aqueous sodium acetate 1 m mol or methanol/acetonitrile/water/sodium acetate (1 mmol) tetrabutyl ammonium bromide (1mmol) with a flow rate of 1 ml-1 and detection UV at 254 nm. Linear calibrations were made with 10-50 ml-1 and detection limit was 0.4 ml-1, corresponding to 2 ng/injection in Co and Hg. The method was used for the determination of mercury in surface water fishes. It was found within 0.125 to 1.18 g-1 of fish muscles with coefficient of variation (C.V) 3.4-5.8%. (author)

  18. Combining molecular docking and QSAR studies for modeling the anti-tyrosinase activity of aromatic heterocycle thiosemicarbazone analogues

    Dong, Huanhuan; Liu, Jing; Liu, Xiaoru; Yu, Yanying; Cao, Shuwen

    2018-01-01

    A collection of thirty-six aromatic heterocycle thiosemicarbazone analogues presented a broad span of anti-tyrosinase activities were designed and obtained. A robust and reliable two-dimensional quantitative structure-activity relationship model, as evidenced by the high q2 and r2 values (0.848 and 0.893, respectively), was gained based on the analogues to predict the quantitative chemical-biological relationship and the new modifier direction. Inhibitory activities of the compounds were found to greatly depend on molecular shape and orbital energy. Substituents brought out large ovality and high highest-occupied molecular orbital energy values helped to improve the activity of these analogues. The molecular docking results provided visual evidence for QSAR analysis and inhibition mechanism. Based on these, two novel tyrosinase inhibitors O04 and O05 with predicted IC50 of 0.5384 and 0.8752 nM were designed and suggested for further research.

  19. ynthesis, theoretical study on Zinc (II and Ni(II complexes of 5-methoxyisatin 3-[N-(4-chlorophenyl thiosemicarbazone

    Fatma Kandemirli

    2012-03-01

    Full Text Available Zinc(II and nickel(II-complexes of 5-methoxyisatin 3-[N-(4-chlorophenyl thiosemicarbazone] (H2MICP were synthesized and characterized by infrared, ultraviolet and 1H-NMR spectroscopies as well as elemental analysis. Model of H2MICP and its zinc(II and nickel(II-complexes were optimized with B3LYP method using 6-31G(d,p, 6-311G(d,p, 6-311++G(d,p, 6-311++G(2d,2p basis sets. The calculated 1H-NMR, UV and IR spectra data were compared with experimental results. In addition to the Natural Bond Orbital (NBO analysis of H2MICP and its Zinc(II and Nickel(II complexes, Fukui functions of H2MICP were also reported.

  20. An investigation of the effects of experimental parameters on the closed-loop control of photoionization/dissociation processes in acetophenone

    Graham, Paul; Menkir, Getahun; Levis, Robert J.

    2003-06-01

    The photodissociation channels of acetophenone (C 6H 5)CO(CH 3), can be controlled by the use of tailored strong-field laser pulses together with a feedback loop incorporating an adaptive algorithm. This optimal control strategy is used to selectively cleave either the OCCH 3 or OCC 6H 5 bonds, monitored by detecting either mass 105 or 77, respectively. Varying the pulse chirp and duration prior to optimization is shown to affect the dynamic range of control. We show that it is possible to decrease the search space by limiting the retardance range of the spatial light modulator (SLM), or by decreasing the number of frequency elements manipulated by the SLM, and still achieve a certain degree of control over acetophenone dissociation. Performing consecutive experiments with identical experimental parameters and search criteria reveals that the learning algorithm may find solutions that have the same degree of control (various local solutions), with either similar SLM retardances or markedly different retardances. Comparison of the dynamic range of control between single-parameter optimizations (pulse energy and duration) with the tailored electric field profiles generated by the adaptive algorithm reveals an enhancement in the control of reaction product distributions in the latter scheme.

  1. Radioactive Indium({sup 114m}In) complexes derived thiosemicarbazones for development of glioma radionuclide therapy tools

    Ribeiro, Thais S.; Menezes, Maria Ângela B.C.; Belo, Luiz Cláudio M.; Santos, Raquel G. dos, E-mail: thaissribeiro01@gmail.com, E-mail: lcmb@cdtn.br, E-mail: menezes@cdtn.br, E-mail: gouvears@gmail.com [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil); Franco, Lucas L.; Oliveira, Alexandre A.; Beraldo, Heloisa O., E-mail: lucas_lopardi@yahoo.com.br, E-mail: a13xandr31@hotmail.com, E-mail: heloisaberaldoufmg@gmail.com [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Departamento de Química

    2017-07-01

    Chemotherapy is widely used as the main course of treatment for various types of cancer. However, the side effects derived from the prolonged use of highly cytotoxic drugs in association with chemotherapy induced resistance are important challenges for effective therapy. In this context, radionuclide therapy (RNT) can be an alternative way to decrease the toxicity and improve the specificity of anti tumoral drugs. Our group has recently demonstrated that Indium (III) coordination to N(4)-Tolyl-2-acetylpyridine-derived thiosemicarbazones improves cytotoxic effects on leukemia cell lines. Once {sup 114m}In is a prolific Auger electron emitter, in this study In (III) complexes and their radioactive analogs were produced by neutron activation and their potential for RNT was further studied. Native and radioactive complexes were tested in different concentrations in U87 and T98 glioblastoma multiform (GBM) cell lines, as well as in MRC5 fibroblast cell line. All drugs presented a dose dependent cytotoxicity against cancer cells at submicromolar concentrations. The treatment with 1 μM of the radioactive analogs containing {sup 114m}In proved to be at least 1.5 times more potent than non-radioactive complexes in GBM cell lines. Due to the innate resistance of glioblastomas to chemotherapy and radiotherapy, the potentiation factor showed by the test radioactive complexes may be interesting in the course of treatment against these tumors. Therefore, the presented data suggests a synergistic effect of the radionuclide therapy conducted in this study, which might be due to the combinations of pharmacological and radiotherapeutic activities of the {sup 114m}In - thiosemicarbazone compounds. (author)

  2. Inhibition of bovine viral diarrhea virus RNA synthesis by thiosemicarbazone derived from 5,6-dimethoxy-1-indanone.

    Castro, Eliana F; Fabian, Lucas E; Caputto, María E; Gagey, Dolores; Finkielsztein, Liliana M; Moltrasio, Graciela Y; Moglioni, Albertina G; Campos, Rodolfo H; Cavallaro, Lucía V

    2011-06-01

    In the present work, we described the activity of the thiosemicarbazone derived from 5,6-dimethoxy-1-indanone (TSC), which we previously characterized as a new compound that inhibits bovine viral diarrhea virus (BVDV) infection. We showed that TSC acts at a point of time that coincides with the onset of viral RNA synthesis and that it inhibits the activity of BVDV replication complexes (RCs). Moreover, we have selected five BVDV mutants that turned out to be highly resistant to TSC but still susceptible to ribavirin (RBV). Four of these resistant mutants carried an N264D mutation in the viral RNA-dependent RNA polymerase (RdRp). The remaining mutant showed an A392E mutation within the same protein. Some of these mutants replicated slower than the wild-type (wt) virus in the absence of TSC, whereas others showed a partial reversion to the wt phenotype over several passages in the absence of the compound. The docking of TSC in the crystal structure of the BVDV RdRp revealed a close contact between the indane ring of the compound and several residues within the fingers domain of the enzyme, some hydrophobic contacts, and hydrogen bonds with the thiosemicarbazone group. Finally, in the mutated RdRp from resistant BVDV, these interactions with TSC could not be achieved. Interestingly, TSC inhibited BVDV replication in cell culture synergistically with RBV. In conclusion, TSC emerges as a new nonnucleoside inhibitor of BVDV RdRp that is synergistic with RBV, a feature that turns it into a potential compound to be evaluated against hepatitis C virus (HCV).

  3. Inhibition of Bovine Viral Diarrhea Virus RNA Synthesis by Thiosemicarbazone Derived from 5,6-Dimethoxy-1-Indanone▿

    Castro, Eliana F.; Fabian, Lucas E.; Caputto, María E.; Gagey, Dolores; Finkielsztein, Liliana M.; Moltrasio, Graciela Y.; Moglioni, Albertina G.; Campos, Rodolfo H.; Cavallaro, Lucía V.

    2011-01-01

    In the present work, we described the activity of the thiosemicarbazone derived from 5,6-dimethoxy-1-indanone (TSC), which we previously characterized as a new compound that inhibits bovine viral diarrhea virus (BVDV) infection. We showed that TSC acts at a point of time that coincides with the onset of viral RNA synthesis and that it inhibits the activity of BVDV replication complexes (RCs). Moreover, we have selected five BVDV mutants that turned out to be highly resistant to TSC but still susceptible to ribavirin (RBV). Four of these resistant mutants carried an N264D mutation in the viral RNA-dependent RNA polymerase (RdRp). The remaining mutant showed an A392E mutation within the same protein. Some of these mutants replicated slower than the wild-type (wt) virus in the absence of TSC, whereas others showed a partial reversion to the wt phenotype over several passages in the absence of the compound. The docking of TSC in the crystal structure of the BVDV RdRp revealed a close contact between the indane ring of the compound and several residues within the fingers domain of the enzyme, some hydrophobic contacts, and hydrogen bonds with the thiosemicarbazone group. Finally, in the mutated RdRp from resistant BVDV, these interactions with TSC could not be achieved. Interestingly, TSC inhibited BVDV replication in cell culture synergistically with RBV. In conclusion, TSC emerges as a new nonnucleoside inhibitor of BVDV RdRp that is synergistic with RBV, a feature that turns it into a potential compound to be evaluated against hepatitis C virus (HCV). PMID:21430053

  4. Synthesis and Characterization of Some New Cu(II, Ni(II and Zn(II Complexes with Salicylidene Thiosemicarbazones: Antibacterial, Antifungal and in Vitro Antileukemia Activity

    Tudor Rosu

    2013-07-01

    Full Text Available Thirty two new Cu(II, Ni(II and Zn(II complexes (1–32 with salicylidene thiosemicarbazones (H2L1–H2L10 were synthesized. Salicylidene thiosemicarbazones, of general formula (XN-NH-C(S-NH(Y, were prepared through the condensation reaction of 2-hydroxybenzaldehyde and its derivatives (X with thiosemicarbazide or 4-phenylthiosemicarbazide (Y = H, C6H5. The characterization of the new formed compounds was done by 1H-NMR, 13C-NMR, IR spectroscopy, elemental analysis, magnetochemical, thermoanalytical and molar conductance measurements. In addition, the structure of the complex 5 has been determined by X-ray diffraction method. All ligands and metal complexes were tested as inhibitors of human leukemia (HL-60 cells growth and antibacterial and antifungal activities.

  5. Synthesis, spectral, thermal and antimicrobial studies on cobalt(II), nickel(II), copper(II), zinc(II) and palladium(II) complexes containing thiosemicarbazone ligand

    El-Sawaf, Ayman K.; El-Essawy, Farag; Nassar, Amal A.; El-Samanody, El-Sayed A.

    2018-04-01

    The coordination characteristic of new N4-morpholinyl isatin-3-thiosemicarbazone (HL) towards Co(II), Ni(II), Cu(II), Zn(II) and Pd(II) has been studies. The structures of the complexes were described by elemental analyses, molar conductivity, magnetic, thermal and spectral (IR, UV-Vis, 1H and 13C NMR and ESR) studies. On the basis of analytical and spectral studies the ligand behaves as monobasic tridentate ONS donor forming two five membered rings towards cobalt, copper and palladium and afforded complexes of the kind [M(L)X], (Mdbnd Co, Cu or Pd; Xdbnd Cl, Br or OAc). Whereas the ligand bound to NiCl2 as neutral tridentate ONS donor and with ZnCl2 as neutral bidentate NS donor. The newly synthesized thiosemicarbazone ligand and some of its complexes were examined for antimicrobial activity against 2 gram negative bacterial strains (Escherichia coli Pseudomonas and aeruginosa), 2 gram positive bacterial strains (Streptococcus pneumoniae and Staphylococcus aureus)} and two Pathogenic fungi (Aspergillus fumigatus and Candida albicans). All metal complexes possess higher antimicrobial activity comparing with the free thiosemicarbazone ligand. The high potent activities of the complexes may arise from the coordination and chelation, which tends to make metal complexes act as more controlling and potent antimicrobial agents, thus hindering the growing of the microorganisms. The antimicrobial results also show that copper bromide complex is better antimicrobial agent as compared to the Schiff base and its metal complexes.

  6. Synthesis, Spectral and Magnetic Studies of Newly Mixed-Ligand Complexes of 4-Formyl-Acetanilide Thiosemicarbazone and 3,4-Dihydrocinnamic Acid with Some Metal Ions

    Shayma A. Shaker

    2010-01-01

    Full Text Available New complexes with thiosemicarbazone derivative and 3, 4-dihydrocinnamic acid were prepared and characterized by elemental analysis, determination of metal, IR, 1H NMR, electronic spectroscopy and magnetic measurements. The thiosemicarbazone derivative forms bidentate ligand complexes of the general formula, [M(Thz(Caf] where Thz = 4-formyl- acetanilide thiosemicarbazone, Caf = 3,4-dihydrocinnamic acid and M=Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+. The IR and 1H NMR spectra indicates that the (Thz was coordinated with the metal ions through the N and S atoms and the (Caf was negatively charged bidentat ligand and was coordinated with the metal ions through the two O atoms. Electronic spectra and magnetic susceptibility measurements of the solid complexes indicates the tetrahedral geometry around the Mn2+, Fe2+, Co2+, Ni2+, Zn2+, Cd2+ and irregular tetrahedral geometry around Pb2+ ion while the Cu2+ complex has squar planer geometry.

  7. Simple, heart-smart substitutions

    Coronary artery disease - heart smart substitutions; Atherosclerosis - heart smart substitutions; Cholesterol - heart smart substitutions; Coronary heart disease - heart smart substitutions; Healthy diet - heart ...

  8. Structure-activity relationships of mononuclear metal-thiosemicarbazone complexes endowed with potent antiplasmodial and antiamoebic activities.

    Bahl, Deepa; Athar, Fareeda; Soares, Milena Botelho Pereira; de Sá, Matheus Santos; Moreira, Diogo Rodrigo Magalhães; Srivastava, Rajendra Mohan; Leite, Ana Cristina Lima; Azam, Amir

    2010-09-15

    A useful concept for the rational design of antiparasitic drug candidates is the complexation of bioactive ligands with transition metals. In view of this, an investigation was conducted into a new set of metal complexes as potential antiplasmodium and antiamoebic agents, in order to examine the importance of metallic atoms, as well as the kind of sphere of co-ordination, in these biological properties. Four functionalized furyl-thiosemicarbazones (NT1-4) treated with divalent metals (Cu, Co, Pt, and Pd) to form the mononuclear metallic complexes of formula [M(L)2Cl2] or [M(L)Cl2] were examined. The pharmacological characterization, including assays against Plasmodium falciparum and Entamoeba histolytica, cytotoxicity to mammalian cells, and interaction with pBR 322 plasmid DNA was performed. Structure-activity relationship data revealed that the metallic complexation plays an essential role in antiprotozoal activity, rather than the simple presence of the ligand or metal alone. Important steps towards identification of novel antiplasmodium (NT1Cu, IC50 of 4.6 microM) and antiamoebic (NT2Pd, IC50 of 0.6 microM) drug prototypes were achieved. Of particular relevance to this work, these prototypes were able to reduce the proliferation of these parasites at concentrations that are not cytotoxic to mammalian cells. Copyright (c) 2010. Published by Elsevier Ltd.

  9. Stability of the resistance to the thiosemicarbazone derived from 5,6-Dimethoxy-1-indanone, a non-nucleoside polymerase inhibitor of bovine viral diarrhea virus

    Castro, Eliana Florencia; Campos, Rodolfo Hector; Cavallaro, Lucía Vicenta

    2017-01-01

    Bovine viral diarrhea virus (BVDV) is the prototype Pestivirus. BVDV infection is distributed worldwide and causes serious problems for the livestock industry. The thiosemicarbazone of 5,6-dimethoxy-1-indanone (TSC) is a non-nucleoside polymerase inhibitor (NNI) of BVDV. All TSC-resistant BVDV variants (BVDV-TSCr T1–5) present an N264D mutation in the NS5B gene (RdRp) whereas the variant BVDV-TSCr T1 also presents an NS5B A392E mutation. In the present study, we carried out twenty passages of...

  10. Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N4-methyl-3-thiosemicarbazone: Crystal structure of a novel sulfur bridged copper(II) box-dimer

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

    2015-03-01

    Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N4-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ = 0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)sbnd I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g|| > g⊥ > 2.0023 and the g values in frozen DMF are consistent with the dx2-y2 ground state. The thermal stabilities of some of the complexes were also determined.

  11. Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N⁴-methyl-3-thiosemicarbazone: crystal structure of a novel sulfur bridged copper(II) box-dimer.

    Jayakumar, K; Sithambaresan, M; Aiswarya, N; Kurup, M R Prathapachandra

    2015-03-15

    Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N(4)-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ=0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g||>g⊥>2.0023 and the g values in frozen DMF are consistent with the d(x2-y2) ground state. The thermal stabilities of some of the complexes were also determined. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Evaluation of the potential application of 2-acetylpyridine N4- phenyl thiosemicarbazones derivatives for cancer therapy and diagnosis

    Soares, Marcella Araugio

    2013-01-01

    Despite the wide range of antineoplastic agents available, resistance of some types of cancer and toxicity to normal cells have been identified as the main causes of treatment failure and death. The lack of early and precise diagnosis is also responsible for reducing survival of cancer patients. In this context, the development of substances with low toxicity and therapeutic potential and/or diagnosis purpose, is the major tool in an attempt to increase the survival of patients and assure the safety and efficacy of treatment. Thiosemicarbazones (TSC) are a class of synthetic compounds that have several biological activities, including antitumor. Although several studies have shown the great potential of TSC as therapeutic and / or diagnostic agents, different chemical modifications performed on this class of molecules indicate new possibilities for applications and still require further studies. The objective of this study was to evaluate the potential applicability of 2-acetylpyridine N-4-phenyl thiosemicarbazones derivatives for cancer therapy and diagnosis. The results showed that all 13 TSC tested were cytotoxic to breast and glioblastoma tumor cell lines, presenting higher in vitro antitumor activity than etoposide, an antineoplastic and inhibitor of topoisomerase II frequently used for cancer therapy. The TSC that have halogen or nitro on ortho position showed higher antitumor activity in vitro than their isomers with halogen or nitro on meta or para position of the phenyl group. H2Ac4oFPh and H2Ac4oClPh compounds showed the highest antitumor activity among all tested compounds, with IC 50 in nanomolar order. These TSC induced cell death by apoptosis and oxidative stress was responsible, at least in part, for this type of cell death. The 5 mg.kg -1 H2Ac4oFPh dose, administered s.c., for 4 consecutive days, did not induce important toxicity; however, the same treatment protocol was not effective for tumor growth reduction in an animal model of brain tumor

  13. [2 × 2] Molecular Grids of Ni(II and Zn(II with Redox-Active 1,4-Pyrazine-Bis(thiosemicarbazone Ligands

    Natalia Arefyeva

    2018-05-01

    Full Text Available Tetranuclear complexes [M4(LR4] with M = Ni(II or Zn(II, with a [2 × 2] grid-type structure, were assembled in good yields and purity from the easily accessible but unprecedented pyrazine-bridged bis(thiosemicarbazone protoligands (ligand precursors H2LR (1,4-pyrazine-2,5-bis(R-carbaldehyde-thiosemicarbazone; R = Me, Et, iPr, or Ph. The complexes were characterised in solution by NMR, MS, IR, and UV-Vis absorption spectroscopy and (spectroelectrochemical methods. HR-MS spectra unequivocally reveal that the tetranuclear species are very stable in solution and any measurements represent these species. Only at higher temperatures (fragmentation in solution: MS and in the solid: TG-DTA or upon the addition of protons (acidic UV-Vis titrations can the tetrameric entities be decomposed. Single crystal XRD measurement remained preliminary. Rapid loss of co-crystallised solvent molecules within the [2 × 2] grid-type structures resulted in crystals of very poor quality, but the results were qualitatively in line with spectroscopy, electrochemistry, and quantum chemical (DFT calculations. IR and NMR spectroscopy point clearly to a thiolate coordination of dianionic (deprotonated ligands. The electrochemistry reveals four electronically coupled and reversible one-electron reductions centred largely at the pyrazine bridges. EPR and UV-Vis spectroelectrochemical measurements in combination with DFT calculation support the assignment.

  14. The radiosensitizing effect of a N(4)-tolyl-2-acetylpyridine derived thiosemicarbazone and its metallic complex against a glioblastoma cell line

    Vilas Boas, Fabricio A.S.; Hudson, Luiza O.; Santos, Raquel G. dos; Mendes, Isolda C.; Beraldo, Heloisa O.

    2009-01-01

    Cancer is one of the most prevalent and difficult diseases to be treated. Despite the efforts at improving diagnose and treatment, the success is still very limited. One of the factors implicated in such limitation is the inherent radioresistance of most tumors, specially the cerebral ones. They are poorly vascularized due to the rapid growth of cells and disorganized angiogenesis that leads to hypoxic tissue that increases radioresistance. Also another issue is the side effects of exposition to high levels of radiation and chemicals. Combined approaches using both chemo and radiotherapy are one of the most effective strategies applied to maximize the results and decrease the side effects of the treatment to the patient. One of the drugs that are commonly used is cisplatin that has some, yet limited result. Given this context, our group has been testing several synthetic compounds of the thiosemicarbazone class. These chemicals have broad pharmacologic profile including antitumoral effect. We have shown in previous works the effective reduction of cell viability and proliferation using very low concentrations of thiosemicarbazones both in free form and complexed with metals like copper. In this work we present another application of this compound that can also be used as a radiosensitization agent in glioblastoma multiform cell line RT-2 present that the combined approach increases de effect of gamma radiation. Also, that the coordination to copper apparently does not increase this activity. (author)

  15. Synthesis, Crystal Structural Characterization and Biological Properties of Thiosemicarbazones of Schiff Bases Derived from 4-Acyl-2-pyrazoline-5-one

    Arjunsinh Rana

    2011-01-01

    Full Text Available A novel synthesis, single crystal and biological activity of 4-acylthiosemicarbazone-3-methyl-1-(4`-methylphenyl-2-pyrazolin-5-one by condensation of 4-acyl-3-methyl-1-(4`-methylphenyl-2-pyrazolin-5-one with thiosemicarbazide was carried out. The compounds were characterized on the basis of elemental analysis, IR, 1H NMR, Mass, DSC and 13C NMR spectral data. The compounds were tested for their antibacterial activity against various gram +ve and -ve bacteria. The results were compared with the marketed drugs. The crystal structure was determined by single x-ray diffraction. 4-Acetyl thiosemicarbazone-3-methyl-1-(4`-methylphenyl-2-pyrazolin-5-one(AcPTMP-ths crystallizes in the monoclinic system, space group P21/n with a=6.0828(7Å, b=29.547(4Å, c=7.9101(15Å, α=90°, γ=95.602(15°, γ=90°, V=1414.9(4 Å3, Z=4, Dc=1.429 mg/m3 and 4-Propionylthiosemicarbazone-3-methyl-1-(4`-methylphenyl-2-pyrazolin-5-one (PropPTMP-ths crystallizes in the monoclinic system, space group P21/c with a=13.5622(10Å, b=13.3671(12Å, c=22.151(2Å, α=90°, β=93.13(7°, γ=90°, V=4010.1(6 Å3, Z=8, Dc=1.310 mg/m3. The compounds were screened for antibacterial properties and exhibited potential activity.

  16. New heteroleptic Zn(II) complexes of thiosemicarbazone and diimine Co-Ligands: Structural analysis and their biological impacts

    Mathan Kumar, Shanmugaiah; Kesavan, Mookkandi Palsamy; Vinoth Kumar, Gujuluva Gangatharan; Sankarganesh, Murugesan; Chakkaravarthi, Ganesan; Rajagopal, Gurusamy; Rajesh, Jegathalaprathaban

    2018-02-01

    A thiosemicarbazone ligand HL appended new Zn(II) complexes [Zn(L)(bpy)] (1) and [Zn(L)(phen)] (2) (where, HL = {2-(3-bromo-5-chloro-2-hydroxybenzylidene)-N-phenylhydrazinecarbothioamide}, bpy = 2, 2‧-bipyridine and phen = 1, 10-phenanthroline) have been synthesized and well characterized using conventional spectroscopic techniques viz.,1H NMR, FTIR and UV-Vis spectra. The crystal structures of complexes 1 and 2 have been determined by single crystal X-ray diffraction studies. Both the complex 1 (τ = 0.5) and 2 (τ = 0.37) possesses square based pyramidally distorted trigonal bipyramidal geometry. The ground state electronic structures of complexes 1 and 2 were investigated by DFT/B3LYP theoretical analysis using 6-311G (d,p) and LANL2DZ basis set level. The superior DNA binding ability of complex 2 has been evaluated using absorption and fluorescence spectral titration studies. Antimicrobial evaluation reveals that complex 2 endowed better screening than HL and complex 1 against both bacterial as well as fungal species. Consequently, complex 2 possesses highest antibacterial screening against Staphylococcus aureus (MIC = 3.0 ± 0.23 mM) and antifungal screening against Candida albicans (MIC = 6.0 ± 0.11 mM). Furthermore, the anticancer activity of the ligand HL, complexes 1 and 2 have been examined against the MCF-7 cell line (Human breast cancer cell line) using MTT assay. It is remarkable that complex 2 (12 ± 0.67 μM) show highest anticancer activity than HL (25.0 ± 0.91 μM) and complex 1 (15 ± 0.88 μM) due to the presence of phen ligand moiety.

  17. Enhancement of photocatalytic degradation of furfural and acetophenone in water media using nano-TiO2-SiO2 deposited on cementitious materials.

    Soltan, Sahar; Jafari, Hoda; Afshar, Shahrara; Zabihi, Omid

    2016-10-01

    In the present study, silicon dioxide (SiO 2 ) nanoparticles were loaded to titanium dioxide (TiO 2 ) nano-particles by sol-gel method to make a high porosity photocatalyst nano-hybrid. These photocatalysts were synthesized using titanium tetrachloride and tetraethyl orthosilicate as titanium and silicon sources, respectively, and characterized by X-ray powder diffraction (XRD) and scanning electron microscope methods. Subsequently, the optimizations of the component and operation conditions were investigated. Then, nano-sized TiO 2 and TiO 2 -SiO 2 were supported on concrete bricks by the dip coating process. The photocatalytic activity of nano photocatalysts under UV irradiation was examined by studying the decomposition of aqueous solutions of furfural and acetophenone (10 mg/L) as model of organic pollutants to CO 2 and H 2 O at room temperature. A decrease in the concentration of these pollutants was assayed by using UV-visible absorption, gas chromatography technique, and chemical oxygen demand. The removal of these pollutants from water using the concrete-supported photocatalysts under UV irradiation was performed with a greater efficiency, which does not require an additional separation stage to recover the catalyst. Therefore, it would be applicable to use in industrial wastewater treatment at room temperature and atmospheric pressure within the optimized pH range.

  18. Medicineringsfejl ved generisk substitution

    Rölfing, Jan

    2012-01-01

    Generic substitution is a major cause of medical mistakes in the general population. Danish legislation obligates pharmacies to substitute prescribed medicine with the cheapest equivalent formulation, despite variations in product name, packaging, shape and colour. Consequently, medical mistakes...... occur. Scientific evidence on the consequences of generic substitution is sparse. Call upon fellow health workers to report medical mistakes to the national entities and scientific peers, in order to increase awareness and scientific evidence about the problem....

  19. Synthesis, DNA Binding, and Antiproliferative Activity of Novel Acridine-Thiosemicarbazone Derivatives

    Sinara Mônica Vitalino de Almeida

    2015-06-01

    Full Text Available In this work, the acridine nucleus was used as a lead-compound for structural modification by adding different substituted thiosemicarbazide moieties. Eight new (Z-2-(acridin-9-ylmethylene-N-phenylhydrazinecarbothioamide derivatives (3a–h were synthesized, their antiproliferative activities were evaluated, and DNA binding properties were performed with calf thymus DNA (ctDNA by electronic absorption and fluorescence spectroscopies. Both hyperchromic and hypochromic effects, as well as red or blue shifts were demonstrated by addition of ctDNA to the derivatives. The calculated binding constants ranged from 1.74 × 104 to 1.0 × 106 M−1 and quenching constants from −0.2 × 104 to 2.18 × 104 M−1 indicating high affinity to ctDNA base pairs. The most efficient compound in binding to ctDNA in vitro was (Z-2-(acridin-9-ylmethylene-N- (4-chlorophenyl hydrazinecarbothioamide (3f, while the most active compound in antiproliferative assay was (Z-2-(acridin-9-ylmethylene-N-phenylhydrazinecarbothioamide (3a. There was no correlation between DNA-binding and in vitro antiproliferative activity, but the results suggest that DNA binding can be involved in the biological activity mechanism. This study may guide the choice of the size and shape of the intercalating part of the ligand and the strategic selection of substituents that increase DNA-binding or antiproliferative properties.

  20. Metformin induces an intracellular reductive state that protects oesophageal squamous cell carcinoma cells against cisplatin but not copper-bis(thiosemicarbazones)

    Damelin, Leonard Howard; Jivan, Rupal; Veale, Robin Bruce; Rousseau, Amanda Louise; Mavri-Damelin, Demetra

    2014-01-01

    Oesophageal squamous cell carcinoma (OSCC) is a highly aggressive carcinoma with a poor survival rate. One of the most commonly used chemotherapeutic drugs, cisplatin, displays varied and often poor efficacy in vivo. Therefore, alternative, cost-effective and more efficacious treatments are required. Metformin has been previously shown to reduce proliferative rates in various carcinoma cell lines. We report for the first time, the effect of metformin on OSCC cell proliferation and show that it antagonises cisplatin-induced but not copper-bis(thiosemicarbazone)-induced cytotoxicity in OSCC cells. Cell proliferation and stage of the cell cycle were quantified by trypan blue counts and flow cytometry, respectively. All cytotoxicity measurements were made using the tetrazolium based MTT assay. Metabolic alterations to cells were determined as follows: glycolysis via a lactate dehydrogenase assay, reducing equivalents by MTT reduction and reduced intracellular thiols by monobromobimane-thiol fluorescence, and glutathione depletion using buthionine sulfoximine. Inductively coupled plasma mass spectrometry was used to quantify cisplatin-DNA adduct formation. Metformin was found to reduce cell proliferation significantly in all OSCC cell lines, with an accumulation of cells in G0/G1 phase of the cell cycle. However, metformin significantly protected OSCC cells against cisplatin toxicity. Our results indicate that a major mechanism of metformin-induced cisplatin resistance results from a significant increase in glycolysis, intracellular NAD(P)H levels with a concomitant increase in reduced intracellular thiols, leading to decreased cisplatin-DNA adduct formation. The glutathione synthesis inhibitor buthionine sulfoximine significantly ablated the protective effect of metformin. We subsequently show that the copper-bis(thiosemicarbazones), Cu-ATSM and Cu-GTSM, which are trapped in cells under reducing conditions, cause significant OSCC cytotoxicity, both alone and in

  1. Synthesis of 4-(2-substituted hydrazinyl)benzenesulfonamides and their carbonic anhydrase inhibitory effects.

    Gul, Halise Inci; Kucukoglu, Kaan; Yamali, Cem; Bilginer, Sinan; Yuca, Hafize; Ozturk, Iknur; Taslimi, Parham; Gulcin, Ilhami; Supuran, Claudiu T

    2016-08-01

    In this study, 4-(2-substituted hydrazinyl)benzenesulfonamides were synthesized by microwave irradiation and their chemical structures were confirmed by (1)H NMR, (13)CNMR, and HRMS. Ketones used were: Acetophenone (S1), 4-methylacetophenone (S2), 4-chloroacetophenone (S3), 4-fluoroacetophenone (S4), 4-bromoacetophenone (S5), 4-methoxyacetophenone (S6), 4-nitroacetophenone (S7), 2-acetylthiophene (S8), 2-acetylfuran (S9), 1-indanone (S10), 2-indanone (S11). The compounds S9, S10 and S11 were reported for the first time, while S1-S8 was synthesized by different method than literature reported using microwave irradiation method instead of conventional heating in this study. The inhibitory effects of 4-(2-substituted hydrazinyl)benzenesulfonamide derivatives (S1-S11) against hCA I and II were studied. Cytosolic hCA I and II isoenzymes were potently inhibited by new synthesized sulphonamide derivatives with Kis in the range of 1.79 ± 0.22-2.73 ± 0.08 nM against hCA I and in the range of 1.72 ± 0.58-11.64 ± 5.21 nM against hCA II, respectively.

  2. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    2010-07-01

    ... naphthalenyl-substituted azonaphthol chromium complex. 721.981 Section 721.981 Protection of Environment...-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new... naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex (PMN P-93-1631) is subject to...

  3. Effect of 4-(N,N-diethylamino)benzaldehyde thiosemicarbazone on the corrosion of aged 18 Ni 250 grade maraging steel in phosphoric acid solution

    Poornima, T.; Nayak, Jagannath; Nityananda Shetty, A.

    2011-01-01

    Highlights: → DEABT as corrosion inhibitor for maraging steel in phosphoric acid. → Inhibition efficiency increases with increase in inhibitor concentration. → Inhibition efficiency decreases with increase in temperature. → Adsorption obeys Langmuir adsorption isotherm. - Abstract: 4-(N,N-diethylamino)benzaldehyde thiosemicarbazone (DEABT) was studied for its corrosion inhibition property on the corrosion of aged 18 Ni 250 grade maraging steel in 0.67 M phosphoric acid at 30-50 deg. C by potentiodynamic polarization, EIS and weight loss techniques. Inhibition efficiency of DEABT was found to increase with the increase in DEABT concentration and decrease with the increase in temperature. The activation energy E a and other thermodynamic parameters (ΔG ads 0 , ΔH ads 0 , ΔS ads 0 ) have been evaluated and discussed. The adsorption of DEABT on aged maraging steel surface obeys the Langmuir adsorption isotherm model and the inhibitor showed mixed type inhibition behavior.

  4. THE INFLUENCE OF THIOSEMICARBAZONE 2,3-DIHYDROXYBENZALDEHYDE ON CATALYTIC CURRENTS IN THE SYSTEM MOLYBDENUM (VI – POTASSIUM CHLORATE IN ACID SULFATE SOLUTIONS

    Ludmila Chiriac

    2011-06-01

    Full Text Available The polarographic catalytic current in acid solutions of Mo(VI, thiosemicarbazone 2,3-dihydroxybenzaldehyde (TSC 2,3-DHBA and chlorate ions has been investigated. The scheme of reactions, taking place in the solutions and on the electrode, has been proposed. The increase of the catalytic current is explained by the formation of an active intermediate complex [Mo(V×TSC 2,3-DHBA (ClO-3]. The rate constant of this complex formation K = 2.56 × 106 mol-1×dm3×s-1, the activation energy Ea = 15.9 kcal×mol-1 and the reaction activation entropy ∆Sa¹ = -23.5 e.u. have been calculated.

  5. Synthesis and Characterization of 4-Benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (Containing Sulphur and Nitrogen Donor Atoms and Its Cd(II Complex

    Lakshmi Narayana Suvarapu

    2015-12-01

    Full Text Available A chelating agent, 4-benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (BBMTSC, containing sulphur and nitrogen donor atoms was synthesized and applied as a ligand for the chelation of Cd(II. Both the BBMTSC and its Cd(II complex were characterized by elemental analysis, UV-Vis absorption spectra, Fourier transform infrared spectroscopy (FT-IR, mass spectra, nuclear magnetic resonance spectroscopy (NMR, X-ray powder diffraction (XRD, and field emission scanning electron microscopy (FESEM. The FTIR spectra confirmed the formation of both BBMTSC and its Cd(II complex. XRD revealed the polycrystalline nature of the synthesized compounds. BBMTSC exhibited a flake-like micro-rod morphology, whereas the Cd(II complex had a flower-like nanorod structure.

  6. Preconcentration and atomic absorption spectrometric determination of cadmium, cobalt, copper, iron, lead, manganese, nickel and zinc in water samples using 6-methyl-2-pyridinecarboxaldehyde-4-phenyl-3-thiosemicarbazone

    Khuhawar, M.Y.; Das, P.; Dewani, V.K.

    2005-01-01

    The reagent 6-methyl-2-pyridinecarboxaldehyde-4-phenyl-3-thiosemicarbazone (MPAPT) has been examined for the pre-concentration of metal ions and determination using air acetylene flame atomic absorption spectrometer. The method is based on the complexation and extraction of cadmium (II), cobalt(III), copper(II), lead(II), nickel(II), iron(II), iron(II), manganese(II) and zinc(II) in chloroform. The metal iron are back extracted in nitric acid (1:1) or after evaporation of solvent the residue is digested in nitric acid. After necessary adjustment of volume the metal ions were determined in aqueous solution. Pre-concentration is obtained 10-25 times. Metal ions recovery was 95.4-100.8% with coefficient of variation 0.2-7.5%. The method used for the determination of metals in canal and sewerage waters, within 2-6433 mu g/L with C. V 0.-5.2%. (author)

  7. Synthesis and antimicrobial activities of new 4-thiazolidones derived from formipyridine thiosemicarbazones; Sintese e avaliacao da atividade antimicrobiana de novas 4-tiazolidinonas obtidas a partir de formilpiridina tiossemicarbazonas

    Vercoza, George Leonardo; Feitoza, Danniel Delmondes; Alves, Antonio Jose; Aquino, Thiago Mendonca de; Lima, Jose Gildo de [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Ciencias Farmaceuticas], e-mail: jgildolima@gmail.com; Araujo, Janete Magali; Cunha, Ivana Glaucia B.; Goes, Alexandre Jose da Silva [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Antibioticos

    2009-07-01

    Twelve novel 4-thiazolidinone derivatives (2a-l) have been synthesized by reacting formylpyridine thiosemicarbazones (1a-l) and anhydride maleic in toluene. Their chemical structures were confirmed by IR, {sup 1}H and {sup 13}C NMR. The new compounds were submitted to in vitro evaluation against pathogenic Gram-positive, Gram-negative bacteria and yeasts. The findings obtained showed that the compounds 2a, 2d, 2e and 2g were effective against some of the bacterial strains used, whereas the compounds 2d, 2e and 2i exhibited a moderate antifungal activity against the yeast strains evaluated. An initial structure activity relationship (SAR) was established. (author)

  8. Theoretical analysis of the binding of iron(III) protoporphyrin IX to 4-methoxyacetophenone thiosemicarbazone via DFT-D3, MEP, QTAIM, NCI, ELF, and LOL studies.

    Nkungli, Nyiang Kennet; Ghogomu, Julius Numbonui

    2017-07-01

    Thiosemicarbazones display diverse pharmacological properties, including antimalarial activities. Their pharmacological activities have been studied in depth, but little of this research has focused on their antimalarial mode of action. To elucidate this antimalarial mechanism, we investigated the nature of the interactions between iron(III) protoporphyrin IX (Fe(III)PPIX) and the thione-thiol tautomers of 4-methoxyacetophenone thiosemicarbazone (MAPTSC). Dispersion-corrected density functional theory (DFT-D3), the quantum theory of atoms in molecules (QTAIM), the noncovalent interaction (NCI) index, the electron localization function (ELF), the localized orbital locator (LOL), and thermodynamic calculations were employed in this work. Fe(III)PPIX-MAPTSC binding is expected to inhibit hemozoin formation, thereby preventing Fe(III)PPIX detoxification in plasmodia. Preliminary studies geared toward the identification of atomic binding sites in the thione-thiol tautomers of MAPTSC were carried out using molecular electrostatic potential (MEP) maps and conceptual DFT-based local reactivity indices. The thionic sulfur and the 2 N-azomethine nitrogen/thiol sulfur of, respectively, the thione and thiol tautomers of MAPTSC were identified as the most favorable nucleophilic sites for electrophilic attack. The negative values of the computed Fe(III)PPIX-MAPTSC binding energies, enthalpies, and Gibbs free energies are indicative of the existence and stability of Fe(III)PPIX-MAPTSC complexes. MAPTSC-Fe(III) coordinate bonds and strong hydrogen bonds (N-H···O) between the NH 2 group in MAPTSC and the C=O group in one propionate side chain of Fe(III)PPIX are crucial to Fe(III)PPIX-MAPTSC binding. QTAIM, NCI, ELF, and LOL analyses revealed a subtle interplay of weak noncovalent interactions dominated by dispersive-like van der Waals interactions between Fe(III)PPIX and MAPTSC that stabilize the Fe(III)PPIX-MAPTSC complexes.

  9. Anti-parasitic action and elimination of intracellular Toxoplasma gondii in the presence of novel thiosemicarbazone and its 4-thiazolidinone derivatives

    C.S. Carvalho

    2010-02-01

    Full Text Available Toxoplasma, which infects all eukaryotic cells, is considered to be a good system for the study of drug action and of the behavior of infected host cells. In the present study, we asked if thiosemicarbazone derivatives can be effective against tachyzoites and which morphological and ultrastructural features of host cells and parasites are associated with the destruction of Toxoplasma. The compounds were tested in infected Vero cell culture using concentration screens (0.1 to 20 mM. The final concentration of 1 mM was chosen for biological assay. The following results were obtained: 1 These new derivatives decreased T. gondii infection with an in vitro parasite IC50% of 0.2-0.7 mM, without a significant effect on host cells and the more efficient compounds were 2, 3 (thiosemicarbazone derivatives and 4 (thiazolidinone derivative; 2 The main feature observed during parasite elimination was continuous morphological disorganization of the tachyzoite secretory system, progressive organelle vesiculation, and then complete disruption; 3 Ultrastructural assays also revealed that progressive vesiculation in the cytoplasm of treated parasites did not occur in the host cell; 4 Vesiculation inside the parasite resulted in death, but this feature occurred asynchronously in different intracellular tachyzoites; 5 The death and elimination of T. gondii was associated with features such as apoptosis-like stage, acidification and digestion of parasites into parasitophorous vacuoles. Our results suggest that these new chemical compounds are promising for the elimination of intracellular parasites by mainly affecting tachyzoite development at 1 mM concentration for 24 h of treatment.

  10. Characterization of the anti tumoral activity of the thiosemicarbazones derived from N(4)-methyl-tolyl-2acetylpyridine And 2-pyridinoformamide and its metal complex: evaluation of the radiopharmaceutical potential

    Silva, Paulo Roberto Ornelas da

    2008-01-01

    Thiosemicarbazones have attracted great pharmacological interest because of their biological properties, such as cytotoxic activity against multiple strains of human tumors. The most studied compounds are pyridine-based because of their resemblance to pyridoxal metabolites that attach to co-enzyme B 6 -dependant enzymes. This work aimed the characterization of the anti tumoral effect of N(4)-methyl-tolyl-2-acetylpyridine and 2-pyridinoformamide-derived thiosemicarbazones and the development of a radiopharmaceutical based on a thiosemicarbazone metal complex for positron emission tomography. In the first phase of this study were synthesized twenty-one thiosemicarbazones, derived from N(4)methyl-2 acetylpyridine and 2-pyridine formamide, as well as their metal complexes (Sn, Ga and Cu). Their cytotoxic potential were evaluated against brain and breast tumor cells in vitro. Our results showed all of them presented powerful cytotoxic and antiproliferative activities against glioblastoma multiform and breast adenocarcinoma at very low concentrations (nanomolar range). Morphological alterations characteristic of apoptosis, such as cell shrinkage, chromatin condensation were observed. Copper chloride was used as control and has presented IC50 at millimolar range suggesting that copper complexation with thiosemicarbazone significantly increases (more than 1 million) the anti tumoral effect of this metal. Due to the potent anti tumoral activity of N(4)-methyl-tolyl-2-acetylpyridine derived thiosemicarbazones and the excellent properties of 64 Cu (T 1/2 = 12.7 hours, β + , β - , and EC decay), at the second part for this work it was developed a new imaging agent (radiopharmaceutical) for tumor detection by positron emission tomography (PET). The radiopharmaceuticals were produced in the nuclear reactor TRIGA-IPR-R1 from CDTN, via neutron capture reaction 63 Cu (n,γ) 64 Cu, of the copper complex N(4)-ortho-toluyl-2-acetylpyridine thiosemicarbazone (Culac). The induced

  11. Electricity/oil substitution

    Melvin, J.G.

    1980-09-01

    The extent to which electricity could substitute for imported oil in Canada is assessed and it is concluded that the bulk of projected oil imports could be displaced. This substitution of electricity for oil could be largely completed within two decades, with existing technology, using Canadian resources. The substitution of electricity for imported oil would result in relatively low energy costs and would stimulate economic growth. Energy self-sufficiency through the substitution of electricity for oil is uniquely a Canadian option; it is not open to other industrial countries. The option exists because of Canada's resources of oil sands for essential liquid fuels, hydraulic and nuclear electrical potential, and natural gas as an interim source of energy. While other countries face an energy crisis due to declining supplies of oil, Canada faces opportunities. The policies of Federal and Provincial governments, as perceived by individual decision makers, will have a major influence on Canada's ability to realize opportunities. (auth)

  12. Synthesis and structural characterization of nickel(II), cobalt(II), Zinc(II), manganese(II), cadmium(II) and uranium(VI) complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazone

    Patel, P.S.; Patel, M.M.; Ray, R.M.

    1993-01-01

    A few metal complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazones (OAOATS)/(OAPATS) with Ni(II), Co(II), Zn(II), Mn(II), Hg(II), Cd(II) and UO 2 (II) have been prepared and characterized by elemental analyses, conductivity, differential scanning calorimetry study, thermogravimetric analyses and infrared and electronic spectral measurements in conjunction with magnetic susceptibility measurements at room temperature. They have also been tested for their antimicrobial activities. (author). 24 refs., 2 tabs

  13. Synthesis and spectroscopic examination of various substituted 1,3-dibenzoylmethane, active agents for UVA/UVB photoprotection.

    Hubaud, Jean-Claude; Bombarda, Isabelle; Decome, Laetitia; Wallet, Jean-Claude; Gaydou, Emile M

    2008-08-21

    We describe the synthesis of eighteen variously substituted 1,3- dibenzoylmethane (1,3-DBM) and their change in absorption spectra depending of the nature of donor or acceptor substituents on one or the two aromatic moieties. These compounds were prepared in two steps starting from the corresponding acetophenones, phenol and benzoyl chlorides. The phenyl benzoate was obtained by condensation of benzoyl chloride with phenol in a classical way. Stirring of the phenyl benzoate and acetophenone in DMSO with powdered sodium hydroxide for a few minutes gave the dibenzoylmethane in yields depending on substituents on the phenyl rings. Changes in absorption of UVA/UVB sunlight of these molecules were observed according to the nature and the position of substituents on the phenyl rings. Molecules 2b (1-phenyl-3-(3,4,5-trimethoxyphenyl)-1,3-propanedione), 2d (1-(3,4-dimethoxyphenyl)-3-phenyl-l,3-propanedione), 2e (1-(2,3-dimethoxyphenyl)-3-phenyl-l,3-propanedione) and 2f (1-(2,3,4-trimethoxyphenyl)-3-phenyl-l,3-propanedione) were the most interesting for cosmetic applications because even after irradiation, they preserve their absorptive in UVA range and also in UVB range The other compounds are too photounstable and so can lose their protective effects. These results showed the lack of phototoxicity of these compounds and the possibility to use them as solar filters. Therefore, variously di- or tri methoxy 1,3-DBM are interesting molecules in term of photoprotection and open new prospects for UVA photostable filters.

  14. Thermal, spectral, magnetic and biological studies of thiosemicarbazones complexes with metal ions: Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO2(VI)

    Mashaly, M.M.; Seleem, H.S.; El-Behairy, M.A.; Habib, H.A.

    2004-01-01

    Thiosemicarbazones ligands, isatin-3-thiosemicarbazone(HIT) and N-acetylisatin-3-thiosemicarbazone (HAIT), which have tridentate ONN coordinating sites were prepared. The complexes of both ligands with Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO 2 (VI) ions were isolated. The ligands and their metal complexes were characterized by elemental analysis, IR, UV-Vis and mass spectra, also by conductance, magnetic moment and TG-DSC measurements. All the transition metal complexes have octahedral configurations, except Cu-complexes which have planar geometry and the UO 2 (VI) complexes which have coordination number 8 and may acquire the distorted dodecahedral geometry. Thermal studies explored the possibility of obtaining new complexes. Inversion from octahedral to square-planar configuration occurred upon heating the parent Ni-HIAT complex to form the corresponding pyrolytic product. The antifungal activity against the tested organisms showed that some metal complexes enhanced the activity with respect to the parent ligands. (author)

  15. Preparation and characterization of a supported system of Ni2P/Ni12P5 nanoparticles and their use as the active phase in chemoselective hydrogenation of acetophenone

    Costa, Dolly C.; Soldati, Analía L.; Pecchi, Gina; Bengoa, José Fernando; Marchetti, Sergio Gustavo; Vetere, Virginia

    2018-05-01

    Ni2P/Ni12P5 nanoparticles were obtained by thermal decomposition of nickel organometallic salt at low temperature. The use of different characterization techniques allowed us to determine that this process produced a mixture of two nickel phosphide phases: Ni2P and Ni12P5. These nickel phosphides nanoparticles, supported on mesoporous silica, showed activity and high selectivity for producing the hydrogenation of the acetophenone carbonyl group to obtain 1-phenylethanol. This is a first report that demonstrates the ability of supported Ni2P/Ni12P5 nanoparticles to produce the chemoselective hydrogenation of acetophenone. We attribute these special catalytic properties to the particular geometry of the Ni–P sites on the surface of the nanoparticles. This is an interesting result because the nickel phosphides have a wide composition range (from Ni3P to NiP3), with different crystallographic structures, therefore we think that different phases could be active and selective to hydrogenate many important molecules with more than one functional group.

  16. Bone substitute biomaterials

    Mallick, K

    2014-01-01

    Bone substitute biomaterials are fundamental to the biomedical sector, and have recently benefitted from extensive research and technological advances aimed at minimizing failure rates and reducing the need for further surgery. This book reviews these developments, with a particular focus on the desirable properties for bone substitute materials and their potential to encourage bone repair and regeneration. Part I covers the principles of bone substitute biomaterials for medical applications. One chapter reviews the quantification of bone mechanics at the whole-bone, micro-scale, and non-scale levels, while others discuss biomineralization, osteoductivization, materials to fill bone defects, and bioresorbable materials. Part II focuses on biomaterials as scaffolds and implants, including multi-functional scaffolds, bioceramics, and titanium-based foams. Finally, Part III reviews further materials with the potential to encourage bone repair and regeneration, including cartilage grafts, chitosan, inorganic poly...

  17. [Delegation yes, substitution no!].

    Schroeder, A

    2014-08-01

    The aging of society leads on the one hand to increasing case numbers and on the other hand to a reduction in the number of physicians available for patient treatment. The delegation and substitution of medical duties as a tried and tested method is increasingly being recommended in order to compensate for the lack of physicians. The Berufsverband der Deutschen Urologen (BDU, Professional Association of German Urologists) supports the guiding principle of the Bundesärztekammer (Federal Medical Council) of "delegation yes, substitution no" and rejects a substitution of medical duties by non-medical academic health personnel. Against the background of the demographic changes, the increasing need for treatment and the current deficiency of junior physicians, a more extensive inclusion of well-qualified and experienced non-medical personnel by the delegation of medically responsible duties (medical scope of practice) can be an appropriate measure to maintain a good medical service in practices, hospitals and nursing homes.

  18. Aryl substitution of pentacenes

    Andreas R. Waterloo

    2014-07-01

    Full Text Available A series of 11 new pentacene derivatives has been synthesized, with unsymmetrical substitution based on a trialkylsilylethynyl group at the 6-position and various aryl groups appended to the 13-position. The electronic and physical properties of the new pentacene chromophores have been analyzed by UV–vis spectroscopy (solution and thin films, thermoanalytical methods (DSC and TGA, cyclic voltammetry, as well as X-ray crystallography (for 8 derivatives. X-ray crystallography has been specifically used to study the influence of unsymmetrical substitution on the solid-state packing of the pentacene derivatives. The obtained results add to our ability to better predict substitution patterns that might be helpful for designing new semiconductors for use in solid-state devices.

  19. Aryl substitution of pentacenes

    Waterloo, Andreas R; Sale, Anna-Chiara; Lehnherr, Dan; Hampel, Frank

    2014-01-01

    Summary A series of 11 new pentacene derivatives has been synthesized, with unsymmetrical substitution based on a trialkylsilylethynyl group at the 6-position and various aryl groups appended to the 13-position. The electronic and physical properties of the new pentacene chromophores have been analyzed by UV–vis spectroscopy (solution and thin films), thermoanalytical methods (DSC and TGA), cyclic voltammetry, as well as X-ray crystallography (for 8 derivatives). X-ray crystallography has been specifically used to study the influence of unsymmetrical substitution on the solid-state packing of the pentacene derivatives. The obtained results add to our ability to better predict substitution patterns that might be helpful for designing new semiconductors for use in solid-state devices. PMID:25161729

  20. Muon substituted free radicals

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Gygax, F.N.; Brinkman, G.A.; Louwrier, P.W.F.; McKenna, D.; Ramos, M.; Webster, B.C.

    1984-01-01

    Spin polarized energetic positive muons are injected as magnetic probes into unsaturated organic liquids. They are implemented via fast chemical processes ( -10 s) in various molecules. Of particular interest among these are muonium substituted free radicals. The technique allows determination of accurate rate coefficients for fast chemical reactions of radicals. Furthermore, radiochemical processes occuring in picoseconds after injection of the muon are studied. Of fundamental interest are also the structural and dynamical implications of substituting a proton by a muon, or in other terms, a hydrogen atom by a muonium atom. Selected examples for each of these three types of experiments are given. (Auth.)

  1. Hazardous solvent substitution

    Twitchell, K.E.

    1995-01-01

    This article is an overview of efforts at INEL to reduce the generation of hazardous wastes through the elimination of hazardous solvents. To aid in their efforts, a number of databases have been developed and will become a part of an Integrated Solvent Substitution Data System. This latter data system will be accessible through Internet

  2. Carbolanthanation of substituted alkynes

    Kalinin, V.N.; Kazimirchuk, E.I.; Vitt, S.V.; Khandozhko, V.N.; Beletskaya, I.P.

    1993-01-01

    Using the reaction between CH 3 YbI and substituted alkynes as an example, agents can enter into carbolanthanation reaction via transfer of a methyl group to carbon atom of acetylene bond with the production of a new olefin carbanion. 5 refs.; 1 fig.; 3 tabs

  3. [Currently available skin substitutes].

    Oravcová, Darina; Koller, Ján

    2014-01-01

    The current trend of burn wound care has shifted to more holistic approach of improvement in the long-term form and function of the healed burn wounds and quality of life. Autologous split or full-thickness skin graft are the best definitive burn wound coverage, but it is constrained by the limited available sources, especially in major burns. Donor site morbidities in term of additional wounds and scarring are also of concern of the autograft application. This has demanded the emergence of various skin substitutes in the management of acute burn injury as well as post burn reconstructions. This paper reviews currently available skin substitutes, produced in not for-profit skin banks as well as commercially available. They are divided according to type of material included, as biological, biosynthetic and synthetic and named respectively.

  4. Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

    Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

    2008-09-01

    The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate ( I), bromo-(2-formylpyridinethiosemicarbazono)copper ( II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate ( III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I III at a concentration of 10-5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

  5. Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

    Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

    2008-01-01

    The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate (I), bromo-(2-formylpyridinethiosemicarbazono)copper (II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate (III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I-III at a concentration of 10 -5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

  6. Ni(II, Pd(II and Pt(II complexes with ligand containing thiosemicarbazone and semicarbazone moiety: synthesis, characterization and biological investigation

    SULEKH CHANDRA

    2008-07-01

    Full Text Available The synthesis of nickel(II, palladium(II and platinum(II complexes with thiosemicarbazone and semicarbazone of p-tolualdehyde are reported. All the new compounds were characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, 1H-NMR, IR and electronic spectral studies. Based on the molar conductance measurements in DMSO, the complexes may be formulated as [Ni(L2Cl2] and [M(L2]Cl2 (where M = Pd(II and Pt(II due to their non-electrolytic and 1:2 electrolytic nature, respectively. The spectral data are consistent with an octahedral geometry around Ni(II and a square planar geometry for Pd(II and Pt(II, in which the ligands act as bidentate chelating agents, coordinated through the nitrogen and sulphur/oxygen atoms. The ligands and their metal complexes were screened in vitro against fungal species Alternaria alternata, Aspergillus niger and Fusarium odum, using the food poison technique.

  7. Simultaneous spectrophotometric determination of copper, cobalt, nickel and iron in foodstuffs and vegetables with a new bis thiosemicarbazone ligand using chemometric approaches.

    Rohani Moghadam, Masoud; Poorakbarian Jahromi, Sayedeh Maria; Darehkordi, Ali

    2016-02-01

    A newly synthesized bis thiosemicarbazone ligand, (2Z,2'Z)-2,2'-((4S,5R)-4,5,6-trihydroxyhexane-1,2-diylidene)bis(N-phenylhydrazinecarbothioamide), was used to make a complex with Cu(2+), Ni(2+), Co(2+) and Fe(3+) for their simultaneous spectrophotometric determination using chemometric methods. By Job's method, the ratio of metal to ligand in Ni(2+) was found to be 1:2, whereas it was 1:4 for the others. The effect of pH on the sensitivity and selectivity of the formed complexes was studied according to the net analyte signal (NAS). Under optimum conditions, the calibration graphs were linear in the ranges of 0.10-3.83, 0.20-3.83, 0.23-5.23 and 0.32-8.12 mg L(-1) with the detection limits of 2, 3, 4 and 10 μg L(-1) for Cu(2+), Co(2+), Ni(2+) and Fe(3+) respectively. The OSC-PLS1 for Cu(2+) and Ni(2+), the PLS1 for Co(2+) and the PC-FFANN for Fe(3+) were selected as the best models. The selected models were successfully applied for the simultaneous determination of elements in some foodstuffs and vegetables. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Highly efficient ultrasonic-assisted removal of Hg(II) ions on graphene oxide modified with 2-pyridinecarboxaldehyde thiosemicarbazone: Adsorption isotherms and kinetics studies.

    Tadjarodi, Azadeh; Moazen Ferdowsi, Somayeh; Zare-Dorabei, Rouholah; Barzin, Ahmad

    2016-11-01

    A novel adsorbent, based on modifying graphene oxide (GO) chemically with 2-pyridinecarboxaldehyde thiosemicarbazone (2-PTSC) as ligand, was designed by facile process for removal of Hg(II) from aqueous solution. Characterization of the adsorbent was performed using various techniques, such as FT-IR, XRD, XPS, SEM and AFM analysis. The adsorption capacity was affected by variables such as adsorbent dosage, pH solution, Hg(2+) initial concentration and sonicating time. These variables were optimized by rotatable central composite design (CCD) under response surface methodology (RSM). The predictive model for Hg(II) adsorption was constructed and applied to find the best conditions at which the responses were maximized. In this conditions, the adsorption capacity of this adsorbent for Hg(2+) ions was calculated to be 309mgg(-1) that was higher than that of GO. Appling the ultrasound power combined with adsorption method was very efficient in shortening the removal time of Hg(2+) ions by enhancing the dispersion of adsorbent and metal ions in solution and effective interactions among them. The adsorption process was well described by second-order kinetic and Langmuir isotherm model in which the maximum adsorption capacity (Qm) was found to be 555mgg(-1) for adsorption of Hg(2+) ions over the obtained adsorbent. The performance of adsorbent was examined on the real wastewaters and confirmed the applicability of adsorbent for practical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. DNA binding, antioxidant, cytotoxicity (MTT, lactate dehydrogenase, NO), and cellular uptake studies of structurally different nickel(II) thiosemicarbazone complexes: synthesis, spectroscopy, electrochemistry, and X-ray crystallography.

    Prabhakaran, R; Kalaivani, P; Huang, R; Poornima, P; Vijaya Padma, V; Dallemer, F; Natarajan, K

    2013-02-01

    Three new nickel(II) thiosemicarbazone complexes have been synthesized and characterized by analytical, spectral, and single-crystal X-ray diffraction studies. In complex 1, the ligand 2-hydroxy-1-naphthaldehydethiosemicarbazone coordinated as a monobasic tridentate donor, whereas in complexes 2 and 3, the ligands salicylaldehyde-4(N)-ethylthiosemicarbazone and 2-hydroxy-1-naphthaldehyde-4(N)-ethylthiosemicarbazone coordinated as a dibasic tridentate donor. The DNA binding ability of the complexes in calf thymus DNA was explored by absorption and emission titration experiments. The antioxidant property of the new complexes was evaluated to test their free-radical scavenging ability. In vitro cytotoxicity assays were performed for the new complexes in A549 and HepG2 cell lines. The new compounds overcome cisplatin resistance in the A549 cell line and they were also active in the HepG2 cell line. The cellular uptake study showed the accumulation of the complexes in tumor cells depended on the nature of the ligand attached to the nickel ion.

  10. Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

    Chumakov, Yu. M., E-mail: chumakov.xray@phys.asm.md [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Tsapkov, V. I. [State University of Moldova (Moldova, Republic of); Jeanneau, E. [Universite Claude Bernard, Laboratoire des Multimateriaux et Interfaces (France); Bairac, N. N. [State University of Moldova (Moldova, Republic of); Bocelli, G. [National Research Council (IMEM-CNR), Institute of Materials for Electronics and Magnetism (Italy); Poirier, D.; Roy, J. [Centre Hospitalier Universitaire de Quebec (CHUQ) (Canada); Gulea, A. P. [State University of Moldova (Moldova, Republic of)

    2008-09-15

    The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate (I), bromo-(2-formylpyridinethiosemicarbazono)copper (II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate (III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I-III at a concentration of 10{sup -5} mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

  11. Hexavalent Chromium Substitution Projects

    2011-05-12

    Hexavalent Chromium Substitution Projects Date (12 May 2011) Gene McKinley ASC/WNV (937) 255-3596 Gene.McKinley@wpafb.af.mil Aeronautical Systems...valid OMB control number. 1. REPORT DATE 12 MAY 2011 2. REPORT TYPE 3. DATES COVERED 00-00-2011 to 00-00-2011 4. TITLE AND SUBTITLE Hexavalent ...A-10) – AETC (T-6, T-38 and T1A) • Both Cr Primers & Non-Cr primers as well as Cr Surface Treatment – F-22 8 Non- Chrome Tie-coat & touch-up

  12. Muonium substituted molecules

    Cox, S.F.J.

    1990-12-01

    The manner in which Muon Spin Rotation and Level Crossing Resonance are used to characterise muonium substituted organic radicals is described, and illustrated with spectra for the ethyl radical and related species. Comparison with electron spin resonance data for the unsubstituted radicals reveals significant structural and hyperfine isotope effects which can be traced to the effects of zero point motion. The first comparable results for a diamagnetic species, exhibiting a quadrupole isotope effect by comparison with conventional nuclear quadrupole resonance data, are presented and discussed. (author)

  13. Resources, recycle, and substitution

    Wymer, R.G.

    A two-fold strategy appears necessary to ensure that the resource needs of the developed and developing nations are met. First, recycle and substitution must be encouraged in those instances where they do find application. Although these measures have limited applicability, they may be of vital importance in those instances where they do apply; in any event, they buy time. Second, practical and economical technologies must be developed to exploit the lower-grade and marginal ores and the oftentimes abundant but highly refractory ores, as well as to greatly increase the recovery of secondary elements present in the ores - elements whose form and amounts in the ores make them economically unrecoverable by themselves, but which are economically recoverable as by-products. It is often the case that if these elements are not recovered during the initial mining and milling operations, they are rendered unrecoverable, in a practical sense, forever. Furthermore, they may even become environmental pollutants. Specific examples of recovery from refractory ores, by-product recovery, and recycle are given. Also, some suggestions of substitutes for important resources are tabulated

  14. Synthesis, characterization, crystal structure and antibacterial activity of new sulfur-bridged dinuclear silver(I) thiosemicarbazone complex [Ag.sub.2./sub.(PPh.sub.3./sub.).sub.2./sub.(μ-S-Brcatsc).sub.2./sub.(η.sup.1./sup.-S-Brcatsc).sub.2./sub.](NO.sub.3./sub.).sub.2./sub..

    Shahsavani, E.; Khalaji, A.D.; Feizi, N.; Kučeráková, Monika; Dušek, Michal

    2015-01-01

    Roč. 429, Apr (2015), 61-66 ISSN 0020-1693 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : sulfur-bridged dinuclear silver(I) * thiosemicarbazone complex * single-crystal * distorted tetrahedron * antibacterial activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.918, year: 2015

  15. Voltammetric behavior, biocidal effect and synthesis of some new nanomeric fused cyclic thiosemicarbazones and their mercuric(II salts

    M.S.T. Makki

    2014-11-01

    Full Text Available New nanomeric 3-thioxo-5-methoxy-4,5-dihydro-6-methyl-9-unsubstituted/substituted-1,2,4-triazino[5,6-b]indoles (2a–c and 3-thioxo-5-methoxy-4,5-dihydro-6,7-dihydroxy-1,2,4-triaino[5,6]-cyclobut-6-ene (3 were prepared via reaction of thiosemicarbazide with 5-unsubstitutedand/substituted-indol-2,3-diones and/or 3,4-dihydroxycyclobutane-1,2-dione in methanol–concentrated HCl at room temperature. A series of mercury(II–ligand salts e.g. compound 4b and Hg(II complexes 5a,b and 6 of cyclic Schiff base were prepared. Structures of these compounds were established by elemental analysis and spectral measurements. The redox characteristics of selected compounds were studied for use as chelating agents for stripping voltammetric determination of mercuric(II ions in aqueous media. The compounds were also screened for their use as molluscicidal agents against Biomophalaria Alexandrina Snails responsible for Bilhariziasis.

  16. Copper complex N(4)-ortho-toluyl-2-acetylpyridine thiosemicarbazone - ({sup 64}Cu)(H2Ac4oT)Cl - internal dosimetry: animal model and human extrapolation

    Rodrigues, Josianne L.; Silva, Paulo R.O.; Santos, Raquel G.; Ferreira, Andrea V., E-mail: jlr@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2011-07-01

    Thiosemicarbazones have attracted great pharmacological interest because of their biological properties, such as cytotoxic activity against multiple strains of human tumors. Due to the excellent properties of {sup 64}Cu, the copper complex N(4)-ortho-toluyl-2-acetylpyridine thiosemicarbazone (({sup 64}Cu)(H2Ac4oT)Cl) was developed for tumor detection by positron emission tomography. The radiopharmaceuticals were produced in the nuclear reactor TRIGA-IPR-R1 from CDTN. At the present work, ({sup 64}Cu)(H2Ac4oT)Cl biokinetic data (evaluated in mice bearing Ehrlich tumor) were treated by MIRD formalism to perform Internal Dosimetry studies. Doses in several organs of mice were determinate, as well as in implanted tumor, for ({sup 64}Cu)(H2Ac4oT)Cl. Doses results obtained for animal model were extrapolated to humans assuming a similar concentration ratio among various tissues between mouse and human. In the extrapolation, it was used human organ masses from Cristy/Eckerman phantom. Both penetrating and non-penetrating radiation from {sup 64}Cu in the tissue were considered in dose calculations. (author)

  17. N-methylisatin-beta-thiosemicarbazone derivative (SCH 16 is an inhibitor of Japanese encephalitis virus infection in vitro and in vivo

    Sriram D

    2008-05-01

    Full Text Available Abstract Background During the early and mid part of 20th century, several reports described the therapeutic effects of N-methylisatin-β-Thiosemicarbazone (MIBT against pox viruses, Maloney leukemia viruses and recently against HIV. However, their ability to inhibit flavivirus replication has not been investigated. Hence the present study was designed to evaluate the antiviral activity of 14 MIBT derivatives against Flaviviruses that are prevalent in India such as Japanese Encephalitis Virus (JEV, Dengue-2 (Den-2 and West Nile viruses (WNV. Results Amongst the fourteen Mannich bases of MIBT derivatives tested one compound – SCH 16 was able to completely inhibit in vitro Japanese encephalitis virus (JEV and West Nile virus (WNV replication. However no antiviral activity of SCH 16 was noted against Den-2 virus replication. This compound was able to inhibit 50% of the plaques (IC50 produced by JEV and WNV at a concentration of 16 μgm/ml (0.000025 μM and 4 μgm/ml (0.000006 μM respectively. Furthermore, SCH 16 at a concentration of 500 mg/kg body weight administered by oral route twice daily was able to completely (100% prevent mortality in mice challenged with 50LD50 JEV by the peripheral route. Our experiments to understand the mechanism of action suggest that SCH 16 inhibited JEV replication at the level of early protein translation. Conclusion Only one of the 14 isatin derivatives -SCH 16 exhibited antiviral action on JEV and WNV virus infection in vitro. SCH 16 was also found to completely inhibit JEV replication in vivo in a mouse model challenged peripherally with 50LD50 of the virus. These results warrant further research and development on SCH 16 as a possible therapeutic agent.

  18. Studies of zinc(II in pharmaceutical and biological samples by extractive spectrophotometry: using pyridoxal-4-phenyl-3-thiosemicarbazone as chelating reagent

    Sarma L. Subramanyam

    2006-01-01

    Full Text Available Pyridoxal-4-phenyl-3-thiosemicarbazone (PPT is proposed as a new sensitive reagent for the sensitive extractive spectrophotometric determination of zinc(II. PPT reacts with zinc(II in the pH range 5.0-6.0 to form a yellow colored complex, which was well extracted into n-butanol. The absorbance value of Zn(II-PPT complex was measured at different intervals of time at 430 nm, to ascertain the stability of the complex. It was observed that the color development was instantaneous and stable for more than 48 h. The system obeyed Beer's law up to 6.0 µg mL-1 of zinc(II, with an excellent linearity in terms of correlation coefficient value of 0.999. The molar absorptivity and Sandell's sensitivity of the extracted species is 1.6 X 10(4 L mol-1 cm-1 and 4.085 X 10-3 µg cm-2 at 430 nm. The detection limit of the method is 0.04 µg mL-1. To assess precision of the method, determinations were carried out at different concentrations; the relative standard deviation does not exceed 3.1%. The composition of the zinc(II complex with PPT was studied by the method of Job's continuous variation, molar ratio method, Asmus' method and slope ratio method. It has been satisfactorily applied for the determination of zinc(II, when present alone or in presence of diverse ions, which are usually associated with zinc(II in pharmaceutical and biological samples. Various certified reference materials (NIST 1573, NBS 1572 and NIST SRM 8435 have been tested for the determination of zinc for evaluating the accuracy of the developed method. The results of the proposed method are in agreement with flame atomic absorption spectometry.

  19. A phase 2 consortium (P2C) trial of 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP) for advanced adenocarcinoma of the pancreas

    Attia, Steven; Kolesar, Jill; Mahoney, Michelle R.; Pitot, Henry C.; Laheru, Daniel; Heun, James; Huang, Wei; Eickhoff, Jens; Erlichman, Charles

    2015-01-01

    Summary 3-Aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP, Triapine®) is a novel small molecule inhibitor of ribonucleotide reductase (RR) with clinical signs of activity in pancreatic cancer. Therefore, the Phase 2 Consortium (P2C) initiated a trial (two single stage studies with planned interim analysis) of 3-AP at 96 mg/m2 intravenously days 1–4 and 15–18 of a 28-day cycle in both chemotherapy-naive and gemcitabine-refractory (GR) patients with advanced pancreatic cancer. The primary endpoint was survival at six months (chemotherapy-naive) and four months (GR). Secondary endpoints were toxicity, response, overall survival, time to progression and mechanistic studies. Fifteen patients were enrolled including one chemotherapy-naïve and 14 GR. The chemotherapy-naïve patient progressed during cycle 1 with grade 3 and 4 toxicities. Of 14 GR patients, seven received two cycles, six received one cycle and one received eight cycles. Progression precluded further treatment in 11 GR patients. Additionally, one died of an ileus in cycle 1 considered related to treatment and two stopped treatment due to toxicity. Five GR patients had grade 4 toxicities possibly related to 3-AP and six GR patients had grade 3 fatigue. Toxicities and lack of meaningful clinical benefit prompted early study closure. Four-month survival in GR patients was 21% (95% CI: 8–58%). Correlative studies confirmed that 3-AP increased the percentage of S-phase buccal mucosal cells, the presence of multidrug resistance gene polymorphisms appeared to predict leukopenia, and baseline pancreatic tumor RR M2 expression was low relative to other tumors treated with 3-AP. In conclusion, this regimen appears inactive against predominantly GR pancreatic cancer. RR M2 protein may not have a critical role in the malignant potential of pancreatic cancer. PMID:18278438

  20. Currency substitution in Eastern Europe

    van Aarle, B.; Budina, N.

    1995-01-01

    Monetary instability during the transition process from a command economy to a market economy has induced a considerable increase in currency substitution in Eastern Europe. Currency substitution itself affects monetary stability since it reduces the stability of velocity. This paper investigates

  1. Why Does Trigonometric Substitution Work?

    Cunningham, Daniel W.

    2018-01-01

    Modern calculus textbooks carefully illustrate how to perform integration by trigonometric substitution. Unfortunately, most of these books do not adequately justify this powerful technique of integration. In this article, we present an accessible proof that establishes the validity of integration by trigonometric substitution. The proof offers…

  2. Substitution of matrices over rings

    Hautus, M.L.J.

    1995-01-01

    For a given commutative ring with an identity element, we define and study the substitution of a matrix with entries in into a matrix polynomial or rational function over . A Bezout-type remainder theorem and a "partial-substitution rule" are derived and used to obtain a number of results. The

  3. Substitution in recreation choice behavior

    George L. Peterson; Daniel J. Stynes; Donald H. Rosenthal; John F. Dwyer

    1985-01-01

    This review discusses concepts and theories of substitution in recreation choice. It brings together the literature of recreation research, psychology, geography, economics, and transportation. Parallel and complementary developments need integration into an improved theory of substitution. Recreation decision behavior is characterized as a nested or sequential choice...

  4. Biological background of dermal substitutes

    van der Veen, V. C.; van der Wal, M.B.; van Leeuwen, M.C.; Ulrich, M.; Middelkoop, E.

    2010-01-01

    Dermal substitutes are of major importance in treating full thickness skin defects, both in acute and chronic wounds. In this review we will outline specific requirements of three classes of dermal substitutes:-natural biological materials, with a more or less intact extracellular matrix

  5. N-substituted iminodiacetic acids

    Nunn, A.; Loberg, M.

    1982-01-01

    The chemical preparation of several new N-substituted iminodiacetic acid derivatives are described. These compounds when complexed with sup(99m)Tc provide useful radiopharmaceuticals for the external imaging of the hepatobiliary system. (U.K.)

  6. Stability of the resistance to the thiosemicarbazone derived from 5,6-dimethoxy-1-indanone, a non-nucleoside polymerase inhibitor of bovine viral diarrhea virus.

    Castro, Eliana F; Campos, Rodolfo H; Cavallaro, Lucía V

    2014-01-01

    Bovine viral diarrhea virus (BVDV) is the prototype Pestivirus. BVDV infection is distributed worldwide and causes serious problems for the livestock industry. The thiosemicarbazone of 5,6-dimethoxy-1-indanone (TSC) is a non-nucleoside polymerase inhibitor (NNI) of BVDV. All TSC-resistant BVDV variants (BVDV-TSCr T1-5) present an N264D mutation in the NS5B gene (RdRp) whereas the variant BVDV-TSCr T1 also presents an NS5B A392E mutation. In the present study, we carried out twenty passages of BVDV-TSCr T1-5 in MDBK cells in the absence of TSC to evaluate the stability of the resistance. The viral populations obtained (BVDV R1-5) remained resistant to the antiviral compound and conserved the mutations in NS5B associated with this phenotype. Along the passages, BVDV R2, R3 and R5 presented a delay in the production of cytopathic effect that correlated with a decrease in cell apoptosis and intracellular accumulation of viral RNA. The complete genome sequences that encode for NS2 to NS5B, Npro and Erns were analyzed. Additional mutations were detected in the NS5B of BVDV R1, R3 and R4. In both BVDV R2 and R3, most of the mutations found were localized in NS5A, whereas in BVDV R5, the only mutation fixed was NS5A V177A. These results suggest that mutations in NS5A could alter BVDV cytopathogenicity. In conclusion, the stability of the resistance to TSC may be due to the fixation of different compensatory mutations in each BVDV-TSCr. During their replication in a TSC-free medium, some virus populations presented a kind of interaction with the host cell that resembled a persistent infection: decreased cytopathogenicity and viral genome synthesis. This is the first report on the stability of antiviral resistance and on the evolution of NNI-resistant BVDV variants. The results obtained for BVDV-TSCr could also be applied for other NNIs.

  7. Stability of the resistance to the thiosemicarbazone derived from 5,6-dimethoxy-1-indanone, a non-nucleoside polymerase inhibitor of bovine viral diarrhea virus.

    Eliana F Castro

    Full Text Available Bovine viral diarrhea virus (BVDV is the prototype Pestivirus. BVDV infection is distributed worldwide and causes serious problems for the livestock industry. The thiosemicarbazone of 5,6-dimethoxy-1-indanone (TSC is a non-nucleoside polymerase inhibitor (NNI of BVDV. All TSC-resistant BVDV variants (BVDV-TSCr T1-5 present an N264D mutation in the NS5B gene (RdRp whereas the variant BVDV-TSCr T1 also presents an NS5B A392E mutation. In the present study, we carried out twenty passages of BVDV-TSCr T1-5 in MDBK cells in the absence of TSC to evaluate the stability of the resistance. The viral populations obtained (BVDV R1-5 remained resistant to the antiviral compound and conserved the mutations in NS5B associated with this phenotype. Along the passages, BVDV R2, R3 and R5 presented a delay in the production of cytopathic effect that correlated with a decrease in cell apoptosis and intracellular accumulation of viral RNA. The complete genome sequences that encode for NS2 to NS5B, Npro and Erns were analyzed. Additional mutations were detected in the NS5B of BVDV R1, R3 and R4. In both BVDV R2 and R3, most of the mutations found were localized in NS5A, whereas in BVDV R5, the only mutation fixed was NS5A V177A. These results suggest that mutations in NS5A could alter BVDV cytopathogenicity. In conclusion, the stability of the resistance to TSC may be due to the fixation of different compensatory mutations in each BVDV-TSCr. During their replication in a TSC-free medium, some virus populations presented a kind of interaction with the host cell that resembled a persistent infection: decreased cytopathogenicity and viral genome synthesis. This is the first report on the stability of antiviral resistance and on the evolution of NNI-resistant BVDV variants. The results obtained for BVDV-TSCr could also be applied for other NNIs.

  8. Commercial formalin substitutes for histopathology

    Prentø, P; Lyon, H

    1997-01-01

    We compared the performance of six commercial fixatives proposed to be formalin substitutes with the performance of buffered formalin, Clarke's ethanol-acetic acid, and ethanol, using rat liver, small intestine, and kidney. We investigated the rate of penetration, mode of fixation, extent of prot...... was obtained by combining formalin fixation with antigen retrieval. We conclude that none of the proposed commercial substitutes for buffered formalin are adequate for critical histology or histopathology....

  9. Stores, Prices, and Currency Substitution

    Gabriele, Camera; Winkler, Johannes

    1999-01-01

    We study endogenous currency substitution in a decentralized trade environment. Sellers maximize profits from sales of imperfectly substitutable goods by posting prices in either one of two currencies. A unique symmetric equilibrium exists where goods are priced only in the local currency. This occurs if foreign trade is sporadic, there is sufficient but not excessive liquidity, and discounting is low. Excess or scarcity of liquidity, however, induces sellers to extract all surplus from bu...

  10. Substitution reactions of technetium complexes

    Omori, T.

    1997-01-01

    Substitution reactions of a series of technetium complexes are considered in comparison with corresponding reactions of rhenium. Rhenium and technetium complexes are rather inert in substitution reactions, the latter are characterized by greater rate constants when they proceed according to dissociative mechanism. In rare cases when k Tc /k Re id little it is assumed that the reaction proceeds according to the associative mechanism. (author)

  11. Characterization of the anti tumoral activity of the thiosemicarbazones derived from N(4)-methyl-tolyl-2acetylpyridine And 2-pyridinoformamide and its metal complex: evaluation of the radiopharmaceutical potential; Caracterizacao da atividade antitumoral das tiossemicarbazonas derivadas de N(4)-metil-toluil-2-acetilpiridina e 2-piridinoformamida e seus complexos metalicos: avaliacao do potencial radiofarmaceutico

    Silva, Paulo Roberto Ornelas da

    2008-07-01

    Thiosemicarbazones have attracted great pharmacological interest because of their biological properties, such as cytotoxic activity against multiple strains of human tumors. The most studied compounds are pyridine-based because of their resemblance to pyridoxal metabolites that attach to co-enzyme B{sub 6}-dependant enzymes. This work aimed the characterization of the anti tumoral effect of N(4)-methyl-tolyl-2-acetylpyridine and 2-pyridinoformamide-derived thiosemicarbazones and the development of a radiopharmaceutical based on a thiosemicarbazone metal complex for positron emission tomography. In the first phase of this study were synthesized twenty-one thiosemicarbazones, derived from N(4)methyl-2 acetylpyridine and 2-pyridine formamide, as well as their metal complexes (Sn, Ga and Cu). Their cytotoxic potential were evaluated against brain and breast tumor cells in vitro. Our results showed all of them presented powerful cytotoxic and antiproliferative activities against glioblastoma multiform and breast adenocarcinoma at very low concentrations (nanomolar range). Morphological alterations characteristic of apoptosis, such as cell shrinkage, chromatin condensation were observed. Copper chloride was used as control and has presented IC50 at millimolar range suggesting that copper complexation with thiosemicarbazone significantly increases (more than 1 million) the anti tumoral effect of this metal. Due to the potent anti tumoral activity of N(4)-methyl-tolyl-2-acetylpyridine derived thiosemicarbazones and the excellent properties of {sup 64}Cu (T{sub 1/2} = 12.7 hours, {beta}{sup +}, {beta}{sup -}, and EC decay), at the second part for this work it was developed a new imaging agent (radiopharmaceutical) for tumor detection by positron emission tomography (PET). The radiopharmaceuticals were produced in the nuclear reactor TRIGA-IPR-R1 from CDTN, via neutron capture reaction {sup 63}Cu (n,{gamma}) {sup 64}Cu, of the copper complex N(4)-ortho-toluyl-2

  12. Approaches in Substitution of Organic Solvents

    Jacobsen, Thomas

    2000-01-01

    In substitution of harmful chemicals or products with less harmful or harmless ones, there are different approaches according to the different situations, the technical requirements to the substitutes, and the goals for the substitution. Three different cases are presented. The substitution process...

  13. 40 CFR 721.2577 - Copper complex of (substituted sulfonaphthyl azo substituted phenyl) disulfonaphthyl azo, amine...

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Copper complex of (substituted... Copper complex of (substituted sulfonaphthyl azo substituted phenyl) disulfonaphthyl azo, amine salt... substances identified generically as copper complex of (substituted sulfonaphthyl azo substituted phenyl...

  14. Substituted decision making: elder guardianship.

    Leatherman, Martha E; Goethe, Katherine E

    2009-11-01

    The goal of this column is to help experienced clinicians navigate the judicial system when they are confronted with requests for capacity evaluations that involve guardianship (conservatorship). The interface between the growing elderly medical population and increasing requests for substituted decision making is becoming more complex. This column will help practicing psychiatrists understand the medical, legal, and societal factors involved in adult guardianship. Such understanding is necessary in order to effectively perform guardianship evaluations and adequately inform courts, patients, and families about the psychiatric diagnoses central to substituted decision making.

  15. Substitution determination of Fmoc‐substituted resins at different wavelengths

    Kley, Markus; Bächle, Dirk; Loidl, Günther; Meier, Thomas; Samson, Daniel

    2017-01-01

    In solid‐phase peptide synthesis, the nominal batch size is calculated using the starting resin substitution and the mass of the starting resin. The starting resin substitution constitutes the basis for the calculation of a whole set of important process parameters, such as the number of amino acid derivative equivalents. For Fmoc‐substituted resins, substitution determination is often performed by suspending the Fmoc‐protected starting resin in 20% (v/v) piperidine in DMF to generate the dibenzofulvene–piperidine adduct that is quantified by ultraviolet–visible spectroscopy. The spectrometric measurement is performed at the maximum absorption wavelength of the dibenzofulvene–piperidine adduct, that is, at 301.0 nm. The recorded absorption value, the resin weight and the volume are entered into an equation derived from Lambert–Beer's law, together with the substance‐specific molar absorption coefficient at 301.0 nm, in order to calculate the nominal substitution. To our knowledge, molar absorption coefficients between 7100 l mol−1 cm−1 and 8100 l mol−1 cm−1 have been reported for the dibenzofulvene–piperidine adduct at 301.0 nm. Depending on the applied value, the nominal batch size may differ up to 14%. In this publication, a determination of the molar absorption coefficients at 301.0 and 289.8 nm is reported. Furthermore, proof is given that by measuring the absorption at 289.8 nm the impact of wavelength accuracy is reduced. © 2017 The Authors Journal of Peptide Science published by European Peptide Society and John Wiley & Sons Ltd. PMID:28635051

  16. Substitution determination of Fmoc-substituted resins at different wavelengths.

    Eissler, Stefan; Kley, Markus; Bächle, Dirk; Loidl, Günther; Meier, Thomas; Samson, Daniel

    2017-10-01

    In solid-phase peptide synthesis, the nominal batch size is calculated using the starting resin substitution and the mass of the starting resin. The starting resin substitution constitutes the basis for the calculation of a whole set of important process parameters, such as the number of amino acid derivative equivalents. For Fmoc-substituted resins, substitution determination is often performed by suspending the Fmoc-protected starting resin in 20% (v/v) piperidine in DMF to generate the dibenzofulvene-piperidine adduct that is quantified by ultraviolet-visible spectroscopy. The spectrometric measurement is performed at the maximum absorption wavelength of the dibenzofulvene-piperidine adduct, that is, at 301.0 nm. The recorded absorption value, the resin weight and the volume are entered into an equation derived from Lambert-Beer's law, together with the substance-specific molar absorption coefficient at 301.0 nm, in order to calculate the nominal substitution. To our knowledge, molar absorption coefficients between 7100 l mol -1  cm -1 and 8100 l mol -1  cm -1 have been reported for the dibenzofulvene-piperidine adduct at 301.0 nm. Depending on the applied value, the nominal batch size may differ up to 14%. In this publication, a determination of the molar absorption coefficients at 301.0 and 289.8 nm is reported. Furthermore, proof is given that by measuring the absorption at 289.8 nm the impact of wavelength accuracy is reduced. © 2017 The Authors Journal of Peptide Science published by European Peptide Society and John Wiley & Sons Ltd. © 2017 The Authors Journal of Peptide Science published by European Peptide Society and John Wiley & Sons Ltd.

  17. Behavioral service substitution (Chapter 9)

    Stahl, C.; Aalst, van der W.M.P.; Bouguettaya, A.; Sheng, Q.Z.; Daniel, F.

    2014-01-01

    Service-oriented design supports system evolution and encourages reuse and modularization. A key ingredient of service orientation is the ability to substitute one service by another without reconfiguring the overall system. This chapter aims to give an overview of the state of the art and open

  18. prismane structure by silicon substitution

    Using the second-order Møller–Plesset perturbation (MP2) theoretic method and the cc-pVDZ basis set, it is shown that with an increase in the number of carbon atoms substituted by silicon, the [6]-prismane structure becomes increasingly more stable, relative to the two isolated benzene (like) structures. A similar trend is ...

  19. Story of skeletally substituted benzenes

    Unknown

    values are extensively used to define aromaticity quantitatively.3 In a recent study on ... studies were directed to unravel the subtle ways in which the stability, reactivity, and ..... The singlet–triplet gaps of all the skeletally substituted benzenes ...

  20. 40 CFR Appendix D to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes

    2010-07-01

    ... the following criteria, derived from Society of Automotive Engineers (SAE) standards and recommended... Substitutes] Application Substitute Decision Conditions Comments Electronics Cleaning w/CFC-113 and MCF HFC... Sector [Acceptable Subject to Narrowed Use Limits] Application Substitute Decision Comments Electronics...

  1. Smart Phones and their Substitutes

    Bødker, Mads; Gimpel, Gregory; Hedman, Jonas

    2009-01-01

    Drawing on data from a longitudinal field study, this paper investigates the influence of existing, better and stand-alone technology substitutes on the use of smart phones. By applying prospect theory, media richness theory, and business model literature, the purpose of this paper is to improve...... our understanding of the role of substitutes, device content fit issues, and implications for business models by asking the question: What is an effective business model to address the relationship between user preference and the fit of the smart phone and everyday task? The field study data suggest...... the need for business models to recognize that adoption decisions are reference-dependent and strongly influenced by the fit between task and smart phone....

  2. Bone healing and bone substitutes.

    Costantino, Peter D; Hiltzik, David; Govindaraj, Satish; Moche, Jason

    2002-02-01

    With the advent of new biomaterials and surgical techniques, the reconstructive surgeon has a wider range of treatment modalities for the rehabilitation and reconstruction of craniofacial skeletal deformities than ever before. These innovative substances act as true bone graft substitutes, thereby allowing the surgeon to avoid the use of autogenous bone grafts and their associated donor site morbidity. Surgeons have long been interested in producing a composite graft that can heal faster by induction, incorporate with surrounding tissues, and be remodeled to resemble native bone. Currently, there are a host of bone graft substitutes available that vary in both their composition and properties. Craniomaxillofacial surgeons must therefore become comfortable with numerous biomaterials to best tailor the treatment for each patient individually. Ongoing investigations into the next phase of tissue engineering will continue to bring us closer to the ability to regenerate or replace bone.

  3. Substituting oil by electric power

    Lichtenberg, H.

    1981-01-01

    Parting from the development of primary energy use the author refers to the latest investigations and results presented on the 1980 World Energy Conference and with special regard to oil points out the threatening exhaustion of fossil energy resources. Maintaining the economic structure of the Federal Republic of Germany implies an orientation away from oil. Due to its flexible application technology and quasi-inexhaustible energy resources electric power may substantially contribute to oil substitution which as a matter of fact is of particular interest in connection with the heat market. Coal alone cannot substitute both oil and nuclear energy. Thus, the above postulates the use of the latter. Leaving nuclear energy inactive today will effect an increase in the demand for oil the negative consequences of which would weight heavily upon the anyhow unbalanced import/export ratio of the Federal Republic of Germany. (orig.) [de

  4. 40 CFR 721.4420 - Substituted hydroxylamine.

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted hydroxylamine. 721.4420... Substances § 721.4420 Substituted hydroxylamine. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted hydroxylamine (PMN P-84-492) is...

  5. Substituted Indoleacetic Acids Tested in Tissue Cultures

    Engvild, Kjeld Christensen

    1978-01-01

    Monochloro substituted IAA inhibited shoot induction in tobacco tissue cultures about as much as IAA. Dichloro substituted IAA inhibited shoot formation less. Other substituted IAA except 5-fluoro- and 5-bromoindole-3-acetic acid were less active than IAA. Callus growth was quite variable...

  6. Substitutes for School Nurses in Illinois

    Vollinger, Linda Jeno; Bergren, Martha Dewey; Belmonte-Mann, Frances

    2011-01-01

    The purpose of this descriptive study was to explore utilization of nurse substitutes in the school setting in Illinois. The literature described personnel who staff the school health office in the absence of the school nurse and the barriers to obtaining nurse substitutes. There were no empirical studies conducted on school nurse substitutes in…

  7. Structure-antiproliferative activity studies on l-proline- and homoproline-4-N-pyrrolidine-3-thiosemicarbazone hybrids and their nickel(ii), palladium(ii) and copper(ii) complexes.

    Dobrova, Aliona; Platzer, Sonja; Bacher, Felix; Milunovic, Miljan N M; Dobrov, Anatolie; Spengler, Gabriella; Enyedy, Éva A; Novitchi, Ghenadie; Arion, Vladimir B

    2016-09-14

    Two water-soluble thiosemicarbazone-proline (H2L(1)) and thiosemicarbazone-homoproline hybrids (H2L(2)) were synthesised. By reaction of H2L(1) with NiCl2·6H2O, PdCl2 and CuCl2·2H2O in ethanol, the series of square-planar complexes [Ni(H2L(1))Cl]Cl·1.3H2O (1·1.3H2O), [Pd(H2L(1))Cl]Cl·H2O (2·H2O) and [Cu(H2L(1))Cl]Cl·0.7H2O (3·0.7H2O) was prepared, and starting from H2L(2) and CuCl2·2H2O in methanol, the complex [Cu(H2L(2))Cl2]·H2O (4·H2O) was obtained. The compounds have been characterised by elemental analysis, spectroscopic methods (IR, UV-vis and NMR spectroscopy), ESI mass spectrometry and single crystal X-ray crystallography (H2L(1), 1, 2 and 4). As a solid, 1 is diamagnetic, while it is paramagnetic in methanolic solution. The effective magnetic moment of 3.26 B.M. at room temperature indicates the change in coordination geometry from square-planar to octahedral upon dissolution. The in vitro anticancer potency of ligand precursors H2L(1) and H2L(2) and metal complexes 1-4 was studied in three human cancer cell lines (A549, CH1 and SW480) and in noncancerous murine embryonal fibroblasts (NIH/3T3), and the mechanism of cell death was also assayed by flow cytometry. Clear-cut structure-activity relationships have been established. The metal ions exert marked effects in a divergent manner: copper(ii) increases, whereas nickel(ii) and palladium(ii) decrease the cytotoxicity of the hybrids. The antiproliferative activity of H2L(1) and metal complexes 1-3 decreases in all three tumour cell lines in the following rank order: 3 > H2L(1) > 1 > 2. The role of square-planar geometry in the underlying mechanism of cytotoxicity of the metal complexes studied seems to be negligible, while structural modifications at the terminal amino group of thiosemicarbazide and proline moieties are significant for enhancing the antiproliferative activity of both hybrids and copper(ii) complexes.

  8. 3-methylcyclohexanone thiosemicarbazone: determination of E/Z isomerization barrier by dynamic high-performance liquid chromatography, configuration assignment and theoretical study of the mechanisms involved by the spontaneous, acid and base catalyzed processes.

    Carradori, Simone; Cirilli, Roberto; Dei Cicchi, Simona; Ferretti, Rosella; Menta, Sergio; Pierini, Marco; Secci, Daniela

    2012-12-21

    Here, we report on the simultaneous direct HPLC diastereo- and enantioseparation of 3-methylcyclohexanone thiosemicarbazone (3-MCET) on a polysaccharide-based chiral stationary phase under normal-phase conditions. The optimized chromatographic system was employed in dynamic HPLC experiments (DHPLC), as well as detection technique in a batch wise approach to determine the rate constants and the corresponding free energy activation barriers of the spontaneous, base- and acid-promoted E/Z diastereomerization of 3-MCET. The stereochemical characterization of four stereoisomers of 3-MCET was fully accomplished by integrating the results obtained by chemical correlation method with those derived by theoretical calculations and experimental investigations of circular dichroism (CD). As a final goal, a deepened analysis of the perturbing effect exercised by the stationary phase on rate constant values measured through DHPLC determinations as a function of the chromatographic separation factor α of the interconverting species was successfully accomplished. This revealed quite small deviations from the equivalent kinetic values obtained by off-column batch wise procedure, and suggested a possible effective correction of rate constants measured by DHPLC approach. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. The preparation and characterization of Cu(II complexes with N,N’,N”,N’”-tetrakis(2-pyridylmethyl-1,4,8,11-tetraazacyclotetradecane and 2,6-diacetylpyridine bis(semi/thiosemicarbazones

    GORDANA VUCKOVIC

    2004-03-01

    Full Text Available Two new Cu(II mixed-ligand complexes with octadentate N,N’,N”,N’”-tetrakis(2-pyridylmethyl-1,4,8,11-tetraazacyclotetradecane (tpmc and potentially pentadentate ligands 2,6-diacetylpyridine bis(semicarbazone (DAPsc2 or 2,6-diacetylpyridine bis(thiosemicarbazone (DAPtsc2 were prepared. The general formulas: [Cu4 DAPsc2(tpmc2]ClO48·5CH3COCH3·H2O and [Cu2 DAPtsc2(tpmc](ClO44·7C2H5OH were proposed on the basis of elemental analyses and conductometric measurements. The complexes were characterized by magnetic measurement, electronic absorption and IR spectroscopy. For the dinuclear complex, an exo coordination of Cu(II with four nitrogens from tpmc and m-bonded DAPtsc2 through sulfurs and possibly terminal hydrazinic (azomethine nitrogens is assumed. For the tetranuclear complex, it is supposed that one DAPsc2 bridges two [Cu2 tpmc]4+ units using oxygens and terminal hydrazinic nitrogens as ligators. Finally, some antibacterial activity of the complexes was found.

  10. Biologic and synthetic skin substitutes: An overview.

    Halim, Ahmad Sukari; Khoo, Teng Lye; Mohd Yussof, Shah Jumaat

    2010-09-01

    The current trend of burn wound care has shifted to more holistic approach of improvement in the long-term form and function of the healed burn wounds and quality of life. This has demanded the emergence of various skin substitutes in the management of acute burn injury as well as post burn reconstructions. Skin substitutes have important roles in the treatment of deep dermal and full thickness wounds of various aetiologies. At present, there is no ideal substitute in the market. Skin substitutes can be divided into two main classes, namely, biological and synthetic substitutes. The biological skin substitutes have a more intact extracellular matrix structure, while the synthetic skin substitutes can be synthesised on demand and can be modulated for specific purposes. Each class has its advantages and disadvantages. The biological skin substitutes may allow the construction of a more natural new dermis and allow excellent re-epithelialisation characteristics due to the presence of a basement membrane. Synthetic skin substitutes demonstrate the advantages of increase control over scaffold composition. The ultimate goal is to achieve an ideal skin substitute that provides an effective and scar-free wound healing.

  11. Biologic and synthetic skin substitutes: An overview

    Halim Ahmad

    2010-10-01

    Full Text Available The current trend of burn wound care has shifted to more holistic approach of improvement in the long-term form and function of the healed burn wounds and quality of life. This has demanded the emergence of various skin substitutes in the management of acute burn injury as well as post burn reconstructions. Skin substitutes have important roles in the treatment of deep dermal and full thickness wounds of various aetiologies. At present, there is no ideal substitute in the market. Skin substitutes can be divided into two main classes, namely, biological and synthetic substitutes. The biological skin substitutes have a more intact extracellular matrix structure, while the synthetic skin substitutes can be synthesised on demand and can be modulated for specific purposes. Each class has its advantages and disadvantages. The biological skin substitutes may allow the construction of a more natural new dermis and allow excellent re-epithelialisation characteristics due to the presence of a basement membrane. Synthetic skin substitutes demonstrate the advantages of increase control over scaffold composition. The ultimate goal is to achieve an ideal skin substitute that provides an effective and scar-free wound healing.

  12. Computational study of cation substitutions in apatites

    Tamm, Toomas; Peld, Merike

    2006-01-01

    Density-functional theory plane-wave modeling of fluor- and hydroxyapatites has been performed, where one or two calcium ions per unit cell were replaced with cadmium or zinc cations. It was found that cadmium ions favor Ca(1) positions in fluorapatites and Ca(2) positions in hydroxyapatites, in agreement with experiment. A similar pattern is predicted for zinc substitutions. In the doubly substituted cases, where only hydroxyapatites were modeled, a preference for the substituting ions to be located in Ca(2) position was also observed. Displacement of the hydroxide ions from their symmetrical positions on the hexagonal axis can be used to explain the preferred configurations of substituting ions around the axis. -- Deformation of the hydroxide ion chain due to substitutions around the ion channel in substituted hydroxyapatites

  13. The Morishima Gross elasticity of substitution

    Blackorby, Charles; Primont, Daniel; Russell, R. Robert

    2007-01-01

    We show that the Hotelling-Lau elasticity of substitution, an extension of the Allen-Uzawa elasticity to allow for optimal output-quantity (or utility) responses to changes in factor prices, inherits all of the failings of the Allen-Uzawa elasticity identified by Blackorby and Russell [1989 AER]. An analogous extension of the Morishima elasticity of substitution to allow for output quantity changes preserves the salient properties of the original Hicksian notion of elasticity of substitution.

  14. Statistical Physics of Complex Substitutive Systems

    Jin, Qing

    Diffusion processes are central to human interactions. Despite extensive studies that span multiple disciplines, our knowledge is limited to spreading processes in non-substitutive systems. Yet, a considerable number of ideas, products, and behaviors spread by substitution; to adopt a new one, agents must give up an existing one. This captures the spread of scientific constructs--forcing scientists to choose, for example, a deterministic or probabilistic worldview, as well as the adoption of durable items, such as mobile phones, cars, or homes. In this dissertation, I develop a statistical physics framework to describe, quantify, and understand substitutive systems. By empirically exploring three collected high-resolution datasets pertaining to such systems, I build a mechanistic model describing substitutions, which not only analytically predicts the universal macroscopic phenomenon discovered in the collected datasets, but also accurately captures the trajectories of individual items in a complex substitutive system, demonstrating a high degree of regularity and universality in substitutive systems. I also discuss the origins and insights of the parameters in the substitution model and possible generalization form of the mathematical framework. The systematical study of substitutive systems presented in this dissertation could potentially guide the understanding and prediction of all spreading phenomena driven by substitutions, from electric cars to scientific paradigms, and from renewable energy to new healthy habits.

  15. Substitution dynamical systems spectral analysis

    Queffélec, Martine

    2010-01-01

    This volume mainly deals with the dynamics of finitely valued sequences, and more specifically, of sequences generated by substitutions and automata. Those sequences demonstrate fairly simple combinatorical and arithmetical properties and naturally appear in various domains. As the title suggests, the aim of the initial version of this book was the spectral study of the associated dynamical systems: the first chapters consisted in a detailed introduction to the mathematical notions involved, and the description of the spectral invariants followed in the closing chapters. This approach, combined with new material added to the new edition, results in a nearly self-contained book on the subject. New tools - which have also proven helpful in other contexts - had to be developed for this study. Moreover, its findings can be concretely applied, the method providing an algorithm to exhibit the spectral measures and the spectral multiplicity, as is demonstrated in several examples. Beyond this advanced analysis, many...

  16. Controversial issues of maternity substitution

    Andy Pușcă

    2009-06-01

    Full Text Available Substitute maternity consists in a woman carrying a pregnancy (the implant of an embryo, at therequest of a sterile couple, most of the times in exchange of a sum of money, with her commitment tounconditionally give away the newborn after birth to the couple she concluded the agreement with. Manycontroversies emerged in what concerns the contract between the sterile couple and the carrying mother,especially when this contract is by onerous title, which happens in most of the cases. In that a civil contract? Is ita sales contract for the child? Is it a contract to provide services? Is it body marketing? Between total prohibitionand excessive liberalism, the middle way, which is the regulation according to ethical religious, cultural andsocial norms of each community, represents a realistic solution.

  17. Photoelectron Spectroscopy of Substituted Phenylnitrenes

    Wijeratne, Neloni R.; Da Fonte, Maria; Wenthold, Paul G.

    2009-06-01

    Nitrenes are unusual molecular structures with unfilled electronic valences that are isoelectronic with carbenes. Although, both can be generated by either thermal or photochemical decomposition of appropriate precursors they usually exhibit different reactivities. In this work, we carry out spectroscopic studies of substituted phenylnitrene to determine how the introduction of substituents will affect the reactivity and its thermochemical properties. All studies were carried out by using the newly constructed time-of-flight negative ion photoelectron spectrometer (NIPES) at Purdue University. The 355 nm photoelectron spectra of the o-, m-, and p-chlorophenyl nitrene anions are fairly similar to that measured for phenylnitrene anion. All spectra show low energy triplet state and a high energy singlet state. The singlet state for the meta isomer is well-resolved, with a well defined origin and observable vibrational structure. Whereas the singlet states for the ortho and para isomers have lower energy onsets and no resolved structure. The isomeric dependence suggests that the geometry differences result from the resonance interaction between the nitrogen and the substituent. Quinoidal resonance structures are possible for the open-shell singlet states of the o- and p-chlorinated phenyl nitrenes. The advantages of this type of electronic structures for the open-shell singlet states is that the unpaired electrons can be more localized on separate atoms in the molecules, minimizing the repulsion between. Because the meta position is not in resonance with the nitrenes, substitution at that position should not affect the structure of the open-shell singlet state. The measured electron affinities (EA) of the triplet phenylnitrenes are in excellent agreement with the values predicted by electronic structure calculations. The largest EA, 1.82 eV is found for the meta isomer, with para being the smallest, 1.70 eV.

  18. Type Substitution for Object-Oriented Programming

    Schwartzbach, Michael Ignatieff; Palsberg, Jens

    1990-01-01

    Genericity allows the substitution of types in a class. This is usually obtained through parameterized classes, although they are inflexible since any class can be inherited but is not in itself parameterized. We suggest a new genericity mechanism, type substitution, which is a subclassing concep...

  19. Multisensory integration, sensory substitution and visual rehabilitation

    Proulx, Michael J; Ptito, Maurice; Amedi, Amir

    2014-01-01

    Sensory substitution has advanced remarkably over the past 35 years since first introduced to the scientific literature by Paul Bach-y-Rita. In this issue dedicated to his memory, we describe a collection of reviews that assess the current state of neuroscience research on sensory substitution...

  20. Educators Take Another Look at Substitutes

    Zubrzycki, Jaclyn

    2012-01-01

    The mythology surrounding the substitute teacher is not a pretty one: Paper airplanes, lost learning, bullying. But as schools collect more information about teacher absenteeism and its consequences, districts and schools are exploring ways to professionalize substitute teaching--or experiment with alternative ways of coping with teacher absences.…

  1. Substitution between cars within the household

    De Borger, Bruno; Mulalic, Ismir; Rouwendal, Jan

    2016-01-01

    In this paper we study the demand for car kilometres in two-car households, focusing on the substitution between cars of different fuel efficiency in response to fuel price changes. We use a large sample of detailed Danish data on two-car households to estimate – for each car owned by the household...... – own and cross-price effects of increases in fuel costs per kilometre. The empirical results show that failure to capture substitution between cars within the household can result in substantial misspecification biases. Ignoring substitution, the basic model yielded fuel price elasticities of 0.......98 and 1.41 for the primary and secondary cars, respectively. Accounting for substitution effects, these figures reduce to, respectively, 0.32 and 0.45. Consistent with substitution behaviour, we find that the fuel price elasticity of fuel demand exceeds the elasticity of kilometre demands with respect...

  2. Elasticity of Substitution and Antidumping Measures

    Drud Hansen, Jørgen; Meinen, Philipp; Nielsen, Jørgen Ulff-Møller

    Abstract This paper analyzes the role of the elasticity of substitution for anti-dumping decisions across countries. In monopolistic competition models with cost heterogeneous firms across countries, price differences vary inversely with the elasticity of substitution. Anti-dumping duties should...... therefore also vary inversely with the elasticity of substitution at least for countries which have a strong focus on prices in the determination of their anti-dumping measures. We test this for ten countries from 1990 to 2009 using data on anti-dumping from Chad Bown (2010) and US-data at 8-digit level...... in our empirical investigation support the predicted role of the elasticity of substitution as we find a significant negative relation between the elasticity of substitution and the final anti-dumping duties for the ‘lesser duty rule’ group of countries. The countries which do not follow the ‘lesser duty...

  3. Substituted Hydroxyapatites with Antibacterial Properties

    Joanna Kolmas

    2014-01-01

    Full Text Available Reconstructive surgery is presently struggling with the problem of infections located within implantation biomaterials. Of course, the best antibacterial protection is antibiotic therapy. However, oral antibiotic therapy is sometimes ineffective, while administering an antibiotic at the location of infection is often associated with an unfavourable ratio of dosage efficiency and toxic effect. Thus, the present study aims to find a new factor which may improve antibacterial activity while also presenting low toxicity to the human cells. Such factors are usually implemented along with the implant itself and may be an integral part of it. Many recent studies have focused on inorganic factors, such as metal nanoparticles, salts, and metal oxides. The advantages of inorganic factors include the ease with which they can be combined with ceramic and polymeric biomaterials. The following review focuses on hydroxyapatites substituted with ions with antibacterial properties. It considers materials that have already been applied in regenerative medicine (e.g., hydroxyapatites with silver ions and those that are only at the preliminary stage of research and which could potentially be used in implantology or dentistry. We present methods for the synthesis of modified apatites and the antibacterial mechanisms of various ions as well as their antibacterial efficiency.

  4. Substituted Hydroxyapatites with Antibacterial Properties

    Kolmas, Joanna; Groszyk, Ewa; Kwiatkowska-Różycka, Dagmara

    2014-01-01

    Reconstructive surgery is presently struggling with the problem of infections located within implantation biomaterials. Of course, the best antibacterial protection is antibiotic therapy. However, oral antibiotic therapy is sometimes ineffective, while administering an antibiotic at the location of infection is often associated with an unfavourable ratio of dosage efficiency and toxic effect. Thus, the present study aims to find a new factor which may improve antibacterial activity while also presenting low toxicity to the human cells. Such factors are usually implemented along with the implant itself and may be an integral part of it. Many recent studies have focused on inorganic factors, such as metal nanoparticles, salts, and metal oxides. The advantages of inorganic factors include the ease with which they can be combined with ceramic and polymeric biomaterials. The following review focuses on hydroxyapatites substituted with ions with antibacterial properties. It considers materials that have already been applied in regenerative medicine (e.g., hydroxyapatites with silver ions) and those that are only at the preliminary stage of research and which could potentially be used in implantology or dentistry. We present methods for the synthesis of modified apatites and the antibacterial mechanisms of various ions as well as their antibacterial efficiency. PMID:24949423

  5. Evaluation of the potential application of 2-acetylpyridine N4- phenyl thiosemicarbazones derivatives for cancer therapy and diagnosis; Avaliacao da potencial aplicacao de derivados de 2-acetilpiridina N-4 fenil tiossemicarbazonas em terapia e diagnostico oncologico

    Soares, Marcella Araugio

    2013-08-01

    Despite the wide range of antineoplastic agents available, resistance of some types of cancer and toxicity to normal cells have been identified as the main causes of treatment failure and death. The lack of early and precise diagnosis is also responsible for reducing survival of cancer patients. In this context, the development of substances with low toxicity and therapeutic potential and/or diagnosis purpose, is the major tool in an attempt to increase the survival of patients and assure the safety and efficacy of treatment. Thiosemicarbazones (TSC) are a class of synthetic compounds that have several biological activities, including antitumor. Although several studies have shown the great potential of TSC as therapeutic and / or diagnostic agents, different chemical modifications performed on this class of molecules indicate new possibilities for applications and still require further studies. The objective of this study was to evaluate the potential applicability of 2-acetylpyridine N-4-phenyl thiosemicarbazones derivatives for cancer therapy and diagnosis. The results showed that all 13 TSC tested were cytotoxic to breast and glioblastoma tumor cell lines, presenting higher in vitro antitumor activity than etoposide, an antineoplastic and inhibitor of topoisomerase II frequently used for cancer therapy. The TSC that have halogen or nitro on ortho position showed higher antitumor activity in vitro than their isomers with halogen or nitro on meta or para position of the phenyl group. H2Ac4oFPh and H2Ac4oClPh compounds showed the highest antitumor activity among all tested compounds, with IC{sub 50} in nanomolar order. These TSC induced cell death by apoptosis and oxidative stress was responsible, at least in part, for this type of cell death. The 5 mg.kg{sup -1} H2Ac4oFPh dose, administered s.c., for 4 consecutive days, did not induce important toxicity; however, the same treatment protocol was not effective for tumor growth reduction in an animal model of brain

  6. Synthesis and application of chloromethylated polystyrene modified with 1-phenyl-1,2-propanedione-2-oxime thiosemicarbazone (PPDOT) as a new sorbent for the on-line preconcentration and determination of copper in water, soil, and food samples by FAAS

    Chamjangali, Mansour Arab, E-mail: marab@shahroodut.ac.ir [College of Chemistry, Shahrood University of Technology, P.O. Box 36155-316, Shahrood (Iran, Islamic Republic of); Bagherian, Ghadamali; Mokhlesian, Ali; Bahramian, Bahram [College of Chemistry, Shahrood University of Technology, P.O. Box 36155-316, Shahrood (Iran, Islamic Republic of)

    2011-09-15

    Highlights: {yields} This paper is the first report on the use of PS-PPDOT resin in the SPE studies. {yields} The proposed adsorbent is highly selective for trace determination of copper. {yields} The method is applicable for copper determination in water, soil, and food samples. - Abstract: In this paper, we report a simple and sensitive on-line solid phase extraction system for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry (FAAS). This method is based upon the on-line retention of copper at pH 5.0 on a minicolumn packed with chloromethylated polystyrene modified by 1-phenyl-1,2-propanedione-2-oxime thiosemicarbazone (PPDOT) as a new solid-phase extraction (SPE) sorbent. The retained Cu(II) ions were eluted with 1.0 M HNO{sub 3}, and transported directly to FAAS for determination. Several chemical and flow variables were studied and optimized for a quantitative preconcentration and determination of copper(II). At the optimized conditions, for preconcentration of 10.0 mL of a sample solution, a linear calibration graph was obtained over the concentration range of 3.00-120.0 {mu}g L{sup -1} for Cu(II). The limit of detection (3{sigma}), limit of quantification (10{sigma}), and enrichment factor are 0.56 {mu}g L{sup -1}, 2.0 {mu}g L{sup -1} and 41, respectively. The relative standard deviation (n = 6) at 20 {mu}g L{sup -1} of Cu(II) is 2.0%. This method could be applied for determination of trace amounts of Cu(II) in water, soil, and food samples with satisfactory results.

  7. Synthesis and application of chloromethylated polystyrene modified with 1-phenyl-1,2-propanedione-2-oxime thiosemicarbazone (PPDOT) as a new sorbent for the on-line preconcentration and determination of copper in water, soil, and food samples by FAAS

    Chamjangali, Mansour Arab; Bagherian, Ghadamali; Mokhlesian, Ali; Bahramian, Bahram

    2011-01-01

    Highlights: → This paper is the first report on the use of PS-PPDOT resin in the SPE studies. → The proposed adsorbent is highly selective for trace determination of copper. → The method is applicable for copper determination in water, soil, and food samples. - Abstract: In this paper, we report a simple and sensitive on-line solid phase extraction system for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry (FAAS). This method is based upon the on-line retention of copper at pH 5.0 on a minicolumn packed with chloromethylated polystyrene modified by 1-phenyl-1,2-propanedione-2-oxime thiosemicarbazone (PPDOT) as a new solid-phase extraction (SPE) sorbent. The retained Cu(II) ions were eluted with 1.0 M HNO 3 , and transported directly to FAAS for determination. Several chemical and flow variables were studied and optimized for a quantitative preconcentration and determination of copper(II). At the optimized conditions, for preconcentration of 10.0 mL of a sample solution, a linear calibration graph was obtained over the concentration range of 3.00-120.0 μg L -1 for Cu(II). The limit of detection (3σ), limit of quantification (10σ), and enrichment factor are 0.56 μg L -1 , 2.0 μg L -1 and 41, respectively. The relative standard deviation (n = 6) at 20 μg L -1 of Cu(II) is 2.0%. This method could be applied for determination of trace amounts of Cu(II) in water, soil, and food samples with satisfactory results.

  8. Modeling competitive substitution in a polyelectrolyte complex

    Peng, B.; Muthukumar, M.

    2015-01-01

    We have simulated the invasion of a polyelectrolyte complex made of a polycation chain and a polyanion chain, by another longer polyanion chain, using the coarse-grained united atom model for the chains and the Langevin dynamics methodology. Our simulations reveal many intricate details of the substitution reaction in terms of conformational changes of the chains and competition between the invading chain and the chain being displaced for the common complementary chain. We show that the invading chain is required to be sufficiently longer than the chain being displaced for effecting the substitution. Yet, having the invading chain to be longer than a certain threshold value does not reduce the substitution time much further. While most of the simulations were carried out in salt-free conditions, we show that presence of salt facilitates the substitution reaction and reduces the substitution time. Analysis of our data shows that the dominant driving force for the substitution process involving polyelectrolytes lies in the release of counterions during the substitution

  9. Determinants of generic drug substitution in Switzerland

    Lufkin Thomas M

    2011-01-01

    Full Text Available Abstract Background Since generic drugs have the same therapeutic effect as the original formulation but at generally lower costs, their use should be more heavily promoted. However, a considerable number of barriers to their wider use have been observed in many countries. The present study examines the influence of patients, physicians and certain characteristics of the generics' market on generic substitution in Switzerland. Methods We used reimbursement claims' data submitted to a large health insurer by insured individuals living in one of Switzerland's three linguistic regions during 2003. All dispensed drugs studied here were substitutable. The outcome (use of a generic or not was modelled by logistic regression, adjusted for patients' characteristics (gender, age, treatment complexity, substitution groups and with several variables describing reimbursement incentives (deductible, co-payments and the generics' market (prices, packaging, co-branded original, number of available generics, etc.. Results The overall generics' substitution rate for 173,212 dispensed prescriptions was 31%, though this varied considerably across cantons. Poor health status (older patients, complex treatments was associated with lower generic use. Higher rates were associated with higher out-of-pocket costs, greater price differences between the original and the generic, and with the number of generics on the market, while reformulation and repackaging were associated with lower rates. The substitution rate was 13% lower among hospital physicians. The adoption of the prescribing practices of the canton with the highest substitution rate would increase substitution in other cantons to as much as 26%. Conclusions Patient health status explained a part of the reluctance to substitute an original formulation by a generic. Economic incentives were efficient, but with a moderate global effect. The huge interregional differences indicated that prescribing behaviours and

  10. Sensory Substitution and Multimodal Mental Imagery.

    Nanay, Bence

    2017-09-01

    Many philosophers use findings about sensory substitution devices in the grand debate about how we should individuate the senses. The big question is this: Is "vision" assisted by (tactile) sensory substitution really vision? Or is it tactile perception? Or some sui generis novel form of perception? My claim is that sensory substitution assisted "vision" is neither vision nor tactile perception, because it is not perception at all. It is mental imagery: visual mental imagery triggered by tactile sensory stimulation. But it is a special form of mental imagery that is triggered by corresponding sensory stimulation in a different sense modality, which I call "multimodal mental imagery."

  11. Biologic and synthetic skin substitutes: An overview

    Halim, Ahmad Sukari; Khoo, Teng Lye; Mohd. Yussof, Shah Jumaat

    2010-01-01

    The current trend of burn wound care has shifted to more holistic approach of improvement in the long-term form and function of the healed burn wounds and quality of life. This has demanded the emergence of various skin substitutes in the management of acute burn injury as well as post burn reconstructions. Skin substitutes have important roles in the treatment of deep dermal and full thickness wounds of various aetiologies. At present, there is no ideal substitute in the market. Skin substit...

  12. Substitution within the Danish printing industry

    Larsen, Henrik Fred; Bøg, Carsten

    2009-01-01

    are running a substitution project. A major part of the work has been mapping the presence of chemicals which are potential candidates for substitution (e.g. PBT, CMR, vPvB, EDS) within the Danish printing industry and this work was recently finished. The mapping comprises a combination of a literature study......The implementation of the EU REACH regulation will most probably promote substitution within sectors handling a lot of different chemicals like the printing industry. With the aim of being at the cutting edge of this development the Danish EPA together with the Danish printing industry and IPU...... total 15 substances) were found in the Danish printing industry. This paper presents the results of the mapping of chemical candidates and the first results on preparing for actual substitutions....

  13. Substituted hydroxyapatites for biomedical applications: A review

    Šupová, Monika

    2015-01-01

    Roč. 41, č. 8 (2015), s. 9203-9231 ISSN 0272-8842 Institutional support: RVO:67985891 Keywords : bioapatite * calcium phosphate * hydroxyapatite * substitution Subject RIV: JJ - Other Materials Impact factor: 2.758, year: 2015

  14. Dodecatungstocobaltate and Sn (IV)-Substituted Polyoxometalate ...

    NICO

    work metals, or substituting different cations for the protons to make their acidic or neutral ... corrosive materials in comparison with traditional Lewis acids. The importance of .... salt by treatment with potassium chloride. Finally, the cobalt (II).

  15. Questioning nuclear waste substitution: a case study.

    Marshall, Alan

    2007-03-01

    This article looks at the ethical quandaries, and their social and political context, which emerge as a result of international nuclear waste substitution. In particular it addresses the dilemmas inherent within the proposed return of nuclear waste owned by Japanese nuclear companies and currently stored in the United Kingdom. The UK company responsible for this waste, British Nuclear Fuels Limited (BNFL), wish to substitute this high volume intermediate-level Japanese-owned radioactive waste for a much lower volume of much more highly radioactive waste. Special focus is given to ethical problems that they, and the UK government, have not wished to address as they move forward with waste substitution. The conclusion is that waste substitution can only be considered an ethical practice if a set of moderating conditions are observed by all parties. These conditions are listed and, as of yet, they are not being observed.

  16. DOES CURRENCY SUBSTITUTION AFFECT EXCHANGE RATE VOLATILITY?

    Hisao Kumamoto

    2014-10-01

    Full Text Available This study investigates the impacts of the degree of currency substitution on nominal exchange rate volatility in seven countries (Indonesia, the Philippines, the Czech Republic, Hungary, Poland, Argentina, and Peru. We use the Threshold ARCH model to consider the ratchet effect of currency substitution and sample periods in the 2000s, during which time the economies of the sample countries stabilized, while the U.S. dollar and euro depreciated against other major currencies following the recent global financial crisis. The presented empirical analyses show that the degree of currency substitution has significant positive effects on the conditional variance of the depreciation rate of the nominal exchange rate in most sample countries. Moreover, a shock to the depreciation rate of the nominal exchange rate has asymmetric effects on the conditional variance, depending on the sign. One possible explanation for these differential effects is the existence of the ratchet effect of currency substitution.

  17. Development of a diesel substitute fuel

    Reiter, Anton; Mair-Zelenka, Philipp [Graz Univ. of Technology (Austria). Inst. of Chemical Engineering and Environmental Technology; Zeymer, Marc [OMV Refining and Marketing GmbH, Vienna (Austria). MRDI-D Product Development and Innovation

    2013-06-01

    Substitute fuels composed of few real chemical compounds are an alternative characterisation approach for conventional fuels as opposed to the traditional pseudo-component method. With the algorithm proposed in this paper the generation of such substitutes will be facilitated and well-established thermodynamic methods can be applied for physical property-data prediction. Based on some quality criteria like true boiling-point curve, liquid density, C/H ratio, or cloud point of a target fuel a surrogate which meets these properties is determined by fitting its composition. The application and capabilities of the algorithm developed are demonstrated by means of an exemplary diesel substitute fuel. The substitute mixture obtained can be generated and used for evaluation of property-prediction methods. Furthermore this approach can help to understand the effects of mixing fossil fuels with biogenic compounds. (orig.)

  18. Hyperfine magnetic fields in substituted Finemet alloys

    Brzózka, K., E-mail: k.brzozka@uthrad.pl [University of Technology and Humanities in Radom, Department of Physics (Poland); Sovák, P. [P.J. Šafárik University, Institute of Physics (Slovakia); Szumiata, T.; Gawroński, M.; Górka, B. [University of Technology and Humanities in Radom, Department of Physics (Poland)

    2016-12-15

    Transmission Mössbauer spectroscopy was used to determine the hyperfine fields of Finemet-type alloys in form of ribbons, substituted alternatively by Mn, Ni, Co, Al, Zn, V or Ge of various concentration. The comparative analysis of magnetic hyperfine fields was carried out which enabled to understand the role of added elements in as-quenched as well as annealed samples. Moreover, the influence of the substitution on the mean direction of the local hyperfine magnetic field was examined.

  19. Trace maps of general substitutional sequences

    Kolar, M.; Nori, F.

    1990-01-01

    It is shown that for arbitrary n, there exists a trace map for any n-letter substitutional sequence. Trace maps are explicitly obtained for the well-known circle and Rudin-Shapiro sequences which can be defined by means of substitution rules on three and four letters, respectively. The properties of the two trace maps and their consequences for various spectral properties are briefly discussed

  20. Product portfolio optimization based on substitution

    Myrodia, Anna; Moseley, A.; Hvam, Lars

    2017-01-01

    The development of production capabilities has led to proliferation of the product variety offered to the customer. Yet this fact does not directly imply increase of manufacturers' profitability, nor customers' satisfaction. Consequently, recent research focuses on portfolio optimization through...... substitution and standardization techniques. However when re-defining the strategic market decisions are characterized by uncertainty due to several parameters. In this study, by using a GAMS optimization model we present a method for supporting strategic decisions on substitution, by quantifying the impact...

  1. Currency Substitution and Inflation in Peru

    Liliana Rojas-Suárez

    1992-01-01

    This paper shows that there is a long-run relationship between the expected rate of depreciation in the black-market-exchange rate and the ratio of domestic to foreign money in Peru; that is, the hypothesis of currency substitution can explain the behavior of real holdings of money in Peru. The paper also shows that, while the importance of currency substitution as a transmission mechanism through which domestic policies affected the dynamics of inflation was relatively small during a period ...

  2. Substituting missing data in compositional analysis

    Real, Carlos, E-mail: carlos.real@usc.es [Area de Ecologia, Departamento de Biologia Celular y Ecologia, Escuela Politecnica Superior, Universidad de Santiago de Compostela, 27002 Lugo (Spain); Angel Fernandez, J.; Aboal, Jesus R.; Carballeira, Alejo [Area de Ecologia, Departamento de Biologia Celular y Ecologia, Facultad de Biologia, Universidad de Santiago de Compostela, 15782 Santiago de Compostela (Spain)

    2011-10-15

    Multivariate analysis of environmental data sets requires the absence of missing values or their substitution by small values. However, if the data is transformed logarithmically prior to the analysis, this solution cannot be applied because the logarithm of a small value might become an outlier. Several methods for substituting the missing values can be found in the literature although none of them guarantees that no distortion of the structure of the data set is produced. We propose a method for the assessment of these distortions which can be used for deciding whether to retain or not the samples or variables containing missing values and for the investigation of the performance of different substitution techniques. The method analyzes the structure of the distances among samples using Mantel tests. We present an application of the method to PCDD/F data measured in samples of terrestrial moss as part of a biomonitoring study. - Highlights: > Missing values in multivariate data sets must be substituted prior to analysis. > The substituted values can modify the structure of the data set. > We developed a method to estimate the magnitude of the alterations. > The method is simple and based on the Mantel test. > The method allowed the identification of problematic variables in a sample data set. - A method is presented for the assessment of the possible distortions in multivariate analysis caused by the substitution of missing values.

  3. Substituting missing data in compositional analysis

    Real, Carlos; Angel Fernandez, J.; Aboal, Jesus R.; Carballeira, Alejo

    2011-01-01

    Multivariate analysis of environmental data sets requires the absence of missing values or their substitution by small values. However, if the data is transformed logarithmically prior to the analysis, this solution cannot be applied because the logarithm of a small value might become an outlier. Several methods for substituting the missing values can be found in the literature although none of them guarantees that no distortion of the structure of the data set is produced. We propose a method for the assessment of these distortions which can be used for deciding whether to retain or not the samples or variables containing missing values and for the investigation of the performance of different substitution techniques. The method analyzes the structure of the distances among samples using Mantel tests. We present an application of the method to PCDD/F data measured in samples of terrestrial moss as part of a biomonitoring study. - Highlights: → Missing values in multivariate data sets must be substituted prior to analysis. → The substituted values can modify the structure of the data set. → We developed a method to estimate the magnitude of the alterations. → The method is simple and based on the Mantel test. → The method allowed the identification of problematic variables in a sample data set. - A method is presented for the assessment of the possible distortions in multivariate analysis caused by the substitution of missing values.

  4. [Guidelines for substitution treatments in prison populations].

    Michel, L; Maguet, O

    2005-01-01

    Care access for the drug addict patients in prison (in particular for the treatments of substitution) in France is very unequal from one establishment to another. This reflects the great variability of the practices of substitution and especially the absence of consensus on the methods of adaptation of these practices to the prison environment. Because of difficulties expressed by prisoners and medical staff on this subject and of stakes (let us recall that approximately 30% of the prisoners are dependent or abusers of one or more psychoactive substances), the formulation of recommendations or of a good practices guide of substitution in prison appeared necessary. Work that we detail here answers a ordering of the Advisory Commission of the Treatments of Substitution (September 2001) whose authors are members. It was presented at the session April 2003. It results from the confrontation of a review of the literature (including legal texts and official reports concerning substitution, the organization of the care in prison environment and the lawful framework), with a vast investigation. The latter was carried out near medical staff (22 prisons), penitentiary staff (3 prisons, 27 people met including directors of these establishments) and prisoners (7 establishments, 28 prisoners met) in the form of individual talks (semi-directing interviews with evaluation of the type of existing device and its knowledge by the penitentiary staff and the prisoners; statement of the suggestions, needs and requests of the medical, penitentiary staffs and of the prisoners). In the whole visited prisons, 7.8% (870) of the prisoners received substitution treatments (6.35% by buprenorphine, 1.44% by methadone), representing a proportion of substituted drug addicts (870 substituted for an evaluation of 3,350 prisoners drug addicts among the 11,168 prisoners of the 22 visited prisons) notably lower than that in free environment (56%, ie 96,000 substituted for an evaluated population of

  5. 40 CFR Appendix B to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes

    2010-07-01

    ... demonstrate it can be used safely in this end-use. CFC-12 Motor Vehicle Air Conditioners (Retrofit and New... Conditions Application Substitute Decision Conditions Comments CFC-12 Automobile Motor Vehicle Air... refrigerant. CFC-12 Automobile Motor Vehicle Air Conditioning (New equipment only) R-152a as a substitute for...

  6. Optimal ordering quantities for substitutable deteriorating items under joint replenishment with cost of substitution

    Mishra, Vinod Kumar

    2017-09-01

    In this paper we develop an inventory model, to determine the optimal ordering quantities, for a set of two substitutable deteriorating items. In this inventory model the inventory level of both items depleted due to demands and deterioration and when an item is out of stock, its demands are partially fulfilled by the other item and all unsatisfied demand is lost. Each substituted item incurs a cost of substitution and the demands and deterioration is considered to be deterministic and constant. Items are order jointly in each ordering cycle, to take the advantages of joint replenishment. The problem is formulated and a solution procedure is developed to determine the optimal ordering quantities that minimize the total inventory cost. We provide an extensive numerical and sensitivity analysis to illustrate the effect of different parameter on the model. The key observation on the basis of numerical analysis, there is substantial improvement in the optimal total cost of the inventory model with substitution over without substitution.

  7. [Contingency management in opioid substitution treatment].

    Specka, M; Böning, A; Scherbaum, N

    2011-07-01

    The majority of opiate-dependent patients in substitution treatment show additional substance-related disorders. Concomitant use of heroin, alcohol, benzodiazepines or cocaine compromises treatment success. Concomitant drug use may be treated by using contingency management (CM) which is based on learning theory. In CM, abstinence from drugs, as verified by drug screenings, is reinforced directly and contingently. Reinforcers used in CM studies with substituted patients were, amongst others, vouchers and take-home privileges. Studies in the USA show a medium average effect of CM on drug consumption rates and abstinence. The effects decrease markedly after the end of the intervention. We discuss whether CM is applicable within the German substitution treatment system and how it can be combined with other interventions such as selective detoxification treatments or cognitive-behavioural programmes. © Georg Thieme Verlag KG Stuttgart · New York.

  8. Biomaterials in search of a meniscus substitute.

    Rongen, Jan J; van Tienen, Tony G; van Bochove, Bas; Grijpma, Dirk W; Buma, Pieter

    2014-04-01

    The menisci fulfill key biomechanical functions in the tibiofemoral (knee) joint. Unfortunately meniscal injuries are quite common and most often treated by (partial) meniscectomy. However, some patients experience enduring symptoms, and, more importantly, it leads to an increased risk for symptomatic osteoarthritis. Over the past decades, researchers have put effort in developing a meniscal substitute able to prevent osteoarthritis and treat enduring clinical symptoms. Grossly, two categories of substitutes are observed: First, a resorbable scaffold mimicking biomechanical function which slowly degrades while tissue regeneration and organization is promoted. Second, a non resorbable, permanent implant which mimics the biomechanical function of the native meniscus. Numerous biomaterials with different (material) properties have been used in order to provide such a substitute. Nevertheless, a clinically applicable cartilage protecting material is not yet emerged. In the current review we provide an overview, and discuss, these different materials and extract recommendations regarding material properties for future developmental research. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Substitution between Cars within the Household

    de Borger, Bruno; Mulalic, Ismir; Rouwendal, Jan

    In this paper we study the demand for car kilometres in two-car households, focusing on the substitution between cars in response to fuel price changes. We use a large sample of detailed Danish data on two-car households to estimate—for each car owned by the household—own and cross-price effects...... of increases in fuel costs per kilometre. The empirical results show that failure to capture substitution between cars within the household can result in substantial misspecification biases. Ignoring substitution, we estimate fuel price elasticities of –0.81 and -0.65 for the primary and secondary cars...... efficient car, finding partial support for the underlying hypothesis. More importantly, the results of this extended model emphasize the importance of behavioural differences related to the position of the most fuel efficient car in the household, suggesting that households’ fuel efficiency choices...

  10. Substitute energy resource policy in Japan

    Umehara, Katsuhiko

    1980-01-01

    Japan depends 88% of energy resources and 99.8% of petroleum on imports. The solution of energy problems is now made internationally. As the means for Japan, there are the substitution of other resources for petroleum and its promotion. However, this involves the considerable funds for the development and utilization, which must be borne by the people in the form of tax. For governmental financing, a special account must be set up for the particular purpose. In the research and development of new energy resources, new institution is required. The following matters are described: petroleum shortage coming even in 1980s, the international need of substitute energy development, the need for establishing measures for substitute energy resources, acquisition of the funds, special-account governmental financing, and an institute of new energy development. (author)

  11. Substituting telecommunications for travel - Feasible or desirable

    Van Vleck, E. M.

    1974-01-01

    This paper reviews recent advances in telecommunications and examines the detailed structure of travel to estimate the feasibility of substituting telecommunications for various travel objectives. The impact of travel is analyzed from a social, economic, energy, and pollution standpoint to assess the desirability of substitution. Perhaps 35-50% of the nation's travel could, in theory, be replaced by very advanced telecommunications (such as a much improved large-screen teleconferencing network), but public resistance would be massive. Much economic dislocation would result since, for example, over 25% of retail sales are travel-related. The energy savings would be modest since only 25% of the nation's energy is consumed by transportation. However, all pollution would be reduced substantially since transportation accounts for 75% of the carbon monoxide, 60% of the hydrocarbon, and 55% of the nitrogen oxide pollution in the nation. Problems related to the implementation of large-scale substitution are discussed.

  12. A New Substitution Cipher - Random-X

    Falguni Patel

    2015-08-01

    Full Text Available Ciphers are the encryption methods to prepare the algorithm for encryption and decryption. The currently known ciphers are not strong enough to protect the data. A new substitution cipher Random-X that we introduce in this paper can be used for password encryption and data encryption. Random-X cipher is a unique substitution cipher which replaces the units of plaintext with triplets of letters. The beauty of this cipher is that the encrypted string of the same plain text is not always same. This makes it strong and difficult to crack. This paper covers the principle the implementation ideas and testing of Random-X cipher.

  13. Hydrophosphorylation of substituted alkynes by phosphonic acids

    Nifant'ev, E.F.; Solovetskaya, L.A.; Maslennikova, V.I.; Sergeev, N.M.

    1987-01-01

    Hydrophosphorylation of functionally substituted alkynes by phosphonic acids can be a convenient method for synthesis of functionally substituted mono- and diphosphine oxides. The ease of hydrophosphorylation is determined by the strength of the negative inductive effect of the substituents on the triple bond and the steric factor. The structure of the bis-adducts was confirmed by elementary analysis and the 31 P and 13 C NMR spectra. The 31 P NMR spectrum is an AB two-spin system. The values of the chemical shifts and spin-spin interaction constants 3 J/sub PP/ are in agreement with the data in the literature for similar compounds

  14. Substitution between cars within the household

    De Borger, Bruno; Mulalic, Ismir; Rouwendal, Jan

    The purpose of this paper is to study to what extent two-car households substitute the use of their less fuel efficient car by the use of their more fuel efficient car after an increase in fuel prices. Based on a simple theoretical framework we use a large sample of detailed Danish data on two-car...... households to estimate, for each car owned by the household, own and cross-price effects of increases in fuel costs per kilometer. The empirical results point at important substitution effects, so that models that estimate responses to fuel prices on the implicit or explicit assumption of one car per...

  15. Synthesis and characterization of chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), cadmium(II) and dioxouranium(VI) complexes of 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone

    Abu El-Reash, G.M.; Ibrahim, M.M.; Kenawy; El-Ayaan, Usama; Khattab, M.A.

    1994-01-01

    A few complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and dioxouranium(VI) with 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone have been synthesised and characterized on the basis of elemental analysis, IR, electronic NMR, and magnetic moment data. An octahedral structure is proposed for the Cr(III), Fe(III), Co(II) and Ni(H 3 PBT) 2 Cl 2 .2H 2 O complexes; a tetrahedral structure for the Mn(II) and Ni 2 (PBT)OAc.H 2 0 complexes and a square planar structure for the Cu(II) complexes. The antimicrobial and antifungal activities of H 3 PBT and of its metal(II) complexes are investigated. The results reveal that H 3 PBT exhibits greater antimicrobial activities than its complexes. (author). 34 refs., 4 figs., 2 tabs

  16. Studies on coordination and addition compounds and anti microbial activity of some mixed ligand complexes of Au(III), Mo(II), Co(II) and Cd(II) with dibasic acid and heterocyclic amines and addition compounds of As(III) and Sb(III) halides with benzamide and acetophenon

    Hossain, M.; Sultana, C.; Saidul Islam, M.; Zakaria, C.M.

    2008-06-01

    Three new mixed ligand complexes of Au(III) and Mo(II) with dibasic acid e.g., homophthalic acid, oxalic acid and heterocylic amines e.g., quinonine, iso-quinonine, bipyridine, Phenylanaline and the two new addition compounds of As(III) and Sb(III) halides with N-donor ligands viz. benzamide and acetophenone and one complex [Cd(DPH)(IQ) 2 ], where IQ = Iso-quinoline and DPH = Deprotonated phthalic acid have been prepared according to the procedure in the literature. Their conventional physical and chemical analyses have been done. Their antibacterial studies against nine gram positive and five gram negative pathogenic bacteria and antifungal activities against eight plant and three human fungi have been evaluated. Kanamycin and Nystatin have been used as a standard for carrying out experiments of antibacterial and antifungal activities, respectively. The minimum inhibitory concentration (MIC) values of these compounds, as antibiotic against two gram positive and two gram negative pathogenic bacteria, have also been carried out and in this case, Amoxacilin antibiotic has been used as a standard antibiotic. (author)

  17. Substituting freshwater: Can ocean desalination and water recycling capacities substitute for groundwater depletion in California?

    Badiuzzaman, Pierre; McLaughlin, Eoin; McCauley, Darren

    2017-12-01

    While the sustainability of resource depletion is a longstanding environmental concern, wider attention has recently been given to growing water scarcity and groundwater depletion. This study seeks to test the substitutability assumption embedded in weak sustainability indicators using a case study of Californian water supply. The volume of groundwater depletion is used as a proxy for unsustainable water consumption, and defined by synthesising existing research estimates into low, medium and high depletion baselines. These are compared against projected water supply increases from ocean desalination and water recycling by 2035, to determine whether new, drought-proof water sources can substitute for currently unsustainable groundwater consumption. Results show that the maximum projected supply of new water, 2.47 million acre-feet per year (MAF/yr), is sufficient to meet low depletion estimates of 2.02 MAF/yr, but fails to come near the high depletion estimate of 3.44 MAF/yr. This does not necessarily indicate physical limitations of substitutability, but more so socio-economic limitations influenced by high comparative costs. By including capacities in demand-substitutability via urban water conservation, maximum predicted capacities reach 5.57 MAF/yr, indicating wide room for substitution. Based on these results, investment in social and institutional capital is an important factor to enhance demand-side substitutability of water and other natural resources, which has been somewhat neglected by the literature on the substitutability of natural resources. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. P. Electricity demand, substitution and resources

    1976-01-01

    This report discusses the demand for electricity in New Zealand, the accuracy of demand predictions, and whether some other form of energy could be substituted for electricity. It then discusses past and possible future electricity generation in New Zealand by geothermal steam and hydro power and the resources of gas and coal that could be made available for electricity generation

  19. Endogenous cueing attenuates object substitution masking.

    Germeys, Filip; Pomianowska, I; De Graef, P; Zaenen, P; Verfaillie, K

    2010-07-01

    Object substitution masking (OSM) is a form of visual masking in which a briefly presented target surrounded by four small dots is masked by the continuing presence of the four dots after target offset. A major parameter in the prediction of OSM is the time required for attention to be directed to the target following its onset. Object substitution theory (Di Lollo et al. in J Exp Psychol Gen 129:481-507, 2000) predicts that the sooner attention can be focused at the target's location, the less masking will ensue. However, recently Luiga and Bachmann (Psychol Res 71:634-640, 2007) presented evidence that precueing of attention to the target location prior to target-plus-mask onset by means of a central (endogenous) arrow cue does not reduce OSM. When attention was cued exogenously, OSM was attenuated. Based on these results, Luiga and Bachmann argued that object substitution theory should be adapted by differentiating the ways of directing attention to the target location. The goal of the present study was to further examine the dissociation between the effects of endogenous and exogenous precueing on OSM. Contrary to Luiga and Bachmann, our results show that prior shifts of attention to the target location initiated by both exogenous and endogenous cues reduce OSM as predicted by object substitution theory and its computational model CMOS.

  20. Substitute fluid examinations for liquid manure

    Schrader Kevin

    2017-01-01

    Full Text Available For the farming industry it is essential to use liquid manure as natural fertilizer. Through new agricultural regulation 2015 in Germany the industry must develop new liquid manure spreader systems because the ammonia and methane emission are limited. In a research project the University of Applied Sciences Zwickau and some other industry partners will develop such a new innovative liquid manure spreader. The new liquid manure spreader should use pulsating air to distribute the liquid manure exactly. The pulsating air, which flows through the pipelines, should be analysed at a test station. For examinations at this test station it is important to find another substitute fluid because liquid manure smells strong, is not transparent and is also not homogeneous enough for scientific investigations. Furthermore it is important to ensure that the substitute fluid is, like liquid manure, a non-Newtonian fluid. The substitute fluid must be a shear-thinning substance - this means the viscosity decrease at higher shear rate. Many different samples like soap-water-farragoes, jelly-water-farragoes, agar-water-farragoes, soap-ethanol-farragoes and more are, for the project, examined in regard of their physical properties to find the best substitute fluid. The samples are examined at the rotational viscometer for viscosity at various shear rates and then compared with the viscosity values of liquid manure.

  1. Substitute fluid examinations for liquid manure

    Schrader, Kevin; Riedel, Marco; Eichert, Helmut

    For the farming industry it is essential to use liquid manure as natural fertilizer. Through new agricultural regulation 2015 in Germany the industry must develop new liquid manure spreader systems because the ammonia and methane emission are limited. In a research project the University of Applied Sciences Zwickau and some other industry partners will develop such a new innovative liquid manure spreader. The new liquid manure spreader should use pulsating air to distribute the liquid manure exactly. The pulsating air, which flows through the pipelines, should be analysed at a test station. For examinations at this test station it is important to find another substitute fluid because liquid manure smells strong, is not transparent and is also not homogeneous enough for scientific investigations. Furthermore it is important to ensure that the substitute fluid is, like liquid manure, a non-Newtonian fluid. The substitute fluid must be a shear-thinning substance - this means the viscosity decrease at higher shear rate. Many different samples like soap-water-farragoes, jelly-water-farragoes, agar-water-farragoes, soap-ethanol-farragoes and more are, for the project, examined in regard of their physical properties to find the best substitute fluid. The samples are examined at the rotational viscometer for viscosity at various shear rates and then compared with the viscosity values of liquid manure.

  2. Trace maps for arbitrary substitution sequences

    Avishai, Y.

    1993-01-01

    The discovery of quasi-crystals and their 1-dimensional modeling have led to a deep mathematical study of Schroedinger operators with an arbitrary deterministic potential sequence. In this work we address this problem and find trace maps for an arbitrary substitution sequence. our trace maps have lower dimensionality than those of Kolar and Nori, which make them quite attractive for actual applications. (authors)

  3. Fossil Fuels, Backstop Technologies, and Imperfect Substitution

    van der Meijden, G.C.; Pittel, Karen; van der Ploeg, Frederick; Withagen, Cees

    2014-01-01

    This chapter studies the transition from fossil fuels to backstop technologies in a general equilibrium model in which growth is driven by research and development. The analysis generalizes the existing literature by allowing for imperfect substitution between fossil fuels and the new energy

  4. 3-Substituted 2-phenyl-indoles

    Johansson, Karl Henrik; Jørgensen, T.B.; Gloriam, D.E.

    2013-01-01

    -indoles with a variety of substituents at the indole 3-position. Herein we describe the development of optimised and efficient synthetic routes to a series of new 2-phenyl-indole building blocks 3 to 9 and show that these can be used to generate a broad variety of 3-substituted 2-phenyl-indoles of interest to medicinal...

  5. Law of substitution for mixed arrays

    Koudelka, A.J.

    1987-01-01

    The nuclear safety justification of a mixed array of dissimilar fissile units of metal units and dilute solution units, according to Clayton, has been a persistent and nagging problem. Dissimilar uranium metal or dissimilar uranium solution units in a mixed array can also create a modeling nightmare for the nuclear criticality safety engineer. Now, a calculational method known as the Law of Substitution has been developed to ensure that the k/sub eff/ of an array of uranium metal and uranium solution units will satisfy any k/sub eff/ limit set by the nuclear safety engineer. The nuclear criticality safety engineer can utilize the Law of Substitution to safely mix or substitute different uranium metal units, different uranium solution units, and more importantly, uranium metal and dilute UO 2 solution units in an array. The Law of Substitution is as follows: (1) calculate the k/sub eff/ of each unit type in its own infinite planar array. (2) Determine the edge-to-edge spacing of the infinite planar array of each type of unit to satisfy a desired k/sub eff/. (3) Select the largest edge-to-edge spacing from among the similar units in their infinite planar arrays and use that spacing for the finite or infinite planar array of mixed units

  6. Thermal stability of 4-substituted benzenediazonium tetrafluoroborates

    Bruner, V.Ya.

    1990-01-01

    Heating of tetraborates of 4-methyl-, 4-phenyl- and 4-dimethylaminobenzenediazonium at 95, 120 and 148 deg, correspondingly, causes their autocatalytic destruction, two moles of gas (nitrogen, boron fluoride) being liberated. The thermal stability of 4-substituted benzenediazonium tetrafluoroborates increases with the increase of the electron-donor activity of the substituent at benzene ring

  7. complexes based on meso-substituted dipyrrins

    Keywords. Coordination polymers; meso-substituted dipyrrins; heteroleptic; acetylacetonato; ... Room temperature magnetic susceptibility measurements were ... After cooling to ambient tem- perature it ... crystals of 1 were obtained from CH2Cl2/ hexane (1. : 1) solution. .... are air-stable, crystalline solids, soluble in common.

  8. Facile Synthesis of N -Substituted Benzimidazoles

    Kurhade, Santosh; Rossetti, Arianna; Dömling, Alexander

    2016-01-01

    A particularly mild and efficient one-pot synthesis of N-substituted benzimidazole derivatives was developed. 2-Fluoro-5-nitrophenylisocyanide reacts with a diverse set of primary amines to afford the respective products in moderate to very good yield (35-95%; 20 examples).

  9. Symptomatic hemorrhagic complications associated with dural substitutes

    Po-Yuan Chen

    2018-01-01

    Conclusion: The increased risk of hemorrhagic complications associated with craniotomy is modified by choice of dural replacement. Our results could assist clinicians in their decision-making with respect to the optimal timing for synthetic dural substitutes in patients with tumor infiltration of the patient's dura, severe brain swelling in traumatic brain injury, or a result of shrinkage from exposure and electrocautery.

  10. Stochastic diffusion models for substitutable technological innovations

    Wang, L.; Hu, B.; Yu, X.

    2004-01-01

    Based on the analysis of firms' stochastic adoption behaviour, this paper first points out the necessity to build more practical stochastic models. And then, stochastic evolutionary models are built for substitutable innovation diffusion system. Finally, through the computer simulation of the

  11. Ultrasound Promoted Synthesis of Bis(substituted pyrazol-4-ylcarbonyl-Substituted Thioureas

    Li Xiao

    2009-03-01

    Full Text Available A series of novel bis(substituted pyrazol-4-ylcarbonyl-substituted thioureas have been synthesized by the reactions of substituted pyrazol-4-ylcarbonyl isothiocyanates with different diamines under ultrasound irradiation and classical heating method at 20-25 °C. In general, substantial improvement in rates and modest yields increases were observed when reactions were carried out under sonication, compared with the classical heating method. The structures of these compounds have been elucidated by elemental and spectral (IR, 1H-NMR analysis.

  12. Currency Substitution and Inflation in Peru Currency Substitution and Inflation in Peru

    Liliana Rojas-Suarez

    1992-01-01

    This paper shows that there is a long-run relationship between the expected rate of depreciation in the black-market-exchange rate and the ratio of domestic to foreign money in Peru: that is, the hypothesis of currency substitution can explain the behavior of real holdings of money in Peru. The paper also shows that, while, the importance of currency substitution as a transmission mechanism through which domestic policies affected the dynamics of inflation was relatively small during a period...

  13. Substitution treatment for opioid addicts in Germany

    Gerlach Ralf

    2007-02-01

    Full Text Available Abstract Background After a long and controversial debate methadone maintenance treatment (MMT was first introduced in Germany in 1987. The number of patients in MMT – first low because of strict admission criteria – increased considerably since the 1990s up to some 65,000 at the end of 2006. In Germany each general practitioner (GP, who has completed an additional training in addiction medicine, is allowed to prescribe substitution drugs to opioid dependent patients. Currently 2,700 GPs prescribe substitution drugs. Psychosocial care should be made available to all MMT patients. Results The results of research studies and practical experiences clearly indicate that patients benefit substantially from MMT with improvements in physical and psychological health. MMT proves successful in attaining high retention rates (65 % to 85 % in the first years, up to 50 % after more than seven years and plays a major role in accessing and maintaining ongoing medical treatment for HIV and hepatitis. MMT is also seen as a vital factor in the process of social re-integration and it contributes to the reduction of drug related harms such as mortality and morbidity and to the prevention of infectious diseases. Some 10 % of MMT patients become drug-free in the long run. Methadone is the most commonly prescribed substitution medication in Germany, although buprenorphine is attaining rising importance. Access to MMT in rural areas is very patchy and still constitutes a problem. There are only few employment opportunities for patients participating in MMT, although regular employment is considered unanimously as a positive factor of treatment success. Substitution treatment in German prisons is heterogeneous in access and treatment modalities. Access is very patchy and the number of inmates in treatment is limited. Nevertheless, substitution treatment plays a substantial part in the health care system provided to drug users in Germany. Conclusion In Germany, a

  14. Substitution treatment for opioid addicts in Germany.

    Michels, Ingo Ilja; Stöver, Heino; Gerlach, Ralf

    2007-02-02

    After a long and controversial debate methadone maintenance treatment (MMT) was first introduced in Germany in 1987. The number of patients in MMT--first low because of strict admission criteria--increased considerably since the 1990s up to some 65,000 at the end of 2006. In Germany each general practitioner (GP), who has completed an additional training in addiction medicine, is allowed to prescribe substitution drugs to opioid dependent patients. Currently 2,700 GPs prescribe substitution drugs. Psychosocial care should be made available to all MMT patients. The results of research studies and practical experiences clearly indicate that patients benefit substantially from MMT with improvements in physical and psychological health. MMT proves successful in attaining high retention rates (65% to 85% in the first years, up to 50% after more than seven years) and plays a major role in accessing and maintaining ongoing medical treatment for HIV and hepatitis. MMT is also seen as a vital factor in the process of social re-integration and it contributes to the reduction of drug related harms such as mortality and morbidity and to the prevention of infectious diseases. Some 10% of MMT patients become drug-free in the long run. Methadone is the most commonly prescribed substitution medication in Germany, although buprenorphine is attaining rising importance. Access to MMT in rural areas is very patchy and still constitutes a problem. There are only few employment opportunities for patients participating in MMT, although regular employment is considered unanimously as a positive factor of treatment success. Substitution treatment in German prisons is heterogeneous in access and treatment modalities. Access is very patchy and the number of inmates in treatment is limited. Nevertheless, substitution treatment plays a substantial part in the health care system provided to drug users in Germany. In Germany, a history of substitution treatment spanning 20 years has meanwhile

  15. [The substitution effect of leadership substitutes for transformational leadership in nursing organization].

    Kim, Jeong-Hee

    2006-04-01

    This paper was conducted to examine the effects of transformational leadership behaviors, within the substitutes for leadership model (Kerr & Jermier, 1978). Data was collected from 181 staff nurses in 3 general hospitals, with self-reporting questionnaires (MLQ developed by Bass, rd-SLS developed by Podsakoff, et al., and MSQ developed by Weiss, et al.). Descriptive statistics, factor analysis, Cronbach's alpha and moderated regression analysis were used. 1) The transformational leader behaviors and substitutes for leadership each had correlations with job satisfaction. 2) The total amount of variance accounted for by the substitutes for leadership was substantially greater than by the transformational leadership behaviors. 3) Few of the substitutes variables moderated the relationships between the transformational leader behaviors and job satisfaction in a manner consistent with that specified by Howell, Dorfman, and Kerr (1986). The finding of this study suggest that leaders need to have a better understanding of those contextual variables that influence job satisfaction. Thus future research should focus attention on the moderating effects of substitutes, as well as the things that leaders can do to influence them. In addition, it may be good to examine the effects of substitutes on other criterion variables.

  16. SUBSTITUTION OF CADMIUM CYANIDE ELECTROPLATING WITH ZINC CHLORIDE ELECTROPLATING

    The study evaluated the zinc chloride electroplating process as a substitute for cadmium cyanide electroplating in the manufacture of industrial connectors and fittings at Aeroquip Corporation. The process substitution eliminates certain wastes, specifically cadmium and cyanide, ...

  17. Convergent synthesis of 6-substituted phenanthridines via anionic ring closure

    Lysén, M.; Kristensen, Jesper Langgaard; Vedsø, P.

    2002-01-01

    Chemical equation presented The addition of organometallic derivatives to the cyano group of 2-(2-fluorophenyl)benzonitrile followed by intramolecular nucleophilic substitution produces 6-substituted phenanthridines. Alkyllithiums, aryllithiums, and sterically nondemanding lithium amides reacted ...

  18. Characterization of hydroxyapatite substituted with silicon

    Silva, H.M. da; Soares, G.A.; Mateescu, M.; Anselme, K.; Palard, M.; Champion, E.

    2009-01-01

    Incorporation of silicon (Si) ions into hydroxyapatite structure (HA) influences on physical, chemical and physiological properties. Some studies reported the improved bioactivity Si substitution, and it also accelerates the biomineralization process. The main objective of this work is to characterize stoichiometric hydroxyapatite and hydroxyapatite substituted with 1.13% in weight of Si (SiHA) using a wet precipitation method followed by a heat treatment. SEM/EDS, AFM, DRX and FTIR analyses were used to characterize the samples. EDS and FTIR results confirmed the presence of Si. Silicon induces small changes on crystal structure of HA, not detected on X-ray diffraction patterns of sintered tablets of SiHA and HA. No secondary phases were observed, that indicates the Si had entered the HA lattice. (author)

  19. The substitution bias of the consumer price index

    Frenger, Petter

    2006-01-01

    Abstract: The paper uses elementary consumer theory to propose an inflation independent ratio definition of the substitution bias of the Laspeyres consumer price index, and derives an approximate substitution bias which depends on the size of the price change as measured by a norm in the Laspeyres plane and on the elasticity of substitution in the direction of the price change. This norm or distance measure can be interpreted as a price substitution index which yields useful in...

  20. Unemployment, Factor Substitution, and Capital Formation

    Leo Kaas; Leopold von Thadden

    2001-01-01

    We incorporate a wage bargaining structure in a dynamic general equilibrium model and show how this feature changes short and long-run properties of equilibria compared with a perfectly competitive setting. We discuss how employment, capital, and income shares respond to wage setting shocks and show that adjustment dynamics depend decisively on the magnitude of the elasticity of substitution between labour and capital. Values of the elasticity below unity add persistence, tend to preserve sta...

  1. Mindfulness as substitute for transformational leadership

    Kroon, B.; van Woerkom, M.; Menting, Charlotte

    2017-01-01

    Purpose Transformational leaders spark the intrinsic motivation of employees, thereby stimulating their extra-role performance. However, not all employees are lucky enough to have a transformational leader. The purpose of this paper is to investigate to what extent mindfulness can function as a substitute for transformational leadership. By being attentive to and aware of what is taking place in the present, mindfulness provides employees with a source of intrinsic motivation that lies within...

  2. Neutron scattering from a substitutional mass defect

    Williams, R.D.; Lovesey, S.W.

    1985-06-01

    The dynamic structure factor is calculated for a low concentration of light mass scatterers substituted in a cubic crystal matrix. A new numerical method for the exact calculation is demonstrated. A local density of states for the low momentum transfer limit, and the shifts and widths of the oscillator peaks in the high momentum transfer limit are derived. The limitations of an approximation which decouples the defect from the lattice is discussed. (author)

  3. Substitution biases in price indices during transition

    Hanousek, Jan; Filer, Randall K.

    2004-01-01

    Roč. 21, č. 2 (2004), s. 167-177 ISSN 0167-8000 R&D Projects: GA MŠk ME 595 Institutional research plan: CEZ:AV0Z7085904 Keywords : price liberalization * substitution bias * transition economies Subject RIV: AH - Economics http://search. ebscohost .com/login.aspx?direct=true&db=a9h&AN=17109091&site=ehost-live

  4. Synthesis of 2-azetidinones substituted quinoline derivative

    Mashelkar Uday C.

    2013-01-01

    Full Text Available Acetanilide is converted into 2-chloro-3-formyl quinoline by reacting with DMF-POCl3 at 80-90ºC and then condensed with aromatic primary amines to give Schiff bases (3a-3c. These Schiff bases are then reacted with acid chlorides in the presence of base in toluene to give 1, 3, 4-substituted 2-azetidinones.

  5. Interfuel substitution in the United States

    Serletis, Apostolos; Vasetsky, Olexandr [Department of Economics, University of Calgary, Calgary, Alberta (Canada); Timilsina, Govinda R. [Development Research Group, The World Bank, 1818 H Street N.W., Washington, DC 20433 (United States)

    2010-05-15

    In this paper, we use the locally flexible translog functional form to investigate the demand for energy and interfuel substitution in the United States and to provide a comparison of our results with most of the existing empirical energy demand literature. Motivated by the widespread practice of ignoring theoretical regularity, we follow Barnett's (2002) suggestions and estimate the model subject to theoretical regularity, using methods developed by Diewert and Wales (1987) and Ryan and Wales (2000), in an attempt to produce inference consistent with neoclassical microeconomic theory. Moreover, we use the most recent data, published by the U.S. Energy Information Administration (EIA), and in addition to investigating interfuel substitution possibilities in total U.S. energy demand, we follow Serletis et al. (2009) and also examine interfuel substitution possibilities in energy demand by sector. Moreover, we test for weak separability, with the objective of discovering the structure of the functional form in total energy demand as well as energy demand by sector. (author)

  6. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Diazo substituted carbomonocyclic... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting under...

  7. 40 CFR 721.5350 - Substituted nitrile (generic name).

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted nitrile (generic name... Substances § 721.5350 Substituted nitrile (generic name). (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted nitrile (PMN P-83...

  8. 40 CFR 721.10043 - Dineopentyl-4-substituted phthalate (generic).

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Dineopentyl-4-substituted phthalate... Specific Chemical Substances § 721.10043 Dineopentyl-4-substituted phthalate (generic). (a) Chemical... as dineopentyl-4-substituted phthalate (PMN P-02-697) is subject to reporting under this section for...

  9. Arylazoindazole Photoswitches : Facile Synthesis and Functionalization via SNAr Substitution

    Travieso-Puente, Raquel; Budzak, Simon; Chen, Juan; Stacko, Peter; Jastrzebski, Johann T B H; Jacquemin, Denis; Otten, Edwin

    2017-01-01

    A straightforward synthetic route to arylazoindazoles via nucleophilic aromatic substitution is presented. Upon deprotonation of the NH group, a C6F5-substituted formazan undergoes facile cyclization as a result of intermolecular nucleophilic substitution (SNAr). This new class of azo photoswitches

  10. Annonaceae substitution rates: a codon model perspective

    Lars Willem Chatrou

    2014-01-01

    Full Text Available The Annonaceae includes cultivated species of economic interest and represents an important source of information for better understanding the evolution of tropical rainforests. In phylogenetic analyses of DNA sequence data that are used to address evolutionary questions, it is imperative to use appropriate statistical models. Annonaceae are cases in point: Two sister clades, the subfamilies Annonoideae and Malmeoideae, contain the majority of Annonaceae species diversity. The Annonoideae generally show a greater degree of sequence divergence compared to the Malmeoideae, resulting in stark differences in branch lengths in phylogenetic trees. Uncertainty in how to interpret and analyse these differences has led to inconsistent results when estimating the ages of clades in Annonaceae using molecular dating techniques. We ask whether these differences may be attributed to inappropriate modelling assumptions in the phylogenetic analyses. Specifically, we test for (clade-specific differences in rates of non-synonymous and synonymous substitutions. A high ratio of nonsynonymous to synonymous substitutions may lead to similarity of DNA sequences due to convergence instead of common ancestry, and as a result confound phylogenetic analyses. We use a dataset of three chloroplast genes (rbcL, matK, ndhF for 129 species representative of the family. We find that differences in branch lengths between major clades are not attributable to different rates of non-synonymous and synonymous substitutions. The differences in evolutionary rate between the major clades of Annonaceae pose a challenge for current molecular dating techniques that should be seen as a warning for the interpretation of such results in other organisms.

  11. Alkylation of N-substituted 2-phenylacetamides

    SLOBODAN D. PETROVIC

    2004-10-01

    Full Text Available Various N-substituted phenylacetamides were alkylated using different alkylating agents under neutral and basic conditions. Reactions were performed at different reaction temperatures and in various solvents. Also, a number of various catalysts were used including phase-transfer catalysts. Reactions were followed using GC or GC-MS technique and the presence as well as the yields of the alkylation products were established. Generally, the best yield and high selectivity in the studied reactions were achieved under basic conditions where in the certain cases some products, mostly N-product, were obtained solely in quantitative yields.

  12. Palladium complexes of pyrrole-2-aldehyde thiosemicarbazone ...

    Chem. Rev. 253 1384; (j) Lobana T S, Sharma. R, Bawa G and Khanna S 2009 Coord. Chem. Rev. 253. 977; (k) Quiroga A G and Ranninger C N 2004 Coord. Chem. Rev. 248 119; (l) Dilworth J R, Arnold P, Morales. D, Wong Y L and Zheng Y 2002 Modern Coord. Chem. 217; (m) West D X, Liberta A E, Padhye S B, Chikate.

  13. Synthesis and Biological Evaluation of Novel Thiosemicarbazone ...

    NICO

    referred to as 'covalent biotherapy', and thus possesses a dual mode of action, namely heme alkylation with the trioxane entity, and heme stacking and inhibition of ... through hydrogen bonding and dipole interactions.15 They are the main structural features of a number of antifungal drugs. (e.g. fluconazole, isavuconazole ...

  14. Advances in Osteobiologic Materials for Bone Substitutes.

    Hasan, Anwarul; Byambaa, Batzaya; Morshed, Mahboob; Cheikh, Mohammad Ibrahim; Shakoor, Rana Abdul; Mustafy, Tanvir; Marei, Hany

    2018-04-27

    A significant challenge in the current orthopedics is the development of suitable osteobiologic materials that can replace the conventional allografts, autografts and xenografts, and thereby serve as implant materials as bone substitutes for bone repair or remodeling. The complex biology behind the nano-microstructure of bones and their repair mechanisms, which involve various types of chemical and biomechanical signaling amongst different cells, has set strong requirements for biomaterials to be used in bone tissue engineering. This review presents an overview of various types of osteobiologic materials to facilitate the formation of the functional bone tissue and healing of the bone, covering metallic, ceramic, polymeric and cell-based graft substitutes, as well as some biomolecular strategies including stem cells, extracellular matrices, growth factors and gene therapies. Advantages and disadvantages of each type, particularly from the perspective of osteoinductive and osteoconductive capabilities, are discussed. Although the numerous challenges of bone regeneration in tissue engineering and regenerative medicine are yet to be entirely addressed, further advancements in osteobiologic materials will pave the way towards engineering fully functional bone replacement grafts. This article is protected by copyright. All rights reserved.

  15. Pressure-induced polymerization in substituted acetylenes

    Chellappa, Raja S.; Dattelbaum, Dana M.; Sheffield, Stephen; Robbins, David (LANL)

    2012-04-10

    A fundamental understanding of shock-induced chemical reactions in organics is still lacking and there are limited studies devoted to determining reaction mechanisms, evolution of bonding, and effect of functional group substitutions. The fast timescale of reactions occurring during shock compression create significant experimental challenges (diagnostics) to fully quantify the mechanisms involved. Static compression combined with temperature provides a complementary route to investigate the equilibrium phase space and metastable intermediates under extreme P-T conditions. In this study, we present our results from our ongoing high pressure in situ synchrotron x-ray diffraction experiments on substituted acetylenes: tert-butyl acetylene [TBA: (CH{sub 3}){sub 3}-C=CH] and ethynyl trimethylsilane [ETMS: (CH{sub 3}){sub 3}-SiC=CH]. We observed that the onset pressure of chemical reactions (at room temperature) in these compounds is higher under static compression (TBA: 12 GPa and ETMS: 17.6 GPa) when compared to shock input pressures (TBA: 6.1 GPa and ETMS: 6.6 GPa). At elevated temperatures, reactivity was observed to occur at pressures comparable to shock conditions. The products were polymeric in nature, recovered to ambient conditions with little degradation.

  16. Challenges in drug discovery for thiazolidinedione substitute

    Jian-ping Ye

    2011-10-01

    Full Text Available Thiazolidinedione (TZD is a powerful insulin sensitizer in the treatment of type 2 diabetes. It acts as a ligand to the nuclear receptor PPARγ (peroxisome proliferator-activated receptor-gamma and induces transcription of PPARγ-responsive genes. TZD controls lipid synthesis and storage in adipose tissue, liver and many other tissues through PPARγ. Derivatives of TZD, such as rosiglitazone (Avandia and pioglitazone (Actos, are more powerful than metformin or berberine in insulin sensitization. Although they have common side effects such as weight gain and edema, these did not influence their clinical application in general. However, recent findings of risk for congestive heart failure and bladder cancer have significantly impaired their future in many countries. European countries have prohibited those drugs, and US will terminate application of rosiglitazone in clinics and hospitals. The multiple country actions may mark the end of TZD era. As a result, there is a strong demand for identification of TZD substitute in the treatment of type 2 diabetes. In this regard, literature about PPARγ ligands and potential TZD substitute are reviewed in this article. Histone deacetylase (HDAC inhibitor is emphasized as a new class of insulin sensitizer here. Regulators of SIRT1, CREB, NO, p38, ERK and Cdk5 are discussed in the activation of PPARγ.

  17. Substitution of thoriated tungsten electrodes in Switzerland

    Kunz, H.; Piller, G.

    2006-01-01

    Thoriated tungsten electrodes are frequently used for inert gas welding (TIG/WIG). The use of these electrodes can lead to doses which are well above the limit for the general population (1mSv/year). This has been shown by different investigations, for example from the ''Berufsgenossenschaft''. With these findings in mind, the regulatory authorities (Swiss Federal Office of Public Health (SFOPH) and Swiss National Accident Insurance Association (Suva)) started in 1999 to examine the justification of thoriated tungsten electrodes and a possible substitution with products containing no radioactive material. Up to this time, the use of thoriated tungsten electrodes could be justified since no thorium-free products leading to comparable results were available on the market. This was also the reason why the SFOPH approved several types of these electrodes. Discussions with formation centers for welding and inquiries made at welding shops, trading companies and producers showed that in the mean-time thorium-free products with comparable welding specifications and results became available on the market. Since the 1 January 2004, thoriated tungsten electrodes can only be used if the user has obtained the corresponding license from the SFOPH. The use of thoriated tungsten electrodes is thus not completely forbidden, but very strict conditions have to be fulfilled. Up to now and due to the involvement of the relevant partners, the substitution process has not met any problem. Neither trading companies nor users made any opposition and no request for obtaining a license for thoriated tungsten electrodes was made. (orig.)

  18. Cation Radical Accelerated Nucleophilic Aromatic Substitution via Organic Photoredox Catalysis.

    Tay, Nicholas E S; Nicewicz, David A

    2017-11-15

    Nucleophilic aromatic substitution (S N Ar) is a direct method for arene functionalization; however, it can be hampered by low reactivity of arene substrates and their availability. Herein we describe a cation radical-accelerated nucleophilic aromatic substitution using methoxy- and benzyloxy-groups as nucleofuges. In particular, lignin-derived aromatics containing guaiacol and veratrole motifs were competent substrates for functionalization. We also demonstrate an example of site-selective substitutive oxygenation with trifluoroethanol to afford the desired trifluoromethylaryl ether.

  19. Perron-Frobenius theory and frequency convergence for reducible substitutions

    Lustig, Martin; Uyanik, Caglar

    2016-01-01

    We prove a general version of the classical Perron-Frobenius convergence property for reducible matrices. We then apply this result to reducible substitutions and use it to produce limit frequencies for factors and hence invariant measures on the associated subshift. The analogous results are well known for primitive substitutions and have found many applications, but for reducible substitutions the tools provided here were so far missing from the theory.

  20. Goods-Time Elasticity of Substitution in Health Production.

    Du, Juan; Yagihashi, Takeshi

    2017-11-01

    We examine how inputs for health production, in particular, medical care and health-enhancing time, are combined to improve health. The estimated elasticity of substitution from a constant elasticity of substitution production function is significantly less than one for the working-age population, rejecting the unit elasticity of substitution used in previous studies. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  1. Import Substitution in Regional Industrial Production: Theoretical and Practical Aspects

    Yevgeniy Georgievich Animitsa

    2015-09-01

    Full Text Available The article proves the important role of import substitution in the economic security protection of state and its regions, especially in times of crisis, geopolitical and economical instability. The authors argue that the problem of import substitution is not modern, trendy scientific stream. The issue of displacement of import goods by domestic ones was brought up in famous classic theories of mercantilists. The particular emphasis is placed on the analysis and systematization of different scientific approaches, which are utilized by native and foreign scientists to bring out the matter of “import substitution,” to determine its essential characteristics. The authors suggest their own interpretation of the import substitution notion. In the article, the most significant pro and contra arguments in import substitution policy are defined. The regional aspects in the import substitution are approved: case study — organization of industrial import substitution in the Sverdlovsk region. In the article, the authors analyze the subject matter of the Program “Development of Intraregional Industrial Cooperation and Implementation of an Import Substitution in Branches of Industry in the Sverdlovsk Region.” It is resumed, that active policy of import substitution in the industry may become the driver of regional economic development.

  2. Zinc and Carbonate Co-Substituted Nano-Hydroxyapatite

    Girija, E. K.; Kumar, G. Suresh; Thamizhavel, A.

    2011-07-01

    Synthesis of Zn or CO32- substituted nano-hydroxyapatite (HA) and its physico-chemical properties have been well documented. However, the effects of the simultaneous substitution of Zn and CO32- in nano-HA have not been reported. In the present study, Zn and CO32- substitutions in nano HA independently and concurrently have been done by wet precipitation method and characterized by XRD and FT-IR for its phase purity and chemical homogeneity. Further modulations of the bioactivity and thermal stability of HA due to the substitutions have been studied.

  3. Technological substitution options for controlling greenhouse gas emissions

    Barbier, E.B.; Burgess, J.C.; Pearce, D.W.

    1991-01-01

    This chapter is concerned with technological options for greenhouse gas substitution. The authors interpret the term substitution to exclude energy conservation/efficiency measures, investments in afforestation (sinks), and greenhouse gas removal or abatement technologies. Their working definition of greenhouse gas substitution includes (1) replacement technologies, for example, substituting a greenhouse gas technology with a nongreenhouse gas technology; and (2) reduction technologies, for example, substituting a greenhouse gas technology with an alternative technology that reduces greenhouse gas emissions. Essentially, replacement technologies involve 100 percent reduction in CO 2 ; reduction technologies involve a partial reduction in CO 2 . Of the man-made sources of greenhouse gases, energy is the most important and is expected to contribute to at least half of the global warming effect in the near future. The majority of this impact is from fossil fuel combustion as a source of carbon dioxide (CO 2 ), although fossil fuels also contribute significantly to methane (CH 4 ), to nitrous oxide (N 2 O), and to low-level ozone (O 3 ) through production of various nitrogen gases (NO x ) and carbon monoxide (CO). This study analyzes the available greenhouse gas substitutions and their costs. The authors concentrate particularly on substitutions for fossil-fuel combustion and CFC production and consumption. They conclude by summarizing the potential for greenhouse gas substitution, the cost-effectiveness of the various options and the design of incentives for substitution

  4. Time and Money - Are they Substitutes?

    Bonke, Jens; Deding, Mette; Lausten, Mette

    In this paper, we analyse the distribution of time and money for Danish wage earner couples, where time is defined as leisure time and money as extended income, i.e. the sum of disposable income and the value of housework. The hypothesis is that individuals being rich in one dimension are more...... likely to be poor in the other dimension, such that individuals can be classified as either money-poor/time-rich or money-rich/time-poor. We analyse two different distributions of income, where the first assumes no sharing and the second complete sharing of income between spouses. The data are from...... the Danish Time-Use Survey 2001, merged with register data. Results show that the substitution of money for time is more prominent for women than for men, because they have a larger income share of time-intensive value of housework, while men have the larger share of disposable income. Furthermore, when...

  5. SYNTHESIS OF SUBSTITUTED QUINOLINE-3-CARBALDEHYDES

    L. G. Klad'ko

    2015-12-01

    Full Text Available Dehalogenation of а series substituted 2-chloroquinoline-3-carbaldehydes was investigated. It was found that zinc dust in alkali ethanol practically do not react with 2-chloro-3-(1,3-dioxolan-2-yl-7-methylquinolines for a 5 day at ambient temperature. Increase temperature to boiling point of reaction mixture lead to increase yield 7-methylquinoline-3-carbaldehyde to 12.5%. This reaction with 2-chloro-3-dimetoxymetyl-7-methylquinoline give 26.5 above aldehyde. Replacement of ethanol to methanol give only traces of desired aldehyde. Neither 2-chloro-7-methylquinoline-3-carbaldehyde, nor his acetals do not react with sodium dithionite. Furthermore for activation of halogen we replaced chloraldehydes to iodoaldehydes by Finkelstein reaction, then protect aldehyde function by formation of dimethylacetals and treatment his by sodium dithionite in mixture pyridine-water. Desired aldehydes was obtained with poor to moderate yields. Increasing yields of this reaction is goal our further investigations.

  6. Porous bioresorbable magnesium as bone substitute

    Wen, C.E.; Yamada, Y.; Shimojima, K.; Chino, Y.; Hosokawa, H.; Mabuchi, M. [Inst. for Structural and Engineering Materials, National Inst. of Advanced Industrial Science and Technology, Nagoya (Japan)

    2003-07-01

    Recently magnesium has been recognized as a very promising biomaterial for bone substitutes because of its excellent properties of biocompatibility, biodegradability and bioresorbability. In the present study, magnesium foams were fabricated by using a powder metallurgical process. Scanning electron microscopy equipped with energy dispersive X-ray spectrometer (EDS) and compressive tester were used to characterize the porous magnesium. Results show that the Young's modulus and the peak stress of the porous magnesium increase with decreasing porosity and pore size. This study suggests that the mechanical properties of the porous magnesium with the low porosity of 35% and/or with the small pore size of about 70 {mu}m are close to those of human cancellous bones. (orig.)

  7. Substitution reactions of carbon nanotube template

    Li, Chi Pui; Chen, Ying; Gerald, John Fitz

    2006-05-01

    Substitution reactions between carbon nanotube (CNT) template and SiO with the formation of carbon rich silicon oxide nanowires (SiO-C-NWs) have been investigated using transmission electron microscopy and x-ray energy dispersive spectroscopy. The reaction was carried out by thermal annealing at 1200°C for 1h of a mixture of silicon monoxide (SiO) and iron (II) phthalocyanine, FeC32N8H16 (FePc) powders. Multiwalled CNTs were produced first via pyrolysis of FePc at a lower temperature (1000°C ). SiO vapors reacted with the CNTs at higher temperatures to produce amorphous SiO-C-NWs with a uniform diameter and a length in tens of micrometers. The special bamboolike structure of the CNTs allows the reaction to start from the external surface of the tubes and transform each CNT into a solid nanowire section by section.

  8. Packing and Disorder in Substituted Fullerenes

    Tummala, Naga Rajesh

    2016-07-15

    Fullerenes are ubiquitous as electron-acceptor and electron-transport materials in organic solar cells. Recent synthetic strategies to improve the solubility and electronic characteristics of these molecules have translated into a tremendous increase in the variety of derivatives employed in these applications. Here, we use molecular dynamics (MD) simulations to examine the impact of going from mono-adducts to bis- and tris-adducts on the structural, cohesive, and packing characteristics of [6,6]-phenyl-C60-butyric acid methyl ester (PCBM) and indene-C60. The packing configurations obtained at the MD level then serve as input for density functional theory calculations that examine the solid-state energetic disorder (distribution of site energies) as a function of chemical substitution. The variations in structural and site-energy disorders reflect the fundamental materials differences among the derivatives and impact the performance of these materials in thin-film electronic devices.

  9. Crossmodal Perceptual Learning and Sensory Substitution

    Michael J Proulx

    2011-10-01

    Full Text Available A sensory substitution device for blind persons aims to provide the missing visual input by converting images into a form that another modality can perceive, such as sound. Here I will discuss the perceptual learning and attentional mechanisms necessary for interpreting sounds produced by a device (The vOICe in a visuospatial manner. Although some aspects of the conversion, such as relating vertical location to pitch, rely on natural crossmodal mappings, the extensive training required suggests that synthetic mappings are required to generalize perceptual learning to new objects and environments, and ultimately to experience visual qualia. Here I will discuss the effects of the conversion and training on perception and attention that demonstrate the synthetic nature of learning the crossmodal mapping. Sensorimotor experience may be required to facilitate learning, develop expertise, and to develop a form of synthetic synaesthesia.

  10. Magnetic disaccommodation in Sn substituted magnetite

    Hernandez-Gomez, P.; Bendimya, K.; Francisco, C. de; Munoz, J.M.; Alejos, O.; Torres, C.

    2001-01-01

    The relaxation of the initial magnetic permeability has been measured in polycrystalline Sn-doped magnetite with nominal composition Sn x Fe 3-x O 4 with x ranging from x=0 to 0.6. In the temperature range between 80 and 500 K, the time decay of the initial permeability after sample demagnetization has been represented by means of isochronal disaccommodation curves, which show the presence of different relaxation processes at 250 K (IV' peak), 275 K (IV), 300 K (III), 400 K (II) and 440 K (I). This behavior is explained on the basis of the disaccommodation of vacancy-doped magnetite and another similar tetravalent substitution, as the previously analyzed Ti-doped magnetite

  11. Hazardous Solvent Substitution Data System tutorial

    Twitchell, K.E.; Skinner, N.L.

    1993-07-01

    This manual is the tutorial for the Hazardous Solvent Substitution Data System (HSSDS), an online, comprehensive system of information on alternatives to hazardous solvents and related subjects. The HSSDS data base contains product information, material safety data sheets, toxicity reports, usage reports, biodegradable data, product chemical element lists, and background information on solvents. HSSDS use TOPIC reg-sign to search for information based on a query defined by the user. TOPIC provides a full text retrieval of unstructured source documents. In this tutorial, a series of lessons is provided that guides the user through basic steps common to most queries performed with HSSDS. Instructions are provided for both window-based and character-based applications

  12. Substitution effects in magnetic and superconducting materials

    Peña, O.

    1999-10-01

    Full Text Available Chemical substitutions at very low level have been proved to be a very effective tool to change important physical parameters in many kinds of materials. These modifications may be the result of, for instance, subtle variations of the position of the Fermi level with respect to the density of states, presence of additional electrons which may change the hole carrier concentration, steric effects which impose contraints in the crystallographic lattice, mixed-valence states resultating from the dismutation of chemical components, etc. We review herein three systems in which the substitution effects are at the origin of new physical states : the high-Tc superconductor bismuth cuprate of the 2212 family, the mixed-valence manganese perovskites representative of giant magneto-resistive compounds, and the Chevrel phase materials in which a structural transition may inhibit the superconducting state.

    Las substituciones químicas a un nivel muy pequeño se han probado como una importante herramienta para cambiar los parámetros físicos en una gran variedad de materiales. Estas modificaciones pueden ser el resultado de, por ejemplo, muy ligeras variaciones de la posición del nivel de Fermi con respecto a la densidad de estados, presencia de electrones adicionales que pueden cambiar la concentración de portadores tipo huecos, efectos estéricos que imponen restricciones en la red cristalográfica, estados de valencia mixtos resultantes de la dismutación de los componentes químicos, etc. Aquí se revisan tres sistemas donde los efectos de substitución son el origen de nuevos estados físicos: los superconductores de alta temperatura basados en cupratos de bismuto de la familia 2212, las perovskitas de manganeso de valencia mixta representantes de compuestos con magnetorresistencia gigante, y los materiales con fases de Chevrelt cuya transición estructural puede inhibir el estado superconductor.

  13. Substituted Pyrazinecarboxamides: Synthesis and Biological Evaluation

    Katarina Kralova

    2006-03-01

    Full Text Available Condensation of the corresponding chlorides of some substituted pyrazine-2-carboxylic acids (pyrazine-2-carboxylic acid, 6-chloropyrazine-2-carboxylic acid, 5-tert-butylpyrazine-2-carboxylic acid or 5-tert-butyl-6-chloropyrazine-2-carboxylic acid withvarious ring-substituted aminothiazoles or anilines yielded a series of amides. Thesyntheses, analytical and spectroscopic data of thirty newly prepared compounds arepresented. Structure-activity relationships between the chemical structures and the anti-mycobacterial, antifungal and photosynthesis-inhibiting activity of the evaluatedcompounds are discussed. 3,5-Bromo-4-hydroxyphenyl derivatives of substitutedpyrazinecarboxylic acid, 16-18, have shown the highest activity against Mycobacteriumtuberculosis H37Rv (54-72% inhibition. The highest antifungal effect againstTrichophyton mentagrophytes, the most susceptible fungal strain tested, was found for5-tert-butyl-6-chloro-N-(4-methyl-1,3-thiazol-2-ylpyrazine-2-carboxamide (8, MIC =31.25 μmol·mL-1. The most active inhibitors of oxygen evolution rate in spinachMolecules 2006, 11 243 chloroplasts were the compounds 5-tert-butyl-6-chloro-N-(5-bromo-2-hydroxyphenyl- pyrazine-2-carboxamide (27, IC50 = 41.9 μmol·L-1 and 5-tert-butyl-6-chloro-N-(1,3- thiazol-2-yl-pyrazine-2-carboxamide (4, IC50 = 49.5 μmol·L-1.

  14. Polyphosphates substitution for zeolite to in detergents

    Restrepo V, Gloria M.; Ocampo G, Aquiles; Saldarriaga M, Carlos

    1996-01-01

    The detergents, as well as the cleaning products, contain active ingredients that are good to increase their efficiency and some of them, as the sodium Tripoli-phosphate (TPF), they have turned out to be noxious for the environment. The zeolites use in the formulation of detergents has grown substantially since they fulfill the same function of the TPF and they have been recommended ecologically as substitutes from these when not being polluting. The objective of this work is to obtain a zeolite with appropriate characteristics for its use in the formulation of detergents, reproducing those of the zeolites used industrially. The zeolite synthesis is studied 4A starting from hydro-gels of different composition, varying the operation conditions and using two raw materials: (sodium meta-silicate, commercial degree and metallic aluminum) and clay type kaolin like silica source and aluminum It is looked for to get a product of beveled cubic morphology, or spherical, with glass size between 1 and 3 microns and that it possesses good capacity of conical exchange. Since the capacity and speed of ionic exchange is influenced by the particle size, time of contact and temperature, experimentation conditions settle down to measure the exchange of ions calcium and magnesium in watery solutions that they simulate the real situation of a laundry process in the country. This way the ability of the zeolite 4A obtained to diminish the concentration of these ions in the laundry waters is evaluated and its possibilities like component in the formulation of detergents non-phosphatates. Of the synthesized zeolites, the best in agreement is chosen with chemical properties as ionic and physical exchange capacity as crystalline, particle size and color, to prepare a detergent in which the polyphosphates is substituted partial and totally for the synthesized zeolite

  15. 49 CFR 383.77 - Substitute for driving skills tests.

    2010-10-01

    ... 49 Transportation 5 2010-10-01 2010-10-01 false Substitute for driving skills tests. 383.77... Substitute for driving skills tests. At the discretion of a State, the driving skill test as specified in... acceptable skills test, or an applicant's driving record in combination with certain driving experience. The...

  16. Substitute equations for index reduction and discontinuity handling

    Fabian, G.; Beek, van D.A.; Rooda, J.E.

    2000-01-01

    Several techniques exist for index reduction and consistent initialization of higher index DAEs. Many such techniques change the original set of equations by differentiation, substitution, and/or introduction of new variables. This paper introduces substitute equations as a new language element. By

  17. Control of Chemical Risks by Substitution of Harmful Substances

    Jacobsen, Thomas

    1997-01-01

    Substitution of volatile, organic solvents with non-volatile, low-toxic esters of fatty acids for cleaning purposes in offset printing has successfully been implemented in several European countries. Similar substitutions in other industrial cleaning processes seem possible, especially regarding...

  18. Mass spectrometric investigation of vinyl-substituted organic boron compounds

    Tarielashvili, V.O.; Ordzhonikidze, K.G.; Parulava, L.P.; Vakhaniya, G.V.

    1992-01-01

    Mass spectrometric investigation of vinyl-substituted organic compounds was conducted. Ionization was performed by electron shock. Possibility of determining boron isotope content is all analyzed organic boron vinyl-substituted compounds by direct method is shown. This simplifies sufficiently and lowers the price of analysis, improves its accuracy and rapidity

  19. Design, Synthesis and Insecticidal Activities of Novel Phenyl Substituted Isoxazolecarboxamides

    LIU Peng-fei; ZHANG Ji-feng; YAN Tao; XIONG Li-xia; LI Zheng-ming

    2012-01-01

    Thirteen novel phenyl substituted isoxazolecarboxamides were synthesized,and their structures were characterized by 1H NMR,elementary analysis and high-resolution mass spectrometry(HRMS) techniques.Their evaluated insecticidal activities against oriental armyworm(Mythimna separata) indicate that the phcnyl substituted isoxazolecarboxamides exhibited moderate insecticidal activities,among which compounds 9c and 9k showed comparatively higher activities.

  20. Sublattice imbalance of substitutionally doped nitrogen in graphene

    Lawlor, James A.; Gorman, Paul D.; Power, Stephen

    2014-01-01

    Motivated by the recently observed sublattice asymmetry of substitutional nitrogen impurities in CVD grown graphene, we show, in a mathematically transparent manner, that oscillations in the local density of states driven by the presence of substitutional impurities are responsible for breaking......, but should be present in other impurities. (C) 2014 Elsevier Ltd. All rights reserved....

  1. Maximum parsimony, substitution model, and probability phylogenetic trees.

    Weng, J F; Thomas, D A; Mareels, I

    2011-01-01

    The problem of inferring phylogenies (phylogenetic trees) is one of the main problems in computational biology. There are three main methods for inferring phylogenies-Maximum Parsimony (MP), Distance Matrix (DM) and Maximum Likelihood (ML), of which the MP method is the most well-studied and popular method. In the MP method the optimization criterion is the number of substitutions of the nucleotides computed by the differences in the investigated nucleotide sequences. However, the MP method is often criticized as it only counts the substitutions observable at the current time and all the unobservable substitutions that really occur in the evolutionary history are omitted. In order to take into account the unobservable substitutions, some substitution models have been established and they are now widely used in the DM and ML methods but these substitution models cannot be used within the classical MP method. Recently the authors proposed a probability representation model for phylogenetic trees and the reconstructed trees in this model are called probability phylogenetic trees. One of the advantages of the probability representation model is that it can include a substitution model to infer phylogenetic trees based on the MP principle. In this paper we explain how to use a substitution model in the reconstruction of probability phylogenetic trees and show the advantage of this approach with examples.

  2. Effect of Honey as Partial Sugar Substitute on Pasting Properties ...

    The effect of partial substitution of sugar with liquid honey on the pasting properties of cooked dough made from cassava-wheat composite (10:90) flour as well as the sensory preference and shelf stability of its bread was investigated. Sucrose (S) in the bread recipe formulation was substituted with honey (H) at levels 0, 10, ...

  3. Thermal stability of substitutional ag in CdTe

    Jahn, SG; Hofsass, H; Restle, M; Ronning, C; Quintel, H; BharuthRam, K; Wahl, U

    The thermal stability of substitutional Ag in CdTe was deduced from lattice location measurements at different temperatures. Substitutional Ag probe atoms were generated via transmutation doping from radioactive Cd isotopes. The lattice sites of Ag isotopes were determined by measuring the

  4. Influence of higher sodium substitutions on magnetic entropy ...

    The change in entropy also decreases with increase in substitution of sodium. A notable change ... of substituting elements for A and B ions, valence states of. Mn and the oxygen ... applied external magnetic field of 7 T.17 Sodium substitu- ..... Bohigas X, Tejada J, Del Barco E, Zhang X X and Sales M. 1998 Appl. Phys. Lett.

  5. 21 CFR 184.1259 - Cocoa butter substitute.

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cocoa butter substitute. 184.1259 Section 184.1259... FOR HUMAN CONSUMPTION (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific Substances Affirmed as GRAS § 184.1259 Cocoa butter substitute. (a) The common or...

  6. 76 FR 8666 - Substitution in Case of Death of Claimant

    2011-02-15

    ... DEPARTMENT OF VETERANS AFFAIRS 38 CFR Parts 3, 14, 20 RIN 2900-AN91 Substitution in Case of Death... Veterans Affairs (VA) proposes to amend its regulations concerning adjudication of claims, representation..., not later than one year after the death of the claimant, request to be substituted for the claimant...

  7. Labour migration and substitution (updated) : Second, revised version

    Cremers, Jan

    2017-01-01

    This (revised) paper compares the outcomes of several national and international studies on substitution as a consequence of migrants entering the labour market. Substitution appears if finding a job by one person results in the job loss (or non-obtaining of a job) of another person. The recruitment

  8. Substitution as a Device of Grammatical Cohesion in English Contexts

    Mohammad Reza Hasannejad

    2012-05-01

    Full Text Available The present study set out to investigate the effect of teaching substitution as a kind of grammatical cohesion on the true identification of confusing substitution elements with cohesive or non-cohesive roles in different contexts and also the production of modal, reporting and conditional contexts through clausal substitution acquaintance. To this end, the following procedures were taken. First 120 male and female EFL students were selected from Iranshahr Azad University. Having administered the language proficiency test, researchers selected 80 students as intermediate subjects according to their TOEFL band scores. First, pretests of cohesion identification (substitution and production of modal, reporting and conditional environments were administered to both control and experimental groups. Then, the experimental group was exposed to the teaching of the above-said above-mentioned cohesive device. Finally, post-tests of substitution elements’ identification and modal, reporting and conditional contexts’ production through clausal substitution familiarity were administered. The results showed that cohesive device treatment helped students on the true identification of substitution elements. Another finding proved that EFL students might have no difficulty in learning certain rules or classification of rules and application of their clausal substitution knowledge in creating modal, reporting and conditional contexts. Our findings can have implications for the field of language learning and teaching.

  9. 40 CFR 721.562 - Substituted alkylamine salt.

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkylamine salt. 721.562 Section 721.562 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.562 Substituted alkylamine salt...

  10. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    2010-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting under...

  11. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    2010-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject to...

  12. Cation substitution induced blue-shift of optical band gap

    Cation substitution induced blue-shift of optical band gap in nanocrystalline Zn ( 1 − x ) Ca x O thin films deposited by sol–gel dip coating technique ... thin films giving 13.03% enhancement in theenergy gap value due to the electronic perturbation caused by cation substitution as well as deterioration in crystallinity.

  13. MOLECULAR THERMODYNAMICS IN THE DESIGN OF SUBSTITUTE SOLVENTS

    The use of physical properties and fluid behavior from molecular thermodynamics can lead to better decision making in the design of substitute solvents and can greatly reduce the expense and time required to find substitutes compared to designing solvents by experiment. this pape...

  14. Antimony substitution in SmFeAsO

    Schmidt, Daniel; Braun, Hans F. [Universitaet Bayreuth (Germany)

    2015-07-01

    In the iron based compounds structural and magnetic phase transitions can be suppressed by applying external hydrostatic pressure and superconductivity emerges. Beside hydrostatic pressure, it is possible to apply chemical pressure by the substitution of atoms in the compounds with smaller ones. Such a substitution was successful for example in LaFeAs{sub 1-x}P{sub x}O, where the parent compound shows a structural and a spin-density-wave transition and the P doped samples become superconducting. We are interested in the opposite way and substitute the As by the bigger Sb. In literature, the substitution in the La-1111 compounds was possible up to a substitution level of 40 %. With Sm, instead of La, we used a smaller rare-earth metal. We present the results obtained on polycrystalline samples characterized by Xray powder diffraction and resistivity measurements.

  15. REACH-related substitution within the Danish printing industry

    Larsen, Henrik Fred; Bøg, Carsten; Markussen, Helene

    are running a substitution project. A major part of the work has been mapping the presence of chemicals which are potential candidates for substitution (e.g. PBT, CMR, vPvB, EDS) within the Danish printing industry. The mapping comprises a combination of a literature study and an investigation of the actual......The accomplishment of the EU REACH regulation will most probably promote substitution within sectors handling a lot of different chemicals like the printing industry. With the aim of being at the cutting edge of this development the Danish EPA together with the Danish printing industry and IPU...... fulfil one or more of the criteria (e.g. CMR, EDS) for the REACH Annex XIV candidate list (authorisation). The paper presents the results of the mapping of chemical candidates and the first results of the actual substitutions. Keywords: REACH, chemicals, substitution, printing industry....

  16. A Group Action Method for Construction of Strong Substitution Box

    Jamal, Sajjad Shaukat; Shah, Tariq; Attaullah, Atta

    2017-06-01

    In this paper, the method to develop cryptographically strong substitution box is presented which can be used in multimedia security and data hiding techniques. The algorithm of construction depends on the action of a projective general linear group over the set of units of the finite commutative ring. The strength of substitution box and ability to create confusion is assessed with different available analyses. Moreover, the ability of resistance against malicious attacks is also evaluated. The substitution box is examined by bit independent criterion, strict avalanche criterion, nonlinearity test, linear approximation probability test and differential approximation probability test. This substitution box is equated with well-recognized substitution boxes such as AES, Gray, APA, S8, prime of residue, Xyi and Skipjack. The comparison shows encouraging results about the strength of the proposed box. The majority logic criterion is also calculated to analyze the strength and its practical implementation.

  17. Potential radiosensitizing agents. 5. 2-Substituted benzimidazole derivatives

    Gupta, R.P.; Larroquette, C.A.; Agrawal, K.C.

    1982-01-01

    A series of 2-substituted benzimidazoles and their derivatives have been synthesized and tested for their ability to selectively sensitize hypoxic Chinese hamster cells (V-79) toward the lethal effect of ionizing radiation. These compounds were prepared by reacting the 2-substituted benzimidazoles with 1,2-epoxy-3-methoxypropane in the presence of potassium carbonate. Reaction of the 2-nitro and 2-methylfonyl analogue with the epoxide also yielded a cyclized material, which was confirmed to be a benzimidazo[2,1-b]oxazole. In an attempt to increase the electron affinity, 5- or 6-nitro-2-substituted-benzimidazoles were also synthesized and then reacted with the epoxide to yield the corresponding 1-substituted derivatives. The results of the biological tests for the radiosensitizing activity of these agents against Chinese hamster cells (V-79) in culture indicated that the 2-nitro-substituted analogues were the most effective sensitizers in this series

  18. Substituted amylose matrices for oral drug delivery

    Moghadam, S H; Wang, H W; El-Leithy, E Saddar; Chebli, C; Cartilier, L

    2007-01-01

    High amylose corn starch was used to obtain substituted amylose (SA) polymers by chemically modifying hydroxyl groups by an etherification process using 1,2-epoxypropanol. Tablets for drug-controlled release were prepared by direct compression and their release properties assessed by an in vitro dissolution test (USP XXIII no 2). The polymer swelling was characterized by measuring gravimetrically the water uptake ability of polymer tablets. SA hydrophilic matrix tablets present sequentially a burst effect, typical of hydrophilic matrices, and a near constant release, typical of reservoir systems. After the burst effect, surface pores disappear progressively by molecular association of amylose chains; this allows the creation of a polymer layer acting as a diffusion barrier and explains the peculiar behaviour of SA polymers. Several formulation parameters such as compression force, drug loading, tablet weight and insoluble diluent concentration were investigated. On the other hand, tablet thickness, scanning electron microscope analysis and mercury intrusion porosimetry showed that the high crushing strength values observed for SA tablets were due to an unusual melting process occurring during tabletting although the tablet external layer went only through densification, deformation and partial melting. In contrast, HPMC tablets did not show any traces of a melting process

  19. Development of a piezoelectric bone substitute material

    Al-Bader, Yousef A.

    2000-01-01

    The thesis deals with the preparation and testing of ceramic compositions to be used as bone substitute. The proposed composition consisted of calcium enriched calcium phosphate, kaolin and barium titanate in different ratios. The homogeneous powder mixture was dry pressed at different pressures and fired at temperatures up to 1350 degC for different soaking times. The physical properties of the fired compacts that were tested are bulk density and porosity. These were determined as function of pressing pressure, firing temperature and soaking time for different compositions. The mechanical properties investigated were the ultimate compressive strength and Young's modulus, which were determined for different compositions and forming pressures. The electrical properties investigated were D.C. characteristics (resistivity) and A.C. characteristics (A.C. resistivity, dielectric constant, dielectric loss and loss tangent). The piezoelectric behaviour of the fired compacts was investigated and the piezoelectric coefficient (d) in the axial direction was obtained as a function of the percent barium titanate added. The development of piezoelectricity when barium titanate is added was interpreted, using XRD, as due to the formation of barium titanate silicate. Compositions determined as having properties comparable to those of natural bone, were tested for in vitro solubility in pure water and saline solution. The results obtained showed that the selected composition (containing 15% kaolin, 10% barium titanate, pressed at 35 MPa and fired at 1350 degC for two hours) has properties comparable to those of dry bone and a reasonable in vitro solubility. (author)

  20. Substitution of photomultiplier tubes by photodiodes

    Teixeira, D.L.

    1990-04-01

    The application of Si semiconductors, either of the conventional or the avalanche type, as light amplifiers in radiation detection, has been studied aiming the substitution of photomultiplier (PM) tubes by photodiodes. The objective of this work is to compare the response of photodiodes and PM tubes when coupled to scintillation crystals. A Hamamatsu Si photodiode, model S 1337-66 B Q, was coupled to a Harshaw NaI (TI) scintillation crystal of window diameter equal to 25,4 mm. Its performance was evaluated by specially designed associated electronics, compatible with the photodiode characteristics. X-ray beams from 30 to 111 KeV were used to determine the response and the repeatability of the scintillator-photodiode and the scintillator-PM tube systems. The repeatability was found to be within 0,27% for the photodiode and 0,57% for the PM tube. This work confirmed that photodiodes can be used as light amplifiers, provided their characteristics, such as light spectrum response, are considered. It also shows that further studies are necessary in order to identify the applications in radiation detection where PM tubes might be replaced by photodiodes. (author)

  1. New substitution models for rooting phylogenetic trees.

    Williams, Tom A; Heaps, Sarah E; Cherlin, Svetlana; Nye, Tom M W; Boys, Richard J; Embley, T Martin

    2015-09-26

    The root of a phylogenetic tree is fundamental to its biological interpretation, but standard substitution models do not provide any information on its position. Here, we describe two recently developed models that relax the usual assumptions of stationarity and reversibility, thereby facilitating root inference without the need for an outgroup. We compare the performance of these models on a classic test case for phylogenetic methods, before considering two highly topical questions in evolutionary biology: the deep structure of the tree of life and the root of the archaeal radiation. We show that all three alignments contain meaningful rooting information that can be harnessed by these new models, thus complementing and extending previous work based on outgroup rooting. In particular, our analyses exclude the root of the tree of life from the eukaryotes or Archaea, placing it on the bacterial stem or within the Bacteria. They also exclude the root of the archaeal radiation from several major clades, consistent with analyses using other rooting methods. Overall, our results demonstrate the utility of non-reversible and non-stationary models for rooting phylogenetic trees, and identify areas where further progress can be made. © 2015 The Authors.

  2. Some comments on the substituted judgement standard.

    Egonsson, Dan

    2010-02-01

    On a traditional interpretation of the substituted judgement standard (SJS) a person who makes treatment decisions on behalf of a non-competent patient (e.g. concerning euthanasia) ought to decide as the patient would have decided had she been competent. I propose an alternative interpretation of SJS in which the surrogate is required to infer what the patient actually thought about these end-of-life decisions. In clarifying SJS it is also important to differentiate the patient's consent and preference. If SJS is part of an autonomy ideal of the sort found in Kantian ethics, consent seems more important than preference. From a utilitarian perspective a preference-based reading of SJS seems natural. I argue that the justification of SJS within a utilitarian framework will boil down to the question whether a non-competent patient can be said to have any surviving preferences. If we give a virtue-ethical justification of SJS the relative importance of consent and preferences depends on which virtue one stresses--respect or care. I argue that SJS might be an independent normative method for extending the patient's autonomy, both from a Kantian and a virtue ethical perspective.

  3. Hazardous Solvent Substitution Data System reference manual

    Branham-Haar, K.A.; Twitchell, K.E.

    1993-07-01

    Concern for the environment, in addition to Federal regulation, mandate the replacement of hazardous solvents with safer cleaning agents. Manufacturers are working to produce these replacement solvents. As these products are developed, potential users need to be informed of their availability. To promote the use of these new products instead of traditional solvents, the Idaho National Engineering Laboratory (INEL) has developed the Hazardous Solvent Substitution Data System (HSSDS). The HSSDS provides a comprehensive system of information on alternatives to hazardous solvents and related subjects, and it makes that information available to solvent users, industrial hygienists, and process engineers. The HSSDS uses TOPIC reg-sign, a text retrieval system produced by Verity, Inc., to allow a user to search for information on a particular subject. TOPIC reg-sign produces a listing of the retrieved documents and allows the use to examine the documents individually and to use the information contained in them. This reference manual does not replace the comprehensive TOPIC reg-sign user documentation (available from Verity, Inc.), or the HSSDS Tutorial (available from the INEL). The purpose of this reference manual is to provide enough instruction on TOPIC reg-sign so the user may begin accessing the data contained in the HSSDS

  4. 40 CFR Appendix H to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes, Effective May 28, 1999

    2010-07-01

    ... 40 Protection of Environment 17 2010-07-01 2010-07-01 false Substitutes Subject to Use Restrictions and Unacceptable Substitutes, Effective May 28, 1999 H Appendix H to Subpart G of Part 82... STRATOSPHERIC OZONE Significant New Alternatives Policy Program Pt. 82, Subpt. G, App. H Appendix H to Subpart G...

  5. Nonsynonymous substitution in abalone sperm fertilization genes exceeds substitution in introns and mitochondrial DNA

    Metz, Edward C.; Robles-Sikisaka, Refugio; Vacquier, Victor D.

    1998-01-01

    Strong positive Darwinian selection acts on two sperm fertilization proteins, lysin and 18-kDa protein, from abalone (Haliotis). To understand the phylogenetic context for this dramatic molecular evolution, we obtained sequences of mitochondrial cytochrome c oxidase subunit I (mtCOI), and genomic sequences of lysin, 18-kDa, and a G protein subunit. Based on mtDNA differentiation, four north Pacific abalone species diverged within the past 2 million years (Myr), and remaining north Pacific species diverged over a period of 4–20 Myr. Between-species nonsynonymous differences in lysin and 18-kDa exons exceed nucleotide differences in introns by 3.5- to 24-fold. Remarkably, in some comparisons nonsynonymous substitutions in lysin and 18-kDa genes exceed synonymous substitutions in mtCOI. Lysin and 18-kDa intron/exon segments were sequenced from multiple red abalone individuals collected over a 1,200-km range. Only two nucleotide changes and two sites of slippage variation were detected in a total of >29,000 nucleotides surveyed. However, polymorphism in mtCOI and a G protein intron was found in this species. This finding suggests that positive selection swept one lysin allele and one 18-kDa allele to fixation. Similarities between mtCOI and lysin gene trees indicate that rapid adaptive evolution of lysin has occurred consistently through the history of the group. Comparisons with mtCOI molecular clock calibrations suggest that nonsynonymous substitutions accumulate 2–50 times faster in lysin and 18-kDa genes than in rapidly evolving mammalian genes. PMID:9724763

  6. Fluid structure and molecular interaction of acetophenone derivatives

    strong hydrogen bond is expected for an acetyl group ortho to the hydroxy atom, ... Earlier the authors [2] have reported the utility of dielectric measurements while ... Theory. The Kirkwood correlation factor g has been calculated by the ...

  7. The role of biomass in US industrial interfuel substitution

    Jones, Clifton T.

    2014-01-01

    The role of biomass in US industrial interfuel substitution in the industrial sector has typically been analyzed using data for the four traditional fuels of coal, oil, electricity and natural gas. However, the use of biomass as an industrial fuel in the US has grown, and now exceeds that of coal. Using data from 1960 to 2011, interfuel substitution in the US industrial sector is modeled with a dynamic linear logit model which includes biomass alongside the other four traditional fuels. Adding biomass to the model reduces somewhat the estimated own-price and cross-price elasticities for the other four fuels, while revealing that biomass and natural gas are substitute fuels. This implies that previous studies excluding biomass may have overestimated the potential for interfuel substitution, giving policy makers an inaccurate impression of the ability of carbon taxes or other environmental regulation to reduce greenhouse gas (GHG) emissions. - Highlights: • Biomass usage by the US industrial sector now exceeds coal usage. • Previous interfuel substitution studies have not included biomass as a fuel. • Linear logit model is used to examine role of biomass in interfuel substitution. • Including biomass in the model lowers estimated price elasticities for traditional fuels. • Biomass is found to be a substitute for natural gas for industrial users

  8. Enhanced osteoconductivity of sodium-substituted hydroxyapatite by system instability.

    Sang Cho, Jung; Um, Seung-Hoon; Su Yoo, Dong; Chung, Yong-Chae; Hye Chung, Shin; Lee, Jeong-Cheol; Rhee, Sang-Hoon

    2014-07-01

    The effect of substituting sodium for calcium on enhanced osteoconductivity of hydroxyapatite was newly investigated. Sodium-substituted hydroxyapatite was synthesized by reacting calcium hydroxide and phosphoric acid with sodium nitrate followed by sintering. As a control, pure hydroxyapatite was prepared under identical conditions, but without the addition of sodium nitrate. Substitution of calcium with sodium in hydroxyapatite produced the structural vacancies for carbonate ion from phosphate site and hydrogen ion from hydroxide site of hydroxyapatite after sintering. The total system energy of sodium-substituted hydroxyapatite with structural defects calculated by ab initio methods based on quantum mechanics was much higher than that of hydroxyapatite, suggesting that the sodium-substituted hydroxyapatite was energetically less stable compared with hydroxyapatite. Indeed, sodium-substituted hydroxyapatite exhibited higher dissolution behavior of constituent elements of hydroxyapatite in simulated body fluid (SBF) and Tris-buffered deionized water compared with hydroxyapatite, which directly affected low-crystalline hydroxyl-carbonate apatite forming capacity by increasing the degree of apatite supersaturation in SBF. Actually, sodium-substituted hydroxyapatite exhibited markedly improved low-crystalline hydroxyl-carbonate apatite forming capacity in SBF and noticeably higher osteoconductivity 4 weeks after implantation in calvarial defects of New Zealand white rabbits compared with hydroxyapatite. In addition, there were no statistically significant differences between hydroxyapatite and sodium-substituted hydroxyapatite on cytotoxicity as determined by BCA assay. Taken together, these results indicate that sodium-substituted hydroxyapatite with structural defects has promising potential for use as a bone grafting material due to its enhanced osteoconductivity compared with hydroxyapatite. © 2013 Wiley Periodicals, Inc.

  9. Substitute natural gas from biomass gasification

    Tunaa, Per (Lund Inst. of Technology, Lund (SE))

    2008-03-15

    Biomass is by many considered as the only alternative to phase-out the usage of fossil fuels such as natural gas and oil especially for the transportation sector where alternative solutions, such as hydrogen fuel cells and batteries, are not yet fully developed. Thermal gasification or other methods such as pyrolysis of the biomass must be applied in order to produce an intermediate product suitable for further upgrading to either gaseous or liquid products. This thesis will evaluate the possibilities of producing, substitute natural gas, (SNG) from biomass gasification by using computer simulation. Three different gasification techniques were evaluated; entrained-flow, fluidized-bed and indirect gasification coupled with two different desulphurisation systems and two methanation processes. The desulphurisation systems were a zinc oxide bed and a Rectisol wash system. Methanation were performed by a series of adiabatic reactors with gas recycling and by an isothermal reactor. The impact on SNG efficiency from system pressure, isothermal methanation temperature and PSA methane recovery were evaluated as well. The results show that the fluidized-bed and the indirect gasifier have the highest SNG efficiency. Furthermore there are little to no difference between the methanation processes and small differences for the gas cleanup systems. SNG efficiencies in excess of 50 % were possible for all gasifiers. SNG efficiency is defined as the energy in the SNG product divided by the total input to the system from biomass, drying and oxygen. Increasing system pressure has a negative impact on SNG efficiency as well as increasing operating costs due to increased power for compression. Isothermal methanation temperature has no significant impact on SNG efficiency. Recovering as much methane as possible in the PSA is the most important parameter. Recovering methane that has been dissolved in condensed process water increases the SNG efficiency by 2-10% depending on system.

  10. From incremental to fundamental substitution in chemical alternatives assessment

    Fantke, Peter; Weber, Roland; Scheringer, Martin

    2015-01-01

    to similarity in chemical structures and, hence, similar hazard profiles between phase-out and substitute chemicals, leading to a rather incremental than fundamental substitution. A hampered phase-out process, the lack of implementing Green Chemistry principles in chemicals design, and lack of Sustainable...... an integrated approach of all stakeholders involved toward more fundamental and function-based substitution by greener and more sustainable alternatives. Our recommendations finally constitute a starting point for identifying further research needs and for improving current alternatives assessment practice....

  11. Kinetics on the reaction of substituted quinolines and p-substituted benzoylchlorides under various pressures

    Kim, Young Cheul; Lim, Jong Wan; Choi, Sung Yong; Kim, Se Kyong

    1999-01-01

    The reaction rates of substituted quinolines(6-CH 3 C 9 H 7 N, C 9 H 7 N) with p-substituted benzoylchlorides(p-CH 3 , p-H, p-NO 2 ) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10,15, 20, 25 .deg. C) and pressures(1, 200, 500, 1000bar). From the values of rate constants, the activation parameters(Ea, ΔV ≠ , ΔS ≠ , and ΔG ≠ ) and the pressure dependence of Hammett ρ values were determined. The rate constants increase as a function of temperatures and pressures, and are further increase by introduction the electron donor substituents in nucleophile(p-CH 3 ) or electron acceptor(p-NO 2 ) substituents in substrate. The activation volume, and the activation entropy are all negative. Hammett ρ values are also negative for nucleophile (ρ X ) and positive for the substrate (ρ Y ) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S N 2 reaction mechanism and 'associative S N 2' in which bond formation favored with increasing pressures

  12. Chitosan Dermal Substitute and Chitosan Skin Substitute Contribute to Accelerated Full-Thickness Wound Healing in Irradiated Rats

    Abu Bakar Mohd Hilmi

    2013-01-01

    Full Text Available Wounds with full-thickness skin loss are commonly managed by skin grafting. In the absence of a graft, reepithelialization is imperfect and leads to increased scar formation. Biomaterials can alter wound healing so that it produces more regenerative tissue and fewer scars. This current study use the new chitosan based biomaterial in full-thickness wound with impaired healing on rat model. Wounds were evaluated after being treated with a chitosan dermal substitute, a chitosan skin substitute, or duoderm CGF. Wounds treated with the chitosan skin substitute showed the most re-epithelialization (33.2 ± 2.8%, longest epithelial tongue (1.62 ± 0.13 mm, and shortest migratory tongue distance (7.11 ± 0.25 mm. The scar size of wounds treated with the chitosan dermal substitute (0.13 ± 0.02 cm and chitosan skin substitute (0.16 ± 0.05 cm were significantly decreased (P<0.05 compared with duoderm (0.45 ± 0.11 cm. Human leukocyte antigen (HLA expression on days 7, 14, and 21 revealed the presence of human hair follicle stem cells and fibroblasts that were incorporated into and surviving in the irradiated wound. We have proven that a chitosan dermal substitute and chitosan skin substitute are suitable for wound healing in full-thickness wounds that are impaired due to radiation.

  13. Hydrogen-bonding interactions in thiosemicarbazones of carboxylic acids: Structure of 2-ketobutyric acid thiosemicarbazone hemihydrate

    Sonawane, P.; Chikate, R.; Kumbhar, A.; Padhye, S.; Doedens, R.J.

    1991-01-01

    2-Thiosemicarbazonobutanoic acid hemihydrate, C 5 H 9 N 3 O 2 S.0.5H 2 O, M r =184.22, triclinic, Panti 1, a=8.163(2), b=8.868(2), c=12.438(2) A, α=72.99(2), β=79.47(2), γ=84.06(2)deg, V=845.3(3) A 3 , Z=4, D x =1.447 Mg m -3 , λ(Mo Kα)=0.71073 A, μ=0.332 mm -1 , F(000)=392, T=296 K, R=0.038 for 3830 independent reflections with I>3σ(I). Three hydrogen bonds link the two crystallographically independent molecules in a pairwise fashion. The two molecules both have E configurations about each C-N and N-N bond, but differ by nearly 180deg in the orientation of the -COOH group. (orig.)

  14. Performance of chicken broilers fed with diets substituted with ...

    Performance of chicken broilers fed with diets substituted with mulberry leaf powder. Carlina Freddie Simol, Andrew Alek Tuen, Humrawali Hazid Ahmad Khan, John Keen Chubo, Patricia Jie Hung King, Kian Huat Ong ...

  15. Modified broken rice starch as fat substitute in sausages

    Valéria Maria Limberger

    2011-09-01

    Full Text Available The demand for low-fat beef products has led the food industry to use fat substitutes such as modified starch. About 14% of broken rice is generated during processing. Nevertheless, this by-product contains high levels of starch; being therefore, great raw material for fat substitution. This study evaluated the applicability of chemically and physically modified broken rice starch as fat substitute in sausages. Extruded and phosphorylated broken rice was used in low-fat sausage formulation. All low-fat sausages presented about 55% reduction in the fat content and around 28% reduction in the total caloric value. Fat replacement with phosphorylated and extruded broken rice starch increased the texture acceptability of low-fat sausages, when compared to low-fat sausages with no modified broken rice. Results suggest that modified broken rice can be used as fat substitute in sausage formulations, yielding lower caloric value products with acceptable sensory characteristics.

  16. Aligning protein sequence and analysing substitution pattern using ...

    Prakash

    Aligning protein sequences using a score matrix has became a routine but valuable method in modern biological ..... the amino acids according to their substitution behaviour ...... which may cause great change (e.g. prolonging the helix) in.

  17. Long term substitution treatment (maintenance treatment of opioid dependent persons

    Wirl, Charlotte

    2007-03-01

    Full Text Available Health political background: Methadone substitution treatment in Germany is introduced in 1988 in the framework of a scientific pilot study in North Rhein Westphalia. Recent statistics show that by now a broad offer of substitution treatment exists. From 1 June 2002 to 31 December 2003 113,000 substitution treatments have been recorded as being started of which around 56,000 have been recorded as ongoing treatments by 1 December 2003. Scientific background: Substitution treatment (treatment of opioid-dependent persons using substitution substances is one part of addiction treatment. Its goals are harm reduction and the stabilisation of opioid dependent persons. Integration of opioid-dependent persons in a treatment-setting, reduction of consumption of psychoactive substances, reduction of risk behaviour (primarily related to infectious diseases, decrease of mortality and improvements concerning the social, psychic and physic situation are seen as a success of substitution treatment as maintenance therapy. Research questions: The aim of this HTA report is to investigate which indicators can be used to evaluate the effectiveness of substitution treatment. Based on these indicators an evaluation of the medical, social and economical benefit of substitution treatment - also in relation to abstinence oriented treatment - is carried out. Methods: A systematic literature search was performed in 31 international databases which yielded 2451 articles with publication date between 1995 and February 2005. Results: After a twofold selection process 32 publications were included for assessment and 276 publications were used as background literature. Despite serious restrictions due to selection bias and dropout in most studies focusing on substitution treatment, reduction of consumption of illegal opioids, reduction of risk behaviour, criminal behaviour, mortality and incidence of HIV can be seen as an empirically proven success of substitution treatment

  18. Computational Modeling of Degradation of Substituted Benzyltrimethyl Ammonium: Preprint

    Long, H.; Pivovar, B. S.

    2014-09-01

    The degradation of cations on the alkaline exchange membranes is the major challenge for alkaline membrane fuel cells. In this paper, we investigated the degradation barriers by density functional theory for substituted benzyltrimethyl ammonium (BTMA+) cations, which is one of the most commonly used cations for alkaline exchange membranes. We found that substituted cations with electron-releasing substituent groups at meta-position of the benzyl ring could result in improved degradation barriers. However, after investigating more than thirty substituted BTMA+ cations with ten different substituent groups, the largest improvement of degradation barriers is only 1.6 kcal/mol. This implies that the lifetime of alkaline membrane fuel cells could increase from a few months to a few years by using substituted BTMA+ cations, an encouraging but still limited improvement for real-world applications.

  19. Gold-catalyzed oxidation of substituted phenols by hydrogen peroxide

    Cheneviere, Yohan; Caps, Valerie; Tuel, Alain

    2010-01-01

    Gold nanoparticles deposited on inorganic supports are efficient catalysts for the oxidation of various substituted phenols (2,6-di-tert-butyl phenol and 2,3,6-trimethyl phenol) with aqueous hydrogen peroxide. By contrast to more conventional

  20. Macroporous synthetic hydroxyapatite bioceramics for bone substitute applications

    Thomas, ME

    1999-08-01

    Full Text Available An improved strategy is described for the manufacture of macroporous hydroxyapatite bioceramics for bone substitute applications. This is based on a modified fugitive phase technique, which allows production of relatively open, high-strength devices...

  1. A Web service substitution method based on service cluster nets

    Du, YuYue; Gai, JunJing; Zhou, MengChu

    2017-11-01

    Service substitution is an important research topic in the fields of Web services and service-oriented computing. This work presents a novel method to analyse and substitute Web services. A new concept, called a Service Cluster Net Unit, is proposed based on Web service clusters. A service cluster is converted into a Service Cluster Net Unit. Then it is used to analyse whether the services in the cluster can satisfy some service requests. Meanwhile, the substitution methods of an atomic service and a composite service are proposed. The correctness of the proposed method is proved, and the effectiveness is shown and compared with the state-of-the-art method via an experiment. It can be readily applied to e-commerce service substitution to meet the business automation needs.

  2. Substitution possibilities and determinants of energy intensity for China

    Ma, Hengyun; Oxley, Les; Gibson, John

    2009-01-01

    This paper measures technological change, factor demand and inter-factor and inter-fuel substitutability measures for China. We use individual fuel price data and a two-stage approach to estimate total factor cost functions and fuel share equations. Both inter-factor and inter-fuel substitution elasticities are calculated and the change in energy intensity is decomposed into its driving forces. The results suggest that energy is substitutable for capital regionally and for labor nationally. Capital substitutes for energy more easily than labor does. Energy intensity changes vary by region but the major drivers seem to be 'budget effect' and the adoption of energy-intensive technologies, which might be embodied in high-level energy-using exports and sectors, capital investment and even old technique and equipment imports. Whether the trend in rising energy intensity continues will be significant for China and the rest of the world. (author)

  3. Industrialization in Sub-Saharan Africa and import substitution policy

    Ana Paula F. Mendes

    2014-03-01

    Full Text Available This article aims to contribute to the understanding of the process of import substitution in Sub-Saharan Africa. The process of industrialization in Sub-Saharan Africa occurred in two phases: a first step, even very early during the colonial regime began around the 1920s and ended in the late forties; a second phase of industrialization began in the late fifties and gained momentum in the sixties, when import substitution was implemented more widely. Although these countries were the last to embark on the strategy of import substitution, they followed the same steps of Latin American countries, and as the structural domestic and external constraints were too strong, the failure of the policy of import substitution arrived early and the negative impact on these economies had a greater magnitude.

  4. Curvature and elasticity of substitution: what is the link?

    Matveenko, Andrei; Matveenko, V.

    2014-01-01

    Roč. 10, č. 2 (2014), s. 7-20 ISSN 1800-5845 Grant - others:UK(CZ) GAUK 308214 Institutional support: PRVOUK-P23 Keywords : curvature * elasticity of substitution * production function Subject RIV: AH - Economics

  5. Substitution possibilities and determinants of energy intensity for China

    Ma, Hengyun [College of Economics and Management, Henan Agricultural University, 95 Wenhua Road, Zhengzhou 450002 (China); Department of Economics, University of Canterbury, Private bag 4800, Christchurch 8140 (New Zealand); Oxley, Les [Department of Economics, University of Canterbury, Private bag 4800, Christchurch 8140 (New Zealand); Gibson, John [Department of Economics, University of Waikato, Private Bag 3105, Hamilton (New Zealand)

    2009-05-15

    This paper measures technological change, factor demand and inter-factor and inter-fuel substitutability measures for China. We use individual fuel price data and a two-stage approach to estimate total factor cost functions and fuel share equations. Both inter-factor and inter-fuel substitution elasticities are calculated and the change in energy intensity is decomposed into its driving forces. The results suggest that energy is substitutable for capital regionally and for labor nationally. Capital substitutes for energy more easily than labor does. Energy intensity changes vary by region but the major drivers seem to be 'budget effect' and the adoption of energy-intensive technologies, which might be embodied in high-level energy-using exports and sectors, capital investment and even old technique and equipment imports. Whether the trend in rising energy intensity continues will be significant for China and the rest of the world. (author)

  6. Calculating stocking rates for game ranches: substitution ratios for ...

    Calculating stocking rates for game ranches: substitution ratios for use in the Mopani ... Reports on a study conducted to quantify the overlap in ungulate resource-use on a game ranch, and to demonstrate how ... AJOL African Journals Online.

  7. 1-Hydroxyethyl-2-Substituted Phenoxymethyl Benzimidazoles: Synthesis and Crystal Structures

    Wu, J.; Wang, Z.; Gu, H.; Chen, W.; Zhao, L.; Zhao, C.

    2016-01-01

    Five novel 1-hydroxyethyl-2-substituted phenoxymethyl benzimidazoles c1-c5 were successfully synthesized by a three-step route. Firstly, five substituted phenoxymethyl acids a1-a5 were prepared by the O-carboxymethylation reaction of the starting substituted phenols under microwave irradiation. Then, these compounds reacted with o-phenylendiamine to get the key intermediates 2-substituted phenoxymethyl benzimidazoles b1-b5. At last, the target compounds were synthesized by the N-hydroxyethylation reaction of b1-b5 with 2-chloroethyl alcohol through the solid-liquid phase transfer catalysis method, where tetrabutyl ammonium bromide (TBAB) was used as the catalyst. The structures of the target compounds were well characterized and verified by elemental analysis, MS, IR, 1H NMR, 13C NMR and single crystal X-ray diffraction analysis. (author)

  8. Loan collaterals and collateral substitutes in rural finance: a review ...

    Loan collaterals and collateral substitutes in rural finance: a review. ... have difficulties in obtaining loans from banks and other financial institutions because ... The limited availability of conventional collaterals in rural financial markets has led ...

  9. Associations between generic substitution and patient-related factors

    Østergaard Rathe, Jette

    Associations between generic substitution and patient-related factors Jette Østergaard Rathe1, Pia V. Larsen1, Morten Andersen2, Janus L. Thomsen3, Maja S. Paulsen1, Jens Søndergaard1 1. Research Unit of General Practice, Institute of Public Health, University of Southern Denmark 2. Centre...... for Pharmacoepidemiology, Karolinska Institutet, Department of Medicine Solna, Stockholm, Sweden 3. Danish Quality Unit of General Practice, Odense, Denmark Background Generic substitution means that chemically equivalent but less expensive drugs are dispensed in place of a brand name product. Although generic medicines...... by definition are bioequivalent to their brand name counterparts there are concerns about whether generic substitution is always accompanied by clinical equivalence in terms of effectiveness and that it may cause concerns and thereby causing some skepticism towards generic substitution. There is, however...

  10. Osseointegration of subperiosteal implants using bovine bone substitute and various membranes

    Aaboe, Merete; Schou, S.; Hjørting-Hansen, E.

    2000-01-01

    Osseointegration, subperiosteal implant, bone substitute, bovine bone, guided bone, regeneration, histology, rabbits......Osseointegration, subperiosteal implant, bone substitute, bovine bone, guided bone, regeneration, histology, rabbits...

  11. Protein substitute for children and adults with phenylketonuria.

    Yi, Sarah H L; Singh, Rani H

    2015-02-27

    Phenylketonuria is an inherited metabolic disorder characterised by an absence or deficiency of the enzyme phenylalanine hydroxylase. The aim of treatment is to lower blood phenylalanine concentrations to the recommended therapeutic range to prevent developmental delay and support normal growth. Current treatment consists of a low-phenylalanine diet in combination with a protein substitute which is free from or low in phenylalanine. Guidance regarding the use, dosage, and distribution of dosage of the protein substitute over a 24-hour period is unclear, and there is variation in recommendations among treatment centres. This is an update of a Cochrane review first published in 2005, and previously updated in 2008. To assess the benefits and adverse effects of protein substitute, its dosage, and distribution of dose in children and adults with phenylketonuria who are adhering to a low-phenylalanine diet. We searched the Cochrane Cystic Fibrosis and Genetic Disorders Group Trials Register which consists of references identified from comprehensive electronic database searches and hand searches of relevant journals and abstract books of conference proceedings. We also contacted manufacturers of the phenylalanine-free and low-phenylalanine protein substitutes for any data from published and unpublished randomised controlled trials.Date of the most recent search of the Group's Inborn Errors of Metabolism Trials Register: 03 April 2014. All randomised or quasi-randomised controlled trials comparing: any dose of protein substitute with no protein substitute; an alternative dosage; or the same dose, but given as frequent small doses throughout the day compared with the same total daily dose given as larger boluses less frequently. Both authors independently extracted data and assessed trial quality. Three trials (69 participants) are included in this review. One trial investigated the use of protein substitute in 16 participants, while a further two trials investigated the

  12. Managing demand uncertainty: probabilistic selling versus inventory substitution

    Zhang, Y.; Hua, Guowei; Wang, Shouyang; Zhang, Juliang; Fernández Alarcón, Vicenç

    2018-01-01

    Demand variability is prevailing in the current rapidly changing business environment, which makes it difficult for a retailer that sells multiple substitutable products to determine the optimal inventory. To combat demand uncertainty, both strategies of inventory substitution and probabilistic selling can be used. Although the two strategies differ in operation, we believe that they share a common feature in combating demand uncertainty by encouraging some customers to give up some specific ...

  13. Factor and Organizational Substitutions to Minimize Costs in the Navy

    2013-12-01

    than mere labour for capital substitutions if the objective is one of cost minimization. Static input substitution principle that cheaper inputs...produced? Is the correct mix of inputs being used? While advanced treatments of production theory can be found in microeconomics textbooks (e.g... Microeconomic Theory, 3rd Edition, Prentice Hall Johnson, D.C. et al. (2009), “Managing Change on Complex Programs: VIRGINIA Class Cost Reduction,” Naval

  14. Currency Substitution and The Law of One Price

    Gabriele Camera; Johannes Winkler

    2000-01-01

    We study endogenous currency substitution in a decentralized trade environment. Sellers maximize profits from sales of imperfectly substitutable goods by posting prices in either one of two currencies. A unique symmetric equilibrium exists where goods are priced only in the local currency. This occurs if foreign trade is sporadic, there is sufficient but not excessive liquidity, and discounting is low. Excess or scarcity of liquidity, however, induces sellers to extract all surplus from buyer...

  15. Diastereoselective Au-Catalyzed Allene Cycloisomerizations to Highly Substituted Cyclopentenes.

    Reeves, Ryan D; Phelps, Alicia M; Raimbach, William A T; Schomaker, Jennifer M

    2017-07-07

    Site- and regiocontrolled Au-catalyzed allene carbocyclizations furnish highly substituted cyclopentenes in >1:1 dr. Significant substitution on the substrate is tolerated, with potential to install five contiguous stereocenters after alkene functionalization. Major challenges include identifying a Au/Cu catalyst that controls both the relative rates of allene epimerization/cyclization and the facial selectivity in addition of a metal enolate to the allene. Experiments to achieve stereodivergent cyclizations and transform key cyclopentenes into useful synthetic building blocks are described.

  16. A Novel Image Stream Cipher Based On Dynamic Substitution

    Elsharkawi, A.; El-Sagheer, R. M.; Akah, H.; Taha, H.

    2016-01-01

    Recently, many chaos-based stream cipher algorithms have been developed. Traditional chaos stream cipher is based on XORing a generated secure random number sequence based on chaotic maps (e.g. logistic map, Bernoulli Map, Tent Map etc.) with the original image to get the encrypted image, This type of stream cipher seems to be vulnerable to chosen plaintext attacks. This paper introduces a new stream cipher algorithm based on dynamic substitution box. The new algorithm uses one substitution b...

  17. The applied theory of energy substitution in production

    Thompson, Henry

    2006-01-01

    This paper reviews the applied theory of energy cross price partial elasticities of substitution, and presents it in a transparent fashion. It uses log linear and translog production and cost functions due to their economic properties and convenient estimating forms, but the theory applies other functional forms. The objective is to encourage increased empirical research that would deepen understanding and appreciation of energy substitution. (author)

  18. The elasticity of substitution of superlative price indices

    Petter Frenger

    2005-01-01

    Abstract: The paper presents a method for computing the curvature implicit in the use of superlative price indices. It extends the quadratic lemma and allows us to compute the elasticity of substitution of the underlying preferences in the direction of the observed price change for the Törnqvist and the quadratic mean of order r indices. It derives the expressions for the directional shadow elasticity of substitution and applies the results to the Norwegian CPI data base. Ke...

  19. Think Again: Higher Elasticity of Substitution Increases Economic Resilience

    P. Dumas; S. Hallegatte

    2009-01-01

    This paper shows that, counter-intuitively, a higher elasticity of substitution in model production function can lead to reduced economic resilience and larger vulnerability to shocks in production factor prices. This result is due to the fact that assuming a higher elasticity of substitution requires a recalibration of the production function parameters to keep the model initial state unchanged. This result has consequences for economic analysis, e.g., on the economic vulnerability to climat...

  20. Laser ablation of Bi-substituted gadolinium iron garnet films

    Watanabe, N.; Hayashida, K.; Kawano, K.; Higuchi, K.; Ohkoshi, M.; Tsushima, K.

    1995-01-01

    Bi-substituted gadolinium iron garnet films were deposited by laser ablation. The composition, the structure and the magnetic properties of the films were found to be strongly dependent both on the compositions of the targets and on the pressure of oxygen. The highest values of Bi-substitution up to x=1.44 with uniform composition were obtained, after annealing in air. ((orig.))

  1. Anthropogenic areas as incidental substitutes for original habitat.

    Martínez-Abraín, Alejandro; Jiménez, Juan

    2016-06-01

    One speaks of ecological substitutes when an introduced species performs, to some extent, the ecosystem function of an extirpated native species. We suggest that a similar case exists for habitats. Species evolve within ecosystems, but habitats can be destroyed or modified by natural and human-made causes. Sometimes habitat alteration forces animals to move to or remain in a suboptimal habitat type. In that case, the habitat is considered a refuge, and the species is called a refugee. Typically refugee species have lower population growth rates than in their original habitats. Human action may lead to the unintended generation of artificial or semiartificial habitat types that functionally resemble the essential features of the original habitat and thus allow a population growth rate of the same magnitude or higher than in the original habitat. We call such areas substitution habitats and define them as human-made habitats within the focal species range that by chance are partial substitutes for the species' original habitat. We call species occupying a substitution habitat adopted species. These are 2 new terms in conservation biology. Examples of substitution habitats are dams for European otters, wheat and rice fields for many steppeland and aquatic birds, and urban areas for storks, falcons, and swifts. Although substitution habitats can bring about increased resilience against the agents of global change, the conservation of original habitat types remains a conservation priority. © 2016 Society for Conservation Biology.

  2. Si-substituted hydroxyapatite nanopowders: Synthesis, thermal stability and sinterability

    Bianco, Alessandra; Cacciotti, Ilaria; Lombardi, Mariangela; Montanaro, Laura

    2009-01-01

    Synthetic hydroxyapatites incorporating small amounts of Si have shown improved biological performances in terms of enhanced bone apposition, bone in-growth and cell-mediated degradation. This paper reports a systematic investigation on Si-substituted hydroxyapatite (Si 1.40 wt%) nanopowders produced following two different conventional wet methodologies: (a) precipitation of Ca(NO 3 ) 2 .4H 2 O and (b) titration of Ca(OH) 2 . The influence of the synthesis process on composition, thermal behaviour and sinterability of the resulting nanopowders is studied. Samples were characterised by electron microscopy, induced coupled plasma atomic emission spectroscopy, thermal analysis, infrared spectroscopy, N 2 adsorption measurements, X-ray diffraction and dilatometry. Semicrystalline Si-substituted hydroxyapatite powders made up of needle-like nanoparticles were obtained, the specific surface area ranged between 84 and 110 m 2 /g. Pure and Si-substituted hydroxyapatite nanopowders derived from Ca(NO 3 ) 2 .4H 2 O decomposed around 1000 deg. C. Si-substituted hydroxyapatite nanopowders obtained from Ca(OH) 2 were thermally stable up to 1200 deg. C and showed a distinct decreased thermal stability with respect to the homologous pure sample. Si-substituted hydroxyapatites exhibited higher sintering temperature and increased total shrinkage with respect to pure powders. Nanostructured dense ceramics were obtained by sintering at 1100 deg. C Si-substituted hydroxyapatites derived from Ca(OH) 2

  3. Eosin-sensitized photooxidation of substituted phenylalanines and tyrosines

    Rizzuto, F.; Spikes, J.D.

    1977-01-01

    The cosin-sensitized photooxidation of tyrosine and a number of compounds related to tyrosine (substituted phenylalanines) was studied by steady-state kinetic and flash photolysis techniques. In particular, the role of the phenolic group and the amino and carboxyl groups of the alanyl side chain in the photooxidation mechanism was investigated in detail. Several relationships between substrate structure and susceptibility to photooxidation as well as effects of substrate structure on photooxidation mechanisms were found. For example, phenylalanine is not photooxidizable, but substitution of electron-donating (activating) groups such as -OH (as in tyrosine) or -NH/sub 2/ (as in p-aminophenylalanine) results in rapidly photooxidized derivatives. However, substituting deactivating groups such as -Cl (as in p-chlorophenylalanine) or weakly activating groups such as -OCH/sub 3/ (as in 4-methoxyphenylalanine) result in non-photooxidizable derivatives. Substitution of additional activating groups to the ring of hydroxy-substituted phenylalanines results in increased rates of photooxidation, whereas additional deactivating groups result in decreased photooxidation rates. The rate-determining step in the photooxidation mechanism is shown to be dependent on the presence and position of an electron-donating substituent on the benzenoid ring. Only minor involvement of the side chain amino and carboxyl groups was found. Both singlet oxygen and hydrogen abstraction mechanisms are involved in the eosin-sensitized photooxidation of hydroxy-substituted phenylalanines (e.g., tyrosine). The hydrogen abstraction mechanism probably predominates at both pH 8 and 11.

  4. Are Synonymous Substitutions in Flowering Plant Mitochondria Neutral?

    Wynn, Emily L; Christensen, Alan C

    2015-10-01

    Angiosperm mitochondrial genes appear to have very low mutation rates, while non-gene regions expand, diverge, and rearrange quickly. One possible explanation for this disparity is that synonymous substitutions in plant mitochondrial genes are not truly neutral and selection keeps their occurrence low. If this were true, the explanation for the disparity in mutation rates in genes and non-genes needs to consider selection as well as mechanisms of DNA repair. Rps14 is co-transcribed with cob and rpl5 in most plant mitochondrial genomes, but in some genomes, rps14 has been duplicated to the nucleus leaving a pseudogene in the mitochondria. This provides an opportunity to compare neutral substitution rates in pseudogenes with synonymous substitution rates in the orthologs. Genes and pseudogenes of rps14 have been aligned among different species and the mutation rates have been calculated. Neutral substitution rates in pseudogenes and synonymous substitution rates in genes are significantly different, providing evidence that synonymous substitutions in plant mitochondrial genes are not completely neutral. The non-neutrality is not sufficient to completely explain the exceptionally low mutation rates in land plant mitochondrial genomes, but selective forces appear to play a small role.

  5. Neutron kerma factors, and water equivalence of some tissue substitutes

    Singh, V. P.; Badiger, N. M.; Vega C, H. R.

    2014-08-01

    The kerma factors and kerma relative to air and water of 24 compounds used as tissue substitutes were calculated for neutron energy from 2.53 x 10 -8 up to 29 MeV. The kerma ratio of the tissue substitutes relative to air and water were calculated by the ratio of kerma factors of the tissue substitute to air and water respectively. The water equivalence of the selected tissue substitutes was observed above neutron energies 100 eV. Kerma ratio relative to the air for Poly-vinylidene fluoride and Teflon are found to be nearest to unity in very low energy (up to 1 eV) and above 63 eV respectively. It was found that the natural rubber as a water equivalent tissue substitute compound. The results of the kerma factors in our investigation shows a very good agreement with those published in ICRU-44. We found that at higher neutron energies, the kerma factors and kerma ratios of the selected tissue substitute compounds are approximately same, but differences are large for energies below 100 eV. (Author)

  6. Noval 1-substituted-3,5-dimethyl-4-[(substituted phenyl diazenyl] pyrazole derivatives: Synthesis and pharmacological activity

    Sabir Hussain

    2015-05-01

    Full Text Available Several-1-carbothioamide-3,5-dimethyl-4-[(substituted phenyl diazenyl] pyrazoles 2a–d, 1-(pyridine-4-ylcarbonyl-3,5-dimethyl-4-[(substituted phenyl diazenyl] pyrazoles 3a–d, 1-(5-chloro-6-fluoro-1,3-benzothiazole-2-ylthiocarbamoyl-3,5-dimethyl-4-[(substituted phenyl diazenyl] pyrazoles 4a–d and 1-[(1,2,4-triazole-4-yl carbothioamide]-3,5-dimethyl-4-[(substituted phenyl diazenyl] pyrazoles 5a–d were synthesized. The structures of the newly synthesized compounds were supported by IR, 1H NMR and mass spectral data. These compounds were investigated for their, anti-inflammatory, analgesic, ulcerogenic, lipid peroxidation, antibacterial and antifungal activities. Some of the synthesized compounds showed potent anti-inflammatory activity along with minimal ulcerogenic effect and lipid peroxidation, compared to ibuprofen and flurbiprofen. Some of the tested compounds also showed moderate antimicrobial activity against tested bacterial and fungal strains.

  7. 26 CFR 601.505 - Revocation, change in representation and substitution or delegation of representative.

    2010-04-01

    ... authorizes the substitution or delegation. An employee of a recognized representative may not be substituted... substitution or delegation of representative. 601.505 Section 601.505 Internal Revenue INTERNAL REVENUE SERVICE... Practice Requirements § 601.505 Revocation, change in representation and substitution or delegation of...

  8. Cannabis as a substitute for alcohol and other drugs

    Reiman Amanda

    2009-12-01

    Full Text Available Abstract Background Substitution can be operationalized as the conscious choice to use one drug (legal or illicit instead of, or in conjunction with, another due to issues such as: perceived safety; level of addiction potential; effectiveness in relieving symptoms; access and level of acceptance. This practice of substitution has been observed among individuals using cannabis for medical purposes. This study examined drug and alcohol use, and the occurrence of substitution among medical cannabis patients. Methods Anonymous survey data were collected at the Berkeley Patient's Group (BPG, a medical cannabis dispensary in Berkeley, CA. (N = 350 The sample was 68% male, 54% single, 66% White, mean age was 39; 74% have health insurance (including MediCal, 41% work full time, 81% have completed at least some college, 55% make less than $40,000 a year. Seventy one percent report having a chronic medical condition, 52% use cannabis for a pain related condition, 75% use cannabis for a mental health issue. Results Fifty three percent of the sample currently drinks alcohol, 2.6 was the average number of drinking days per week, 2.9 was the average number of drinks on a drinking occasion. One quarter currently uses tobacco, 9.5 is the average number of cigarettes smoked daily. Eleven percent have used a non-prescribed, non OTC drug in the past 30 days with cocaine, MDMA and Vicodin reported most frequently. Twenty five percent reported growing up in an abusive or addictive household. Sixteen percent reported previous alcohol and/or drug treatment, and 2% are currently in a 12-step or other recovery program. Forty percent have used cannabis as a substitute for alcohol, 26% as a substitute for illicit drugs and 66% as a substitute for prescription drugs. The most common reasons given for substituting were: less adverse side effects (65%, better symptom management (57%, and less withdrawal potential (34% with cannabis. Conclusion The substitution of one

  9. Fine structure study on low concentration zinc substituted hydroxyapatite nanoparticles

    Hu, Wei; Ma, Jun; Wang, Jianglin; Zhang, Shengmin

    2012-01-01

    The fine structure of zinc substituted hydroxyapatite was studied using experimental analysis and first-principles calculations. The synthetic hydroxyapatite nanoparticles containing low Zn concentration show rod-like morphology. The crystallite sizes and unit-cell volumes tended to decrease with the increased Zn concentration according to X-ray diffraction patterns. The Zn K-edge X-ray absorption spectra and fitting results suggest that the hydroxyapatite doped with 0.1 mole% zinc is different in the zinc coordination environments compared with that containing more zinc. The density function theory calculations were performed on zinc substituted hydroxyapatite. Two mechanisms included replacing calcium by zinc and inserting zinc along the hydroxyl column and were investigated, and the related substitution energies were calculated separately. It is found that the substitution energies are negative and lowest for inserting zinc between the two oxygen atoms along the hydroxyl column (c-axis). Combined with the spectral analysis, it is suggested that the inserting mechanism is favored for low concentration zinc substituted hydroxyapatite. Highlights: ► We investigate the fine structure of hydroxyapatite with low content of Zn. ► XANES spectra are similar but a little different at low zinc content. ► Zinc ions influence hydroxyapatite crystal formation and lattice parameters. ► Formation energies are calculated according to plane-wave density function theory. ► Low content of zinc prefers to locate at hydroxyl column in hydroxyapatite lattice.

  10. A test of the substitution-habitat hypothesis in amphibians.

    Martínez-Abraín, Alejandro; Galán, Pedro

    2017-12-08

    Most examples that support the substitution-habitat hypothesis (human-made habitats act as substitutes of original habitat) deal with birds and mammals. We tested this hypothesis in 14 amphibians by using percentage occupancy as a proxy of habitat quality (i.e., higher occupancy percentages indicate higher quality). We classified water body types as original habitat (no or little human influence) depending on anatomical, behavioral, or physiological adaptations of each amphibian species. Ten species had relatively high probabilities (0.16-0.28) of occurrence in original habitat, moderate probability of occurrence in substitution habitats (0.11-0.14), and low probability of occurrence in refuge habitats (0.05-0.08). Thus, the substitution-habitat hypothesis only partially applies to amphibians because the low occupancy of refuges could be due to the negligible human persecution of this group (indicating good conservation status). However, low occupancy of refuges could also be due to low tolerance of refuge conditions, which could have led to selective extinction or colonization problems due to poor dispersal capabilities. That original habitats had the highest probabilities of occupancy suggests amphibians have a good conservation status in the region. They also appeared highly adaptable to anthropogenic substitution habitats. © 2017 Society for Conservation Biology.

  11. Fat substitutes in processing of sausages using piramutaba waste.

    de Fátima Henriques Lourenço, Lúcia; Dos Santos Galvão, Giane Célia; da Conceição Amaral Ribeiro, Suezilde; de Fátima Amaral Ribeiro, Carmelita; Park, Kil Jin

    2014-07-01

    The aim of this study was to evaluate fat substitute in processing of sausages prepared with surimi of waste from piramutaba filleting. The formulation ingredients were mixed with the fat substitutes added according to a fractional planning 2(4-1), where the independent variables, manioc starch (Ms), hydrogenated soy fat (F), texturized soybean protein (Tsp) and carrageenan (Cg) were evaluated on the responses of pH, texture (Tx), raw batter stability (RBS) and water holding capacity (WHC) of the sausage. Fat substitutes were evaluated in 11 formulations and the results showed that the greatest effects on the responses were found to Ms, F and Cg, being eliminated from the formulation Tsp. To find the best formulation for processing piramutaba sausage was made a complete factorial planning of 2(3) to evaluate the concentrations of fat substitutes in an enlarged range. The optimum condition found for fat substitutes in the sausages formulation were carrageenan (0.51%), manioc starch (1.45%) and fat (1.2%).

  12. Photophysical investigation of cyano-substituted terrylenediimide derivatives.

    Kennes, Koen; Baeten, Yannick; Vosch, Tom; Sempels, Wouter; Yordanov, Stoyan; Stappert, Sebastian; Chen, Long; Müllen, Klaus; Hofkens, Johan; Van der Auweraer, Mark; Fron, Eduard

    2014-12-18

    Two new terrylenediimide (TDI) chromophores with cyano substituents in the bay and core area (BCN-TDI and OCN-TDI, respectively) have been characterized by a wide range of techniques, and their applicability for stimulated emission depletion (STED) microscopy has been tested. By cyano substitution an increase of the fluorescence quantum yield and a decrease of the nonradiative rate constant is achieved and attributed to a reduced charge-transfer character of the excited state due to a lower electron density of the TDI core. For BCN-TDI, the substitution in the bay area induces a strong torsional twist in the molecule which, similar to phenoxy bay-perylenediimide (PDI), has a strong effect on the fluorescence lifetime but appears to prevent the aggregation that is observed for OCN-TDI. The single-molecule photobleaching stability of BCN- and OCN-TDI is lower than that of a reference TDI without cyano substitution (C7-TDI), although less so for OCN-TDI. The photophysical properties of the excited singlet state are only slightly influenced by the cyano groups. The observed intense stimulated emission, the pump-dump-probe experiments, and STED single-molecule imaging indicate that STED experiments with the cyano-substituted TDIs are possible. However, because of aggregation and more efficient photobleaching, the performance of BCN- and OCN-TDI is worse than that of the reference compound without cyano groups (C7-TDI). Bay-substituted TDIs are less suitable for STED microscopy.

  13. Pesticide Substitution: Combining Food Safety with Environmental Quality

    Fantke, Peter

    2015-01-01

    Various pesticides are authorized for use on agricultural food crops. Despite regulatory risk assessments aiming at ensuring consumer and environmental safety, pesticides contribute to human and environmental impacts. Guidance is needed to optimize pesticide use practice and minimize human...... and environmental exposure. Comparative pesticide substitution scenarios are presented to address this need. In a case study on wheat, different pesticides have been compared with respect to their substitution potential with focus on human health. Results demonstrate that health impacts can be reduced up to 99......% by defining adequate substitution scenarios. Comprehensive scenarios need to also consider worker and environmental burden, and information on crop rotation, pest pressure, environmental conditions, application costs and efficacy. Such scenarios help to increase food safety and more sustainable use...

  14. Application of queuing theory in inventory systems with substitution flexibility

    Seyedhoseini, S. M.; Rashid, Reza; Kamalpour, Iman; Zangeneh, Erfan

    2015-03-01

    Considering the competition in today's business environment, tactical planning of a supply chain becomes more complex than before. In many multi-product inventory systems, substitution flexibility can improve profits. This paper aims to prepare a comprehensive substitution inventory model, where an inventory system with two substitute products with ignorable lead time has been considered, and effects of simultaneous ordering have been examined. In this paper, demands of customers for both of the products have been regarded as stochastic parameters, and queuing theory has been used to construct a mathematical model. The model has been coded by C++, and it has been analyzed due to a real example, where the results indicate efficiency of proposed model.

  15. Ionic Liquids: An Environmentally Friendly Media for Nucleophilic Substitution Reactions

    Jorapur, Yogesh R.; Chi, Dae Yoon

    2006-01-01

    Ionic liquids are alternative reaction media of increasing interest and are regarded as an eco-friendly alternatives, of potential use in place of the volatile organic solvents typically used in current chemical processing methods. They are emerging as the smart and excellent solvents, which are made of positive and negative ions that they are liquids near room temperature. The nucleophilic substitution reaction is one of the important method for inserting functional groups into a carbon skeleton. Many nucleophilic substitution reactions have been found with enhanced reactivity and selectivity in ionic liquid. In this review, some recent interesting results of nucleophilic substitution reactions such as hydroxylations, ether cleavages, carbon-X (X = carbon, oxygen, nitrogen, fluorine) bond forming reactions, and ring opening of epoxides in ionic liquids are discussed

  16. Selected polyethylene glycols as DOP substitutes. Addendum 1

    Gerber, B.V.

    1981-01-01

    The recommendation is made that Polyethylene glycol (PEG) 400 be considered as a substitute for DOP in aerosol generators producing a polydisperse distribution for testing the integrity of filters and for testing respirator fit. Further, the recommendation is made that pentaethylene glycol (PTAEG) and possibly hexaethylene glycol be considered as a substitute for DOP in aerosol generators thermally producing monodisperse aerosol for quality acceptance tests according tu US federal specifications and standards. The toxicology data base available on the polyethylene glycol family of chemical compounds is discussed and the conclusion is drawn that the probability of approval and acceptance as a non-hazardous substance in the filter and filter media test role is high. Data and analysis supporting PTAEG performance equivalent to DOP in the filter and filter media test role are given or referenced. Cost and availability of the substitute materials is discussed. Conclusions based on the present data and information are given and recommendations for further work are made

  17. Substituting fields within the action: Consistency issues and some applications

    Pons, Josep M.

    2010-01-01

    In field theory, as well as in mechanics, the substitution of some fields in terms of other fields at the level of the action raises an issue of consistency with respect to the equations of motion. We discuss this issue and give an expression which neatly displays the difference between doing the substitution at the level of the Lagrangian or at the level of the equations of motion. Both operations do not commute in general. A very relevant exception is the case of auxiliary variables, which are discussed in detail together with some of their relevant applications. We discuss the conditions for the preservation of symmetries--Noether as well as non-Noether--under the reduction of degrees of freedom provided by the mechanism of substitution. We also examine how the gauge fixing procedures fit in our framework and give simple examples on the issue of consistency in this case.

  18. Tissue reaction and material characteristics of four bone substitutes

    Jensen, S S; Aaboe, M; Pinholt, E M

    1996-01-01

    and Interpore 500 HA/CC) were implanted into 5-mm bur holes in rabbit tibiae. There was no difference in the amount of newly formed bone around the four biomaterials. Interpore 500 HA/CC resorbed completely, whereas the other three biomaterials did not undergo any detectable biodegradation. Bio......The aim of the present study was to qualitatively and quantitatively compare the tissue reactions around four different bone substitutes used in orthopedic and craniofacial surgery. Cylinders of two bovine bone substitutes (Endobon and Bio-Oss) and two coral-derived bone substitutes (Pro Osteon 500......-Oss was osseointegrated to a higher degree than the other biomaterials. Material characteristics obtained by diffuse reflectance infrared Fourier transform spectrometry analysis and energy-dispersive spectrometry did not explain the differences in biologic behavior....

  19. Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

    Satoru Mori

    2017-10-01

    Full Text Available Phthalocyanines and subphthalocyanines are attracting attention as functional dyes that are applicable to organic solar cells, photodynamic therapy, organic electronic devices, and other applications. However, phthalocyanines are generally difficult to handle due to their strong ability to aggregate, so this property must be controlled for further applications of phthalocyanines. On the other hand, trifluoroethoxy-substituted phthalocyanines are known to suppress aggregation due to repulsion of the trifluoroethoxy group. Furthermore, the electronic characteristics of phthalocyanines are significantly changed by the strong electronegativity of fluorine. Therefore, it is expected that trifluoroethoxy-substituted phthalocyanines can be applied to new industrial fields. This review summarizes the synthesis and application of trifluoroethoxy-substituted phthalocyanine and subphthalocyanine derivatives.

  20. Electronic and magnetic properties of Si substituted Fe3Ge

    Shanavas, K. V.; McGuire, Michael A.; Parker, David S.

    2015-01-01

    Using first principles calculations, we studied the effect of Si substitution in the hexagonal Fe 3 Ge. We find the low temperature magnetic anisotropy in this system to be planar and originating mostly from the spin-orbit coupling in Fe-d states. Reduction of the unitcell volume reduces the magnitude of in-plane magnetic anisotropy, eventually turning it positive which reorients the magnetic moments to the axial direction. Substituting Ge with the smaller Si ions also increases the anisotropy, potentially enhancing the region of stability of the axial magnetization, which is beneficial for magnetic applications such as permanent magnets. Our experimental measurements on samples of Fe 3 Ge 1−x Si x confirm these predictions and show that substitution of about 6% of the Ge with Si increases by approximately 35 K the temperature range over which anisotropy is uniaxial

  1. Synthesis of Randomly Substituted Anionic Cyclodextrins in Ball Milling

    László Jicsinszky

    2017-03-01

    Full Text Available A number of influencing factors mean that the random substitution of cyclodextrins (CD in solution is difficult to reproduce. Reaction assembly in mechanochemistry reduces the number of these factors. However, lack of water can improve the reaction outcomes by minimizing the reagent’s hydrolysis. High-energy ball milling is an efficient, green and simple method for one-step reactions and usually reduces degradation and byproduct formation. Anionic CD derivatives have successfully been synthesized in the solid state, using a planetary ball mill. Comparison with solution reactions, the solvent-free conditions strongly reduced the reagent hydrolysis and resulted in products of higher degree of substitution (DS with more homogeneous DS distribution. The synthesis of anionic CD derivatives can be effectively performed under mechanochemical activation without significant changes to the substitution pattern but the DS distributions were considerably different from the products of solution syntheses.

  2. How Firms Substitute for Authority in Strategic Decision-Making

    Dobrajska, Magdalena; Billinger, Stephan; Becker, Markus C.

    Strategic decisions are often made by multiple organizational members who form decision-making structures specialized for a given strategic decision. We study a series of strategic decisions in a business unit of a global Fortune 500 firm, identifying for each decision the hierarchical...... takes place in response to changes in decision characteristics, including decision complexity, decision importance, CEO proximity, and the degree to which a decision is routine. We show various manifestations of the substitution mechanism and discuss implications for strategic decision-making....... and departmental positions of all participating organizational members. We find that firms substitute between different structural components in decision-making structures to combine hierarchical authority with cross-departmental coordination and redundant knowledge. This substitution between structural components...

  3. Substitution of sugar-sweetened beverages with other beverage alternatives

    Zheng, Miaobing; Allman-Farinelli, Margaret; Heitmann, Berit Lilienthal

    2015-01-01

    alternatives on long-term health outcomes. METHOD: We systematically retrieved studies from six electronic databases from inception to November 2013. Prospective cohort studies and randomized controlled trials (RCTs) examining the effects of substituting beverage alternatives for SSBs on long-term health...... to high. Evidence from both cohort studies and RCTs showed substitution of SSBs by various beverage alternatives was associated with long-term lower energy intake and lower weight gain. However, evidence was insufficient to draw conclusions regarding the effect of beverage substitution on other health...... outcomes, and which beverage alternative is the best choice. CONCLUSIONS: Although studies on this topic are sparse, the available evidence suggests a potential beneficial effect on body weight outcomes when SSBs are replaced by water or low-calorie beverages. Further studies in this area are warranted...

  4. Effect of substitution groups in carbon-13 NMR of tri-substituted camphors; Efeitos de substituintes em RMN de carbono-13 de canforas 3-substituidas

    Kaiser, Carlos R; Rittner, Roberto [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica; Basso, Ernani A [Universidade Estadual de Maringa, PR (Brazil). Dept. de Quimica Inorganica

    1994-12-31

    This work presents and discusses the empirical effects of substitution groups in the carbon-13 NMR spectra of tri-substituted camphors and their correlation with the chemical properties of such substitution groups such as electronegativity. The obtained results are presented and discussed

  5. Carbonate hydroxyapatite and silicon-substituted carbonate hydroxyapatite

    Bang, L T; Long, B D; Othman, R

    2014-01-01

    The present study investigates the chemical composition, solubility, and physical and mechanical properties of carbonate hydroxyapatite (CO3Ap) and silicon-substituted carbonate hydroxyapatite (Si-CO3Ap) which have been prepared by a simple precipitation method. X-ray diffraction (XRD), Fourier......(3-)) site and also entered simultaneously into the hydroxyapatite structure. The Si-substituted CO3Ap reduced the powder crystallinity and promoted ion release which resulted in a better solubility compared to that of Si-free CO3Ap. The mean particle size of Si-CO3Ap was much finer than that of CO3Ap...

  6. Heterogenous Intertemporal Elasticity of Substitution and Relative Risk Aversion

    Khorunzhina, Natalia; Gayle, Wayne-Roy

    This paper investigates the existence and degree of variation across house holds and over time in the intertemporal elasticity of substitution (IES) and the coefficient of relative risk aversion (RRA) that is generated by habit forming preferences. To do so, we develop a new nonlinear GMM estimator...... in food consumption. Using these estimates, we develop bounds for the expectation of the implied heterogenous intertemporal elasticity of substitution and relative risk aversion that account for measurement errors and compute asymptotically valid confidence intervals on these bounds. We find...

  7. Exfoliation and thermal transformations of Nb-substituted layered titanates

    Song, H.; Sjåstad, Anja O.; Fjellvåg, Helmer

    2011-01-01

    Single-layer Nb-substituted titanate nanosheets of ca. 1 nm thickness were obtained by exfoliating tetrabutylammonium (TBA)-intercalated Nb-substituted titanates in water. AFM images and turbidity measurements reveal that the exfoliated nanosheets crack and corrugate when sonicated. Upon heating...... factors for increasing the transformation temperatures for conversion of the nanosheets to anatase and finally into rutile. It is further tempting to link the delay in crystallization to morphology limitations originating from the nanosheets. The present work shows that layered Nb-titanates...

  8. Minority anion substitution by Ni in ZnO

    Pereira, Lino Miguel da Costa; Correia, João Guilherme; Amorim, Lígia Marina; Silva, Daniel José; David-Bosne, Eric; Decoster, Stefan; da Silva, Manuel Ribeiro; Temst, Kristiaan; Vantomme, André

    2013-01-01

    We report on the lattice location of implanted Ni in ZnO using the $\\beta$− emission channeling technique. In addition to the majority substituting for the cation (Zn), a significant fraction of the Ni atoms occupy anion (O) sites. Since Ni is chemically more similar to Zn than it is to O, the observed O substitution is rather puzzling. We discuss these findings with respect to the general understanding of lattice location of dopants in compound semiconductors. In particular, we discuss potential implications on the magnetic behavior of transition metal doped dilute magnetic semiconductors.

  9. The electronic configuration of substitutional Fe in silicon

    Weyer, G; Fanciulli, M; Fedosseev, V; Gunnlaugsson, H P; Mishin, V I; Sielemann, R

    1999-01-01

    Ion implantations of radioactive /sup 57/Mn/sup +/ into differently doped silicon single crystals held at 300-600 K have been utilized for /sup 57/Fe Mossbauer studies of interstitial and substitutional Fe. Site and charge state assignments have been made on the basis of the determined hyperfine interaction parameters and Debye temperatures. Substantial fractions of substitutional /sup 57/Mn probe atoms are proposed to occur due to annealing reactions. This site is maintained in the subsequent decay to /sup 57/Fe by

  10. Antimalarial Activity of C-10 Substituted Triazolyl Artemisinin.

    Park, Gab-Man; Park, Hyun; Oh, Sangtae; Lee, Seokjoon

    2017-12-01

    We synthesized C-10 substituted triazolyl artemisinins by the Huisgen cycloaddition reaction between dihydroartemisinins (2) and variously substituted 1, 2, 3-triazoles (8a-8h). The antimalarial activities of 32 novel artemisinin derivatives were screened against a chloroquine-resistant parasite. Among them, triazolyl artemisinins with electron-withdrawing groups showed stronger antimalarial activities than those shown by the derivatives having electron-donating groups. In particularly, m-chlorotriazolyl artemisinin (9d-12d) showed antimalarial activity equivalent to that of artemisinin and could be a strong drug candidate.

  11. Synthesis and biological evaluation of 2-substituted benzimidazole derivatives

    Gurusamy Mariappan

    2015-09-01

    Full Text Available A novel series of 2-substituted benzimidazole derivatives (3a–3j were synthesized by the reaction of 2-chloro methyl benzimidazole with substituted primary aromatic amines. All the compounds were characterized by UV, IR, 1H NMR, mass spectral data and CHN elemental analysis. The synthesized derivatives were screened for analgesic and anti-inflammatory activities. All the compounds showed significant effect at 100 mg/kg p.o. and the experimental data are statistically significant at p < 0.01 level.

  12. A Novel Non-Toxic Xylene Substitute (SBO) for Histology

    Kunhua, Wang; Chuming, Fan; Tao, Lai; Yanmei, Yang; Xin, Yang; Xiaoming, Zhang; Xuezhong, Guo; Xun, Lai

    2011-01-01

    Xylene has been generally used as a clearing and deparaffinizing agent in histology. Because of the potential toxic and flammable nature of xylene, its substitutes have been introduced into some laboratories. In this study, we introduced a novel, non-toxic xylene substitute (SBO), which was generated through a mixture of 86% of white oil No.2 and 14% of N-heptane. SBO had a high boiling point (188°C) and flash point (144°C) coupled with a scentless and decreased volatility. To compare the eff...

  13. Researcher’s Perspective of Substitution Method on Text Steganography

    Zamir Mansor, Fawwaz; Mustapha, Aida; Azah Samsudin, Noor

    2017-08-01

    The linguistic steganography studies are still in the stage of development and empowerment practices. This paper will present several text steganography on substitution methods based on the researcher’s perspective, all scholar paper will analyse and compared. The objective of this paper is to give basic information in the substitution method of text domain steganography that has been applied by previous researchers. The typical ways of this method also will be identified in this paper to reveal the most effective method in text domain steganography. Finally, the advantage of the characteristic and drawback on these techniques in generally also presented in this paper.

  14. Synthesis, characterization and in vitro biological activities of new water-soluble copper(II), zinc(II), and nickel(II) complexes with sulfonato-substituted Schiff base ligand

    Hosseini-Yazdi, S.A.; Mirzaahmadi, A.; Khandar, A.A.; Eigner, Václav; Dušek, Michal; Lotfipour, F.; Mahdavi, M.; Soltani, S.; Dehghan, G.

    2017-01-01

    Roč. 458, Mar (2017), s. 171-180 ISSN 0020-1693 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk(CZ) LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : water-soluble Schiff base * thiosemicarbazone * antimicrobial * antioxidant * cytotoxicity * crystal structure Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 2.002, year: 2016

  15. Synthesis of Novel Benzimidazolyl-substituted Acrylonitriles and Amidino-substituted Benzimidazo[1,2-a]Quinolines

    Grace Karminski-Zamola

    2006-08-01

    Full Text Available A series of novel benzimidazole derivatives 3-10 were synthesized. Benzimidazolyl-substituted acrylonitriles 3 and 4 underwent a photochemical dehydrocyclization reaction to give the corresponding mono- and dicyano-substituted benzimidazo[1,2-a] quinolines 5 and 6. Pinner reaction of these compounds did not give the expected mono- and diamidines, but rather only compounds 7-10, with amido groups at 6-position were isolated. A mechanism for the reaction is proposed. Acyclic compounds 3 and 4, as well as cyclic benzimidazo[1,2-a]quinolines 5-8, exhibit interesting spectroscopic properties and are potential biologically active compounds.

  16. More similar but less satisfying: comparing preferences for and the efficacy of within- and cross-category substitutes for food

    Huh, Young Eun; Vosgerau, Joachim; Morewedge, Carey

    2016-01-01

    When people cannot get what they want, they often satisfy their desire by consuming a substitute. Substitutes can originate from within the taxonomic category of the desired stimulus (i.e., within-category substitutes) or from a different taxonomic category that serves the same basic goal (i.e., cross-category substitutes). Both a store-brand chocolate (within-category substitute) and a granola bar (cross-category substitute), for example, can serve as substitutes for gourmet chocolate. Here,...

  17. Synthesis of 1-Substituted-4-(Pyridin-4-yl)

    Purpose: To synthesize a new series of 1-substituted-4-(pyridin-4-yl) [1,2,4] triazolo [4,3-a]quinazolin- 5(4H)-ones and evaluate them for H1-antihistaminic activity with negligible side effects in guinea pigs. Methods: The synthesized compounds were characterized by Infrared spectroscopy (IR), proton nuclear magnetic ...

  18. Stiffness compatibility of coralline hydroxyapatite bone substitute under dynamic loading

    2009-01-01

    When hydroxyapatite bone substitutes are implanted in human bodies,bone tissues will grow into their porous structure,which will reinforce their strength and stiffness.The concept of mechanical com-patibility of bone substitutes implies that their mechanical properties are similar to the bone tissues around,as if they were part of the bone.The mechanical compatibility of bone substitutes includes both static and dynamic behavior,due to the mechanical properties of bone depending on the strain rate.In this study,split Hopkinson pressure bar technique(SHPB) was employed to determine the dy-namic mechanical properties of coralline hydroxyapatite,bones with and bones without organic com-ponents,and their dynamic stress-strain curves of the three materials were obtained.The mechanical effects of collagens in bone were assessed,by comparing the difference between the Young’s moduli of the three materials.As the implanted bone substitute becomes a part of bone,it can be regarded as an inclusion composite.The effective modulus of the composite was also evaluated in order to estimate its mechanical compatibility on stiffness.The evaluated result shows that the suitable porosity of HA is 0.8,which is in favor of both static and dynamic stiffness compatibility.

  19. Stiffness compatibility of coralline hydroxyapatite bone substitute under dynamic loading

    REN ChaoFeng; HOU ZhenDe; ZHAO Wei

    2009-01-01

    When hydroxyapatite bone substitutes are implanted in human bodies, bone tissues will grow into their porous structure, which will reinforce their strength and stiffness. The concept of mechanical com-patibility of bone substitutes implies that their mechanical properties are similar to the bone tissues around, as if they were part of the bone. The mechanical compatibility of bone substitutes includes both static and dynamic behavior, due to the mechanical properties of bone depending on the strain rate. In this study, split Hopkinson pressure bar technique (SHPB) was employed to determine the dy-namic mechanical properties of coralline hydroxyapatite, bones with and bones without organic com-ponents, and their dynamic stress-strain curves of the three materials were obtained. The mechanical effects of collagens in bone were assessed, by comparing the difference between the Young's moduli of the three materials. As the implanted bone substitute becomes a part of bone, it can be regarded as an inclusion composite. The effective modulus of the composite was also evaluated in order to estimate its mechanical compatibility on stiffness. The evaluated result shows that the suitable porosity of HA is0.8, which is in favor of both static and dynamic stiffness compatibility.

  20. Clinical review: impact of statin substitution policies on patient outcomes

    Atar, Dan; Carmena, Rafael; Clemmensen, Peter; K-Laflamme, Annik; Wassmann, Sven; Lansberg, Peter; Hobbs, Richard

    2009-01-01

    The increasing awareness of cost issues in health care has led to the increasing use of policy-driven substitution of branded for generic medications, particularly relative to statin treatment for cardiovascular diseases. While there are potential short-term health care savings, the consequences for

  1. influence of the substitution on the electronic properties of perylene ...

    Preferred Customer

    The higher performance found in single crystal OFETs compared to thin-film. OFETs is related to the high ... Influence of substitution on electronic properties of perylene-3,4:9,10-bis(dicarboximides). Bull. Chem. Soc. .... be good n-type materials for OFETs due to the efficient electron injection from common gold electrode, ca.

  2. Index Reduction and Discontinuity Handling Using Substitute Equations

    Fabian, G.; Beek, van D.A.; Rooda, J.E.

    2001-01-01

    Download at: http://se.wtb.tue.nl/~vanbeek/. Several techniques exist for index reduction and consistent initialization of higher index DAEs. Many such techniques change the original set of equations by differentiation, substitution, and/or introduction of new variables. This paper introduces

  3. Sodium-carbonate co-substituted hydroxyapatite ceramics

    Zoltan Z. Zyman

    2013-12-01

    Full Text Available Powders of sodium-carbonate co-substituted hydroxyapatite, having sodium content in the range of 0.25–1.5 wt.% with a 0.25 wt.% step, were prepared by a precipitation-solid state reaction route. Compacts of the powders were sintered in a CO2 flow (4 mL/min at 1100 °C for 2 h. The sintered ceramics contained sodium and carbonate ions in the ranges of 0–1.5 wt.% and 1.3–6 wt.%, respectively, which are typical impurity concentrations in biological apatite. A relationship between sodium and carbonate contents and the type of carbonate substitution was found. The total carbonate content progressively increased with the sodium content. The obtained ceramics showed an AB-type carbonate substitution. However, the substitution became more B-type as the sodium content increased. As a result, the carbonation was almost B-type (94 % for the highest sodium content (1.5 wt.%.

  4. Elasticity of substitution and anti-dumping decisions

    Hansen, Jørgen Drud; Meinen, Philipp; Nielsen, Jørgen Ulff-Møller

    2014-01-01

    Motivated by a monopolistic competition model with market segmentation and international price discrimination, this paper analyzes whether there is an inverse relation between the elasticity of substitution and final ad valorem anti-dumping duties across products. We test this for 19 countries...

  5. Substitutional Doping for Aluminosilicate Mineral and Superior Water Splitting Performance

    Zhang, Yi; Fu, Liangjie; Shu, Zhan; Yang, Huaming; Tang, Aidong; Jiang, Tao

    2017-07-01

    Substitutional doping is a strategy in which atomic impurities are optionally added to a host material to promote its properties, while the geometric and electronic structure evolution of natural nanoclay mineral upon substitutional metal doping is still ambiguous. This paper first designed an efficient lanthanum (La) doping strategy for nanotubular clay (halloysite nanotube, HNT) through the dynamic equilibrium of a substitutional atom in the presence of saturated AlCl3 solution, and systematic characterization of the samples was performed. Further density functional theory (DFT) calculations were carried out to reveal the geometric and electronic structure evolution upon metal doping, as well as to verify the atom-level effect of the La doping. The CdS loading and its corresponding water splitting performance could demonstrate the effect of La doping. CdS nanoparticles (11 wt.%) were uniformly deposited on the surface of La-doped halloysite nanotube (La-HNT) with the average size of 5 nm, and the notable photocatalytic hydrogen evolution rate of CdS/La-HNT reached up to 47.5 μmol/h. The results could provide a new strategy for metal ion doping and constructive insight into the substitutional doping mechanism.

  6. Are news media substitutes? Gratifications, contents, and uses

    van der Wurff, R.

    2011-01-01

    Internet is generally expected to have one of two effects on traditional news media: It displaces them, or it forces them into distinct market niches. A shared assumption underlying both expectations is that news media displacement, or substitution, is a function of the degree to which news media

  7. Synthesis, characterization of N-, S-, O-substituted naphtho- and ...

    obtained on a Thermo Finnigan LCQ Advantage MAX. LC/MS/MS spectrometer .... organic layer was washed with water (4 × 30 mL), and dried with Na2SO4. ..... mono(thio)-substituted compounds containing chlorine atom derivatives were.

  8. Substitution Value of toasted Pigeon pea ( Cajanus cajan ) seed ...

    One hundred and eighty 7-day old broilers were used in a 28-day feeding trial to determine the substitution value of toasted pigeon pea seeds meal (TPSM) for soybean meal and maize in boiler starter diet. The brown coat coloured pigeon pea seeds were toasted at 100oC for 15minutes and milled. The inclusion levels of ...

  9. Cooperation in Experimental Games of Strategic Complements and Substitutes

    Potters, J.J.M.; Suetens, S.

    2006-01-01

    Results are reported of a laboratory experiment aimed at examining whether strategic substitutability and strategic complementarity have an impact on the tendency to cooperate in two-player dominancesolvable games with a Pareto-inefficient Nash equilibrium.We find that there is significantly more

  10. KINETICS OF SUBSTITUTION OF CIS-BIS(MALONATO ...

    Preferred Customer

    In this process, it indicated that the substitution reaction occurs through an Ia mechanism in the ... isotopic water exchange and other anation processes. ... The potassium salt of cis-bis(malonato)diaquochromate(III) was prepared by a reported [26] ... of the synthesized metal complex showed maxima at 415 nm (ε = 41.6 M-1 ...

  11. 41 CFR 101-26.304 - Substitution policy.

    2010-07-01

    ... 41 Public Contracts and Property Management 2 2010-07-01 2010-07-01 true Substitution policy. 101-26.304 Section 101-26.304 Public Contracts and Property Management Federal Property Management Regulations System FEDERAL PROPERTY MANAGEMENT REGULATIONS SUPPLY AND PROCUREMENT 26-PROCUREMENT SOURCES AND...

  12. Substitution of strontium for calcium in glass ionomer cements (Part ...

    Objectives: To investigate the effects of substituting strontium for calcium in fluoroaluminosilicate glass on the mechanical and ion-releasing properties of high-viscosity glass ionomer cements. Design: An exploratory, laboratory-based study. Setting: Dental biomaterials research laboratory, Dental Physical Sciences Unit, ...

  13. An extended gravity model with substitution applied to international trade

    Bikker, J.A.|info:eu-repo/dai/nl/06912261X

    The traditional gravity model has been applied many times to international trade flows, especially in order to analyze trade creation and trade diversion. However, there are two fundamental objections to the model: it cannot describe substitutions between flows and it lacks a cogent theoretical

  14. The Doubting System 1: Evidence for automatic substitution sensitivity.

    Johnson, Eric D; Tubau, Elisabet; De Neys, Wim

    2016-02-01

    A long prevailing view of human reasoning suggests severe limits on our ability to adhere to simple logical or mathematical prescriptions. A key position assumes these failures arise from insufficient monitoring of rapidly produced intuitions. These faulty intuitions are thought to arise from a proposed substitution process, by which reasoners unknowingly interpret more difficult questions as easier ones. Recent work, however, suggests that reasoners are not blind to this substitution process, but in fact detect that their erroneous responses are not warranted. Using the popular bat-and-ball problem, we investigated whether this substitution sensitivity arises out of an automatic System 1 process or whether it depends on the operation of an executive resource demanding System 2 process. Results showed that accuracy on the bat-and-ball problem clearly declined under cognitive load. However, both reduced response confidence and increased response latencies indicated that biased reasoners remained sensitive to their faulty responses under load. Results suggest that a crucial substitution monitoring process is not only successfully engaged, but that it automatically operates as an autonomous System 1 process. By signaling its doubt along with a biased intuition, it appears System 1 is "smarter" than traditionally assumed.

  15. 12 CFR 27.6 - Substitute monitoring program.

    2010-01-01

    ... 12 Banks and Banking 1 2010-01-01 2010-01-01 false Substitute monitoring program. 27.6 Section 27.6 Banks and Banking COMPTROLLER OF THE CURRENCY, DEPARTMENT OF THE TREASURY FAIR HOUSING HOME LOAN... (12 CFR 202.13(d)). A bank collecting the data in compliance with § 27.3 of this part will be in...

  16. Clinical review: impact of statin substitution policies on patient outcomes

    Atar, Dan; Carmena, Rafael; Clemmensen, Peter

    2009-01-01

    BACKGROUND: The increasing awareness of cost issues in health care has led to the increasing use of policy-driven substitution of branded for generic medications, particularly relative to statin treatment for cardiovascular diseases. While there are potential short-term health care savings...

  17. Bone Graft Substitutes : Developed for Trauma and Orthopaedic Surgery

    J. van der Stok (Johan)

    2015-01-01

    markdownabstract__Abstract__ Bone grafting was established in the 19th century and has become a common procedure in which bone defects are filled with bone grafts or bone graft substitutes. Bone defects that require bone grafting are encountered in approximately 10% of trauma and orthopaedic

  18. Bioefficacy And Economics Of Ronozyme™ P As A Substitute For ...

    The biological and economic efficiencies of Ronozyme ™ p as a substitute for bone meal in female Turkey poults was investigated. A total of eighty local female poults were brooded and fed commercial broiler starter diet containing 23% CP and 2800kcal/kg ME from day-old to four weeks of age. Sixty (60) female poults ...

  19. Iron-substituted AB5-type MH electrode

    To study their electrochemical properties via measurements of discharge capacity, activation ... the higher electron attracting power of Fe, when substituted in small .... The phase analysis through XRD .... Only a small extra XRD peak of CeO2 is present in the alloy .... The open circuit voltage of MH electrode with respect to ...

  20. The kinetics of substitution reaction of oxydiacetate and ...

    molar ratio 1:1 and the ternary complex Cu(R)B were recorded to confirm that ... tion, the values of the rate constants were determined. Figure 2. .... Table 4. The free enthalpy of activation values for the substitution reaction of CuODA with bipy.

  1. SO2 policy and input substitution under spatial monopoly

    Gerking, Shelby; Hamilton, Stephen F.

    2010-01-01

    Following the U.S. Clean Air Act Amendments of 1990, electric utilities dramatically increased their utilization of low-sulfur coal from the Powder River Basin (PRB). Recent studies indicate that railroads hauling PRB coal exercise a substantial degree of market power and that relative price changes in the mining and transportation sectors were contributing factors to the observed pattern of input substitution. This paper asks the related question: To what extent does more stringent SO 2 policy stimulate input substitution from high-sulfur coal to low-sulfur coal when railroads hauling low-sulfur coal exercise spatial monopoly power? The question underpins the effectiveness of incentive-based environmental policies given the essential role of market performance in input, output, and abatement markets in determining the social cost of regulation. Our analysis indicates that environmental regulation leads to negligible input substitution effects when clean and dirty inputs are highly substitutable and the clean input market is mediated by a spatial monopolist. (author)

  2. Synthesis of meta-substituted monodentate phosphinite ligands and ...

    SATEJ S DESHMUKH

    from organic synthesis, phosphinite ligands find appli- cations in a variety of ... thesis of meta-substituted phosphinite ligands is rarely reported.18 This is most ... 1.9 μm; mobile phase used, 90% methanol + 10% water +. 0.1% formic acid) ...

  3. An environmentally benign one pot synthesis of substituted ...

    Instance of Plagiarism in Journal of Chemical Sci- ences and withdrawal of published article. The Journal of Chemical Sciences office received a complaint from an alert reader to the effect that the paper 'An environmentally benign one pot syn- thesis of substituted quinolines catalysed by fluo- roboric acid based ionic ...

  4. Effect of substitution of titanium by magnesium and niobium on ...

    Administrator

    Effect of substitution of titanium by magnesium and niobium on structure and piezoelectric properties in (Bi1/2. Na1/2. )TiO3 ceramics. ZHOU CHANG-RONG*, LIU XIN-YU, LI WEI-ZHOU. † and YUAN CHANG-LAI. Department of Information Material Science and Engineering, Guilin University of Electronic Technology,. Guilin ...

  5. Thermodynamic studies on charge-coupled substituted synthetic monazite

    Rawat, D. [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Phapale, S. [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Mishra, R., E-mail: mishrar@barc.gov.in [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Dash, S. [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India)

    2017-04-15

    Phosphate-based monazite ceramic is considered worldwide as a potential crystalline host matrix for immobilization of long-lived tri- and tetra-valent actinides present in high-level nuclear waste. Monazite is chemically stable with respect to the leaching processes and has high radiation stability. The present paper describes the influence of charged coupled (Ca{sup 2+}, Th{sup 4+}) substitution in place of La{sup 3+} on thermodynamic stability of synthetic monazite ceramics. XRD-analysis of Ca, Th substituted LaPO{sub 4} viz., La{sub 1-x}Ca{sub x/2}Th{sub x/2}PO{sub 4} (0 ≤ x ≤ 1) points to the formation of ideal solid-solution in the entire range of composition. However, thermodynamic analysis indicates deviation from ideal solid-solution with a minima at x = 0.25. The substituted La{sub 1-x}Ca{sub x/2}Th{sub x/2}PO{sub 4} system is found to be iso-entropic and stabilized mainly by enthalpy. Enthalpies of formation as a function of Ca{sup 2+}, Th{sup 4+} substitution were analysed to provide insights into the development of thermodynamically stable nuclear waste matrix.

  6. Cu 2 + and Al 3 + co-substituted cobalt ferrite

    X-ray diffraction (XRD) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, field emissionscanning electron microscopy (FESEM) and vibrating sample magnetometer (VSM) are used for studying the effect of variation in the Cu–Al substitution and its impact on particle size, magnetic properties such as Ms and Hc.

  7. The Synthesis of Substituted Piperazine-cholesterol Conjugates for ...

    A small library of cholesterol-piperazine conjugates were synthesized by the reaction of cholesteryl chloroformate with a set of substituted piperazines in dichloromethane at room temperature. The conjugates, all obtained in good to excellent yields, were synthesized to be key components of nucleic acid transfection ...

  8. Stabilisation of the [6]-prismane structure by silicon substitution

    Asif Equbal

    structure becomes increasingly more stable, relative to the two isolated benzene (like) structures. A similar trend is observed ... a theoretical point of view.1–4 However, experimental evidence .... For multi-Si-substituted benzene, the stability of the dimer depends on .... The light green color in the ring indicates silicon atoms.

  9. Implementing opioid substitution in Lebanon: Inception and challenges.

    El-Khoury, Joseph; Abbas, Zeinab; Nakhle, Pascale E; Matar, Marie-Therese

    2016-05-01

    Opioid Substitution Treatment (OST) is a firmly established method of treating and managing dependence to opioids in Europe, the US and rest of the developed world. It has a solid evidence base and a positive safety track record. Dissemination of its practice, in parallel to the acceptance of harm reduction as an effective approach, is still timid in low and middle Income countries. After years of advocacy on the parts of clinicians and the voluntary sector, the government of Lebanon launched a national opioid substitution program in 2011 using buprenorphine as the substance of substitution. Lebanon is one of the first countries in the MENA region to establish such a program despite a difficult socio-political context. This paper provides the background of harm reduction efforts in the region and presents the outline of the program from inception to present date. Challenges and recommendations for the future are also discussed. The Lebanese experience with opioid substitution is encouraging so far and can be used as a template for others in the region who might be contemplating broadening the range of services available to tackle addiction to heroin and related substances. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Substitutability and Independence: Matching Analyses of Brands and Products

    Foxall, Gordon R.; Wells, Victoria K.; Chang, Shing Wan; Oliveira-Castro, Jorge M.

    2010-01-01

    This article presents a comprehensive examination of panel data for 1,847 consumers and 2,209 brands of "biscuits" (a total of 76,682 records) in which matching analysis is employed to define brand substitutability and potential product clusters within the overall category. The results indicate that, while brands performed as expected as perfect…

  11. Placebo substitution for tnethyldopa in geriatric hypertensive patients

    and the benefit of treatment is still disputed.6 The aim of this study was to substitute a matching placebo for methyldopa in order to evaluate the effect of removal of a drug from the antihypertensive regimen of elderly patients without concomitantly inducing a sense of in- security. Sex (female/male) 16/2. Mean age (yrs). 75,7.

  12. Biological relevance and synthesis of C-substituted morpholine derivatives

    Wijtmans, R.; Vink, M.K.S.; Schoemaker, H.E.; Delft, F.L. van; Blaauw, R.H.; Rutjes, F.P.J.T.

    2004-01-01

    C-Functionalized morpholines are found in a variety of natural products and biologically active compounds, but have also for other reasons been applied in organic synthesis. This review deals with the biological relevance of C-substituted morpholines, their synthesis and important applications in

  13. 1,3- and 1,4-Substituted tetrazolium salts

    Voitekhovich, Sergei V; Gaponik, Pavel N; Ivashkevich, Oleg A

    2002-01-01

    The published data on the synthesis, physicochemical properties, structures and reactions of 1,3-(1,3,5)- and 1,4-(1,4,5)-substituted tetrazolium salts are systematised and generalised. Their applications as starting compounds in the preparative chemistry of heterocyclic derivatives and some other branches of science and technology are reviewed. The bibliography includes 122 references.

  14. Preparation, characterization and biological activity of C8-substituted cytokinins

    Zahajská, Lenka; Nisler, Jaroslav; Voller, Jiří; Gucký, Tomáš; Pospíšil, Tomáš; Spíchal, Lukáš; Strnad, Miroslav

    2017-01-01

    Roč. 135, MAR (2017), s. 115-127 ISSN 0031-9422 Institutional support: RVO:61389030 Keywords : potential purine antagonists * arabidopsis-thaliana * nucleosides * derivatives * thidiazuron * specificity * receptors * kinetin * Organic synthesis * Cytokinin bioassay * AHK3 and CRE1/AHK4 bacterial receptor assay * C8-substituted cytokinin Subject RIV: CE - Biochemistry OBOR OECD: Organic chemistry Impact factor: 3.205, year: 2016

  15. 12 CFR 229.53 - Substitute check indemnity.

    2010-01-01

    ... expenses of representation) related to the substitute check. (2) Comparative negligence. (i) If a loss... negligence or failure to act in good faith, then the indemnity amount described in paragraph (b)(1) of this section shall be reduced in proportion to the amount of negligence or bad faith attributable to the...

  16. Protein substitution to produce a processed cheese with high ...

    Multiple studies report the beneficial effects of BCAAs supplementation to improve plasma amino acids imbalance, several neurologic diseases, protein energy malnutrition, and subsequently the survival rate of cirrhotic patients. Methods: In the present study we used a protein substitution technique to synthesize a new ...

  17. Assessing a Currency Substitution Persistency in the Western Balkan Region

    Mehmed Ganić

    2017-12-01

    Full Text Available The study aims to examine the euroization phenomenon in seven Western Balkan countries (Albania, Bosnia and Herzegovina, Bulgaria, Croatia, Romania, Serbia and Macedonia between 2000 and 2015 and a number of –specific challenges faced by the region. More precisely, the paper analyzes the impact of the latest global financial crisis on the extent of currency substitution persistency by exploring the trends before, in wake of the financial crisis, and after the financial crisis. The study employed several indicators as a proxy variable for measuring of the overall level of currency substitution or euroization and cross country analysis in selected countries (liability euroization, credit euroization and deposit euroization and asset substitution- overall euroization index. Finally, the study found that deposit euroisation, credit euroization, and liabilities euroization in seven Western Balkan countries is still high with relatively high degree of heterogeneity. In some countries of the Western Balkan region the process of euroisation was further intensified in spite of the consequences of the latest global financial crises, while in the other ones the crisis years were marked by the trend of de-euroisation. In overall, this study does not find any significant evidence on significantly increases or decreases in currency substitution at the region sub-samples. Finally, Student t-test results indicate that there is no significant difference in means of before, in wake and after the financial crises at level of Western Balkan region.

  18. Molecular substitution rate increases with latitude in butterflies

    Schär, Sämi; Vila, Roger; Petrović, Andjeljko

    2017-01-01

    of five lycaenid butterfly species with varied ecological adaptations, sampled across a latitudinal gradient in the Holarctic region. We found a positive correlation between latitude and substitution rate of mitochondrial DNA sequences in all species investigated. We propose that this result is the signal...

  19. Substitution reactions of [Pd(bipy)(malonate)] explored with a ...

    −3. NaClO4. Table 1. Metal-Ligand ratios and structures of the product complexes. Metal:Ligand. Ligand. Structure ratio. Product complex. L1 Thioglycolic acid. HS ..... O. Scheme 1. Plausible mechanistic pathway. molecules substitute the bidentate malonate in a consec- utive fashion. Among the three sulphur donor ligands.

  20. Maximum potential cost-savings attributable to generic substitution ...

    D. Husselmann

    community. ... Conclusions: Potential economic benefits can be generated with generic substitution. ... Available online at www.sciencedirect.com ... supply of safe, cost-effective drugs of acceptable quality to all citizens of South Africa, and the rational use of drugs by .... different types of schizophrenic diagnosis) with a claim.

  1. The Effects of Substituting Soyabean Meal for Breadfruit Meal on ...

    Increasing substitutions of soyabean meal for breadfruit meal in diets fed to Heterobranchus bidorsalis (♂) x Clarias gariepinus (♀) hybrid fingerlings led to weight increases in all dietary types with exception of diet G and higher growth induction in catfishes fed all diets with exception of diet B. Diets C had induced better ...

  2. Ortho lithiation-in situ borylation of substituted morpholine benzamides

    Cederbalk, Anna; Lysén, Morten; Kehler, Jan

    2017-01-01

    Morpholine amides are cheap and safe alternative to Weinreb amides as acylating agents of organometallic species. Herein, the in-situ lithiation/borylation of 18 ortho- meta- and para-substituted morpholine benzamides has been investigated. 10 of the 18 substrates provided the desired boronic est...

  3. Competing for Consciousness: Prolonged Mask Exposure Reduces Object Substitution Masking

    Goodhew, Stephanie C.; Visser, Troy A. W.; Lipp, Ottmar V.; Dux, Paul E.

    2011-01-01

    In object substitution masking (OSM) a sparse, temporally trailing 4-dot mask impairs target identification, even though it has different contours from, and does not spatially overlap with the target. Here, we demonstrate a previously unknown characteristic of OSM: Observers show reduced masking at prolonged (e.g., 640 ms) relative to intermediate…

  4. Synthesis and antibacterial activities of N-substituted maleopimarimide

    LI Hui

    2016-02-01

    Full Text Available With Macrogol 600(PEG-600 as solvent and toluene as dehydrant,eight N-Substituted maleopimarimide compounds were synthesized from maleopimaric acid and aniline or its derivatives by one-step reaction;Their structures were confirmed and the antimicrobial activities of these compounds were also preliminarily investigated.

  5. Quantum Dots Embedded in Graphene Nanoribbons by Chemical Substitution

    Carbonell-Sanroma, Eduard; Brandimarte, Pedro; Balog, Richard

    2017-01-01

    Bottom-up chemical reactions of selected molecular precursors on a gold surface can produce high quality graphene nanoribbons (GNRs). Here, we report on the formation of quantum dots embedded in an armchair GNR by substitutional inclusion of pairs of boron atoms into the GNR backbone. The boron...

  6. Structure and magnetic properties of Zr–Mn substituted strontium ...

    2Department of Materials Engineering, Najafabad Branch, Islamic Azad ... ions prefer to occupy both 4f1 and 2b however, at higher level of substitution, they prefer exclusively 4f1 site. ... Up to authors' knowledge, the effect of Zr–Mn substitu-.

  7. 76 FR 41685 - Electronic Substitutions for Form SSA-538

    2011-07-15

    ... visit our Internet site, Social Security Online, at http://www.socialsecurity.gov . SUPPLEMENTARY... SOCIAL SECURITY ADMINISTRATION 20 CFR Part 416 [Docket No. SSA-2009-0027] RIN 0960-AH02 Electronic Substitutions for Form SSA-538 AGENCY: Social Security Administration. ACTION: Final rule with request for...

  8. preparation and nucleophilic substitution of the 2,4,6

    Mgina

    Three methods for preparation of D-amino acids by nucleophilic substitution on derivatives of ... bioactivity of the peptide (Wenger 1985, ... Acetic acid (0.29 mL, 5 mmol) was added, and the mixture was further stirred for 5 h at rt under ... methanol/dichloromethane) to yield a white ... temperature, diluted with water, extracted.

  9. Substitution and defect chemistry of La-Cu-O systems

    Gai, P.L.; McCarron, E.M.; Kunchur, M.

    1991-01-01

    In this paper substitutional effects of strontium in La-Cu-O system and defects accommodating stoichiometric deviations is investigated. The extended shear defects are analyzed using electron microscopy and the role in superconducting transport properties has been examined by magnetic measurements. The initial results suggest that the defects enhance flux pinning

  10. 40 CFR 721.10048 - Substituted anthraquinone (generic).

    2010-07-01

    ..., and consumer activities. Requirements as specified in § 721.80(s) (4,500 kilograms). (ii) [Reserved... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted anthraquinone (generic). 721.10048 Section 721.10048 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED...

  11. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    2010-07-01

    ... are: (i) Industrial, commercial, and consumer activities. Requirements as specified in § 721.80(s... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl phosphine oxide (generic). 721.10087 Section 721.10087 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED...

  12. 7 CFR 4287.135 - Substitution of lender.

    2010-01-01

    ... Agriculture Regulations of the Department of Agriculture (Continued) RURAL BUSINESS-COOPERATIVE SERVICE AND RURAL UTILITIES SERVICE, DEPARTMENT OF AGRICULTURE SERVICING Servicing Business and Industry Guaranteed... borrower, the proposed substitute lender, and the original lender if still in existence. (b) Where the...

  13. Hydrophobic core substitutions in calbindin D9k

    Kragelund, B B; Jönsson, M; Bifulco, G

    1998-01-01

    Hydrophobic core residues have a marked influence on the Ca2+-binding properties of calbindin D9k, even though there are no direct contacts between these residues and the bound Ca2+ ions. Eleven different mutants with substitutions in the hydrophobic core were produced, and their equilibrium Ca2+...... that the hydrophobic core residues promote Ca2+ binding both by contributing to the preformation of the Ca2+ sites in the apo state and by preferentially stabilizing the Ca2+-bound state.......Hydrophobic core residues have a marked influence on the Ca2+-binding properties of calbindin D9k, even though there are no direct contacts between these residues and the bound Ca2+ ions. Eleven different mutants with substitutions in the hydrophobic core were produced, and their equilibrium Ca2...... that the mutation causes only very minimal perturbations in the immediate vicinity of residue 61. Substitutions of alanines or glycines for bulky residues in the center of the core were found to have significant effects on both Ca2+ affinity and dissociation rates. These substitutions caused a reduction in affinity...

  14. A safer alternative: Cannabis substitution as harm reduction.

    Lau, Nicholas; Sales, Paloma; Averill, Sheigla; Murphy, Fiona; Sato, Sye-Ok; Murphy, Sheigla

    2015-11-01

    Substitution is operationalised as a conscious choice made by users to use one drug instead of, or in conjunction with another based on: perceived safety, level of addiction potential, effectiveness in relieving symptoms, access and level of acceptance. Harm reduction is a set of strategies that aim to minimise problems associated with drug use while recognising that for some users, abstinence may be neither a realistic nor a desirable goal. In this paper, we aim for deeper understandings of older adult cannabis users' beliefs and substitution practices as part of the harm reduction framework. We present selected findings from our qualitative study of Baby Boomer (born 1946-1964) marijuana users in the San Francisco Bay Area. Although the sample consisted of primary cannabis users, many had personal experience with other drugs throughout their lifetimes. Data collection consisted of an audio-recorded, semi-structured in-depth life history interview followed by a questionnaire and health survey. Qualitative interviews were analysed to discover users' harm reduction beliefs and cannabis substitution practices. Study participants described using cannabis as a safer alternative for alcohol, illicit drugs and pharmaceuticals based on their perceptions of less adverse side effects, low-risk for addiction and greater effectiveness at relieving symptoms, such as chronic pain. Cannabis substitution can be an effective harm reduction method for those who are unable or unwilling to stop using drugs completely. More research is needed on cannabis as a safer alternative. © 2015 Australasian Professional Society on Alcohol and other Drugs.

  15. A novel non-toxic xylene substitute (SBO) for histology.

    Kunhua, Wang; Chuming, Fan; Tao, Lai; Yanmei, Yang; Xin, Yang; Xiaoming, Zhang; Xuezhong, Guo; Xun, Lai

    2012-01-01

    Xylene has been generally used as a clearing and deparaffinizing agent in histology. Because of the potential toxic and flammable nature of xylene, its substitutes have been introduced into some laboratories. In this study, we introduced a novel, non-toxic xylene substitute (SBO), which was generated through a mixture of 86% of white oil No.2 and 14% of N-heptane. SBO had a high boiling point (188°C) and flash point (144°C) coupled with a scentless and decreased volatility. To compare the effectiveness of SBO and xylene in histology, a wide range of tissue samples from rats and human beings were processed in parallel in SBO and xylene, subjected to various staining procedures. Similar to the xylene-processed paraffin blocks, the SBO-processed counterparts were easy to section without any evidence of cell shrinkage. Assessment of the SBO-treated sections stained with hematoxylin-eosin revealed a good maintenance of cell morphology and structure, and a clear definition of the cytoplasm and the nucleus. Moreover, comparable good results were achieved between the SBO- and xylene-processed tissues in other histochemical and immunohistochemical stainings. Six-month clinical applications at one department of pathology supported the potentials of SBO as a xylene substitute. In conclusion, we suggest that SBO is a safe and efficient substitute of xylene and may probably replace xylene without losing valuable diagnostic information.

  16. The synthesis of some unsaturated 4-substituted-g-lactones

    SUREN HUSINEC

    2000-02-01

    Full Text Available The synthesis of conjugated and nonconjugated unsaturated 4-substituted lactones of type 1 and 2 are described. The type 1 lactone was prepared by a two step procedure employing Bredereck's reagent. The type 2 lactone was synthesised by combining the Claisen-Ireland rearrangement and selenolactonisation.

  17. Effects of substituting fishmeal with immobilized urea periodate ...

    Growth trails were conducted with Oreochromis niloticus fingerlings (mean weight 0.88 + 0.02 g) to evaluate the suitability of incorporating immobilized urea periodate oxidized Lignocellulosic Materials (LCMs) namely, Acha (Digitaria exilis (Staph) and Rice (Oryza sativa (L.) straws for substituting fishmeal from the reference ...

  18. Kinetics and mechanism of the oxidation of substituted ...

    Unknown

    Oxidation of meta- and para-substituted benzylamines by cetyltrimethyl- ... method.12 As per this method, the aldimine is hydrolysed to the aldehyde and then ... reactions were studied at constant temperature (± 0⋅1 K) and were followed by .... electronic interaction between the substituent and the reaction centre, (σ+–σ0) is ...

  19. Substitution of lucerne hay by ammoniated wheat straw in growth ...

    Lucerne hay (LH) was substituted by urea-ammoniated wheat straw (AWS) in four lamb-growth diets, all containing 60% roughage. ... Die ekonomiese voordeel van die verplasing van 'n hoë kwaliteit ruvoer, soos LH, met'n goedkoper bron (AKS), moet opgeweeg word teen die laer DMI en GDT, sowel as die nadelige effek ...

  20. Substitution rate and natural selection in parvovirus B19

    Stamenković, Gorana G.; Ćirković, Valentina S.; Šiljić, Marina M.; Blagojević, Jelena V.; Knežević, Aleksandra M.; Joksić, Ivana D.; Stanojević, Maja P.

    2016-01-01

    The aim of this study was to estimate substitution rate and imprints of natural selection on parvovirus B19 genotype 1. Studied datasets included 137 near complete coding B19 genomes (positions 665 to 4851) for phylogenetic and substitution rate analysis and 146 and 214 partial genomes for selection analyses in open reading frames ORF1 and ORF2, respectively, collected 1973–2012 and including 9 newly sequenced isolates from Serbia. Phylogenetic clustering assigned majority of studied isolates to G1A. Nucleotide substitution rate for total coding DNA was 1.03 (0.6–1.27) x 10−4 substitutions/site/year, with higher values for analyzed genome partitions. In spite of the highest evolutionary rate, VP2 codons were found to be under purifying selection with rare episodic positive selection, whereas codons under diversifying selection were found in the unique part of VP1, known to contain B19 immune epitopes important in persistent infection. Analyses of overlapping gene regions identified nucleotide positions under opposite selective pressure in different ORFs, suggesting complex evolutionary mechanisms of nucleotide changes in B19 viral genomes. PMID:27775080

  1. Prioritizing substitution of organic solvents in industrial cleaning processes

    Rasmussen, Pia Brunn; Jacobsen, Thomas

    1997-01-01

    A method for prioritizing the substitution of volatile organic compounds (VOC) used in industrial cleaning processes is developed. The result is a matrix, which, if all information can be obtained, gives a comprehensive description of the effects, exposure and emission of VOC, as well as the pros...

  2. Substitution of Organic Solvents in Selected Industrial Cleaning Processes

    Jacobsen, Thomas; Rasmussen, Pia Brunn

    1997-01-01

    Volatile organic solvents (VOC)are becoming increasingly unwanted in industrial processes. Substitution of VOC with non-volatile, low-toxic compounds is a possibility to reduce VOC-use. It has been successfully demonstrated, that organic solvents used in cleaning processes in sheet offset printing...

  3. Synthesis and characterization of new meso-substituted ...

    WINTEC

    tems. 10. Their ability to carry out the reactions rather unusual in organic chemistry has been the object of intensive investigations aiming to utilize them as a model compounds for biological systems and as catalysts. 11. Therefore, the synthesis of well defined meso-substituted unsymmetrical porphyrin deriva- tives (A3B) is ...

  4. The Substitution of IVD (Ion Vapor Deposition) Aluminum for Cadmium

    1989-08-01

    thus lose the anvantages the substitution nay offer suco as improveu perfornance arc/or the elimination of hazaruous waste production. This report...various processe-s are snown in Tlaole 31. The lVU alumiinum capitai cost includes the cooTter arc ucoicoted equipmient suco as a grit olaster ano glass

  5. Substitution of strontium for calcium in glass ionomer cements (Part ...

    Substitution of strontium for calcium in glass ionomer cements (Part 1): Glass synthesis and characterisation, and the effects on the cement handling variables and ... acid to form glass ionomer cements, whose properties were investigated at different time points: working and setting times were determined by rheometry; and, ...

  6. Interpretation of substitution experiments by homogenisation two-group method

    Sotic, O.

    1970-02-01

    This paper describes methods for interpretation of progressive substitution experiments for determining material buckling in homogeneous two-group approximation. These methods were applied for experiments on the zero power RB reactor in Vinca. Experiments were done on the reflected heavy water reactor core, the lattice pitch had unisotropy properties

  7. Synthesis of 3-Substituted 1,4-Benzodiazepin-2-ones

    Kyungjin Kim

    1998-01-01

    Full Text Available The preparation of 3-substituted 1,4-benzodiazepines by benzodiazepine enolate alkylation has been explored. Employing this approach, multigram quantities of benzodiazepine 1 have been prepared for animal studies to evaluate a new approach for the treatment of the autoimmune disease systemic lupus erythematosus (SLE.

  8. Substitution af organiske opløsningsmidler med estre af

    Jacobsen, Thomas

    1999-01-01

    Substitution of organic solvents, which are harmful to both man and environment, is often possible. Cleaning of machines in offset printing may to a large extent be performed with products, which are neither volatile nor toxic to man and environment. Apparently this experience may be transferred...

  9. Hydrothermal synthesis and characterizations of Ti substituted Mn-ferrites

    Mostafa, Nasser Y., E-mail: nmost69@yahoo.com [Faculty of Science, Taif University, P.O. Box 888 Al-Haweiah, Taif (Saudi Arabia); Chemistry Department, Faculty of Science, Suez Canal University, Ismailia 41522 (Egypt); Hessien, M.M. [Faculty of Science, Taif University, P.O. Box 888 Al-Haweiah, Taif (Saudi Arabia); Advanced materials Division-Central metallurgical R and D Institute (CMRDI), P.O. Box 87 Helwan, Cairo (Egypt); Shaltout, Abdallah A. [Faculty of Science, Taif University, P.O. Box 888 Al-Haweiah, Taif (Saudi Arabia); Spectroscopy Department, Physics Division, National Research Center, El Behooth Str., 12622 Dokki, Cairo (Egypt)

    2012-07-15

    Highlights: Black-Right-Pointing-Pointer Hydrothermal synthesized of well-crystallized Ti-substituted MnFe{sub 2}O{sub 4} nanoparticles at 180 Degree-Sign C without any calcination step. The chemical composition was represented by Mn{sub 1-2x}Ti{sub x}Fe{sub 2}O{sub 4} with x having values 0.0, 0.1, 0.2, 0.3 and 0.4. Black-Right-Pointing-Pointer The change in lattice parameter and saturation magnetization with increasing Ti-substitution was investigated and explained. Black-Right-Pointing-Pointer The change in microstructure due to Ti{sup 4+} ions substitutions was investigated using TEM analysis. - Abstarct: A series of well-crystallized Mn{sub 1-2x}Ti{sub x}Fe{sub 2}O{sub 4} nanoparticles with x values of 0.0, 0.1, 0.2, 0.3 and 0.4 have been synthesized by hydrothermal route at 180 Degree-Sign C in the presence of NaOH as mineralizer. The obtained ferrite samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and vibrating sample magnetometer (VSM). The XRD analysis showed that pure single phases of cubic ferrites were obtained with x up to 0.2. However, samples with x > 0.2 showed traces of unreacted anatase. The increase in Ti-substitution up to x = 0.2 leads to an increase in the lattice parameter of the prepared ferrites. On the other hand, the increase in Ti-substitution over x = 0.2 leads to a decrease in the lattice parameter. The average crystallite size was in the range of 39-57 nm, where it is increased by increasing the Ti-substitution up to x = 0.3, then decreased for x = 0.4. According to VSM results, the saturation magnetization increased with Ti ion substitution of x = 0.1 and decreased for x > 0.1.

  10. Sucrose substitutes affect the cariogenic potential of Streptococcus mutans biofilms.

    Durso, S C; Vieira, L M; Cruz, J N S; Azevedo, C S; Rodrigues, P H; Simionato, M R L

    2014-01-01

    Streptococcus mutans is considered the primary etiologic agent of dental caries and contributes significantly to the virulence of dental plaque, especially in the presence of sucrose. To avoid the role of sucrose on the virulence factors of S. mutans, sugar substitutes are commonly consumed because they lead to lower or no production of acids and interfere with biofilm formation. This study aimed to investigate the contribution of sugar substitutes in the cariogenic potential of S. mutans biofilms. Thus, in the presence of sucrose, glucose, sucralose and sorbitol, the biofilm mass was quantified up to 96 h, the pH of the spent culture media was measured, the expression of biofilm-related genes was determined, and demineralization challenge experiments were conduct in enamel fragments. The presence of sugars or sugar substitutes profoundly affected the expression of spaP, gtfB, gtfC, gbpB, ftf, vicR and vicX in either biofilm or planktonic cells. The substitution of sucrose induced a down-regulation of most genes involved in sucrose-dependent colonization in biofilm cells. When the ratio between the expression of biofilm and planktonic cells was considered, most of those genes were down-regulated in biofilm cells in the presence of sugars and up-regulated in the presence of sugar substitutes. However, sucralose but not sorbitol fulfilled the purpose of reducing the cariogenic potential of the diet since it induced the biofilm formation with the lowest biomass, did not change the pH of the medium and led to the lowest lesion depth in the cariogenic challenge.

  11. Synthesis, characterization and pharmacological evaluation of substituted phenoxy acetamide derivatives

    Rani Priyanka

    2015-01-01

    Full Text Available A novel series of 2-(substituted phenoxy-N-(1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylacetamide and N-(2-bromocyclohexyl-2-(substituted phenoxyacetamide derivatives having cyclohexyl nucleus as common in both types were synthesized and assessed for their anti-inflammatory activity by a carrageenan induced rat paw oedema method, analgesic activity by Eddy’s hot plate method and antipyretic activity by brewer’s yeast induced pyrexia method. All the novel derivatives have been synthesized by the reaction of camphor and similar ketone having cyclohexane nucleus (e.g. 2-bromocyclohexanone with ammonium carbonate and formic acid resulting in the formation of aromatic amines (1a-b. These amines on further chloroacetylation with chloroacetylchloride give compounds (2a-b. Compounds (2a-b are converted to 2-(substituted phenoxy-N-(1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl acetamide and N-(2-bromocyclohexyl-2-(substituted phenoxyacetamide derivatives on treatment with substituted phenol. Among the series 3a-f, 3i, 3k, 3l compounds showed significant anti-inflammatory activity as compared to the standard drug diclofenac sodium and also compound 3a-f, 3h, 3j, 3k exhibit significant analgesic activity as compared to the standard drug. Compounds 3a-f and 3k showed antipyretic activity nearly to the standard drug indomethacin. Compounds 3a-f and 3k possess anti-inflammatory, analgesic and antipyretic activities near to the standard.

  12. Substitution Effects and Linear Free Energy Relationships During Reduction of 4- Benzoyl-n-(4-substituted Benzyl)pyridinium Cations

    Leventis, Nicholas; Zhang, Guo-Hui; Rawashdeh, Abdel-Monem M.; Sotiriou-Leventis, Chariklia; Gray, Hugh R. (Technical Monitor)

    2003-01-01

    In analogy to 4-(para-substituted benzoyl)-N-methylpyridinium cations (1-X's), the title species (2-X's, -X = -OCH3, -CH3, -H, -Br, -COCH3, -NO2) undergo two reversible, well-separated (E(sub 1/2) greater than or equal to 650 mV) one-electron reductions. The effect of substitution on the reduction potentials of 2-X's is much weaker than the effect of the same substituents on 1-X's: the Hammett rho-values are 0.80 and 0.93 for the 1st- and 2nd-e reduction of 2-X's vs. 2.3 and 3.3 for the same reductions of 1-X's, respectively. Importantly, the nitro group of 2-NO2 undergoes reduction before the 2nd-e reduction of the 4-benzoylpyridinium system. These results suggest that the redox potentials of the 4-benzoylpyridinium system can be course-tuned via p-benzoyl substitution and fine-tuned via para-benzyl substitution. Introducing the recently derived substituent constant of the -NO2(sup)- group (sigma para-NO2(sup)- = -0.97) yields an excellent correlation for the 3rd-e reduction of 2- NO2 (corresponding to the reduction of the carbonyl group) with the 2nd-e reduction of the other 2-X's, and confirms the electron donating properties of -NO2(sup)-.

  13. Educating T-Shaped professionals to meet substitution challenges and developing business models for substitution and recycling

    Arroyo, Ana; Mendibil Eguiluz, Javier; Sánchez Cupido, Laura

    2018-03-01

    One strategy to overcome the challenges related to critical raw materials (CRMs) is their substitution and recycling. However, the bright scientific idea, proof of concept or laboratory demonstration need to cross the valley of death in order to become stated as ‘a substitute’ instead of ‘a potential substitute’. Most PhD students and Post Docs specialize within a given thematic area; for example on specific materials or on substitution in a certain application. This specialization could limit the ability to generate innovations and profitable business models if there are not enough tools and skills to transform new knowledge and research results into an appealing value proposition towards customers and to a business opportunity for the current markets. The project proposes a framework for developing substitution and recycling related cross-sectorial skills and tools. These are applied for training business-related competences e.g. teamwork, management, communication, value proposition and business models design, especially within RTOs and industries. The proposed learning itinerary can radically improve the path from scientific proof of concept into innovation and lean start up or industrial market launch. The developed framework is tested by a pilot group having several topics within the areas of substitution and recycling of critical raw materials.

  14. Estimating intertemporal and intratemporal substitutions when both income and substitution effects are present: the role of durable goods

    Pakoš, Michal

    2011-01-01

    Roč. 29, č. 3 (2011), s. 439-454 ISSN 0735-0015 Institutional research plan: CEZ:AV0Z70850503 Keywords : durable goods * intertemporal substitution * nonhomotheticity Subject RIV: AH - Economics Impact factor: 1.779, year: 2011

  15. Substituent effects on mono-substituted and poly-substituted nitriles; Efeitos dos substituintes em nitrilas mono- e polissubstituidas

    Sofia, Raquel C.R.; Carneiro, Paulo I.B.; Rittner, Roberto [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica; Fabi, Marino T [Rhodia S.A., Sao Paulo, SP (Brazil)

    1992-12-31

    This work studies various mono substituted aliphatic nitriles, Y C H{sub 2} (Y=H, F, Cl, Br, I, OMe, S Me, SEt{sub 2}, Me and Ph), and some reference nitriles (Y=Et, n-Pr, n-Bu, n-Am, n-Hex and n-Hept) 12 refs., 3 tabs.

  16. Stereotype threat and social function in opioid substitution therapy patients.

    von Hippel, Courtney; Henry, Julie D; Terrett, Gill; Mercuri, Kimberly; McAlear, Karen; Rendell, Peter G

    2017-06-01

    People with a history of substance abuse are subject to widespread stigmatization. It seems likely that this societal disapproval will result in feelings of stereotype threat, or the belief that one is the target of demeaning stereotypes. If so, stereotype threat has the potential to contribute to functional difficulties including poor social outcomes. Eighty drug users on opioid substitution therapy and 84 demographically matched controls completed measures of mental health and social function. The opioid substitution therapy group were additionally asked to complete a measure that focused on their feelings of stereotype threat in relation to their drug use history. Bivariate correlations and hierarchical regression analyses were conducted to establish the magnitude and specificity of the relationship between stereotype threat and social functioning. Relative to controls, the opioid substitution therapy group reported higher levels of negative affect and schizotypy, and poorer social functioning, with all three of these indices significantly correlated with their feelings of stereotype threat. The results also showed that stereotype threat contributed significant unique variance to social functioning in the opioid substitution therapy group, even after taking into account other background, clinical, and mental health variables. Social functioning is an important aspect of recovery, yet these data indicate that people with a history of drug abuse who believe they are the target of stereotypical attitudes have poorer social functioning. This relationship holds after controlling for the impact of other variables on social functioning, including mental health. The theoretical and practical implications of these findings are discussed. Concerns about being stereotyped can shape the social experiences of opioid substitution therapy patients. Opioid substitution therapy patients who feel negatively stereotyped experience greater social function deficits, and this

  17. Multifaceted Material Substitution: The Case of NdFeB Magnets, 2010-2015

    Smith, Braeton J.; Eggert, Roderick G.

    2016-07-01

    Substitution is an important response for material users when faced with disruption to the availability or price of an essential material. In economic terms, substitution refers to the ability of firms to alter their patterns of material use in response to exogenous market shocks. Substitution comes in different forms which vary from situation to situation. This paper uses expert opinion to identify the specific forms of substitution that occurred in permanent magnets, specifically neodymium-iron-boron magnets, following the significant increase in rare earth prices in 2010-2011. The paper provides a framework for understanding the multifaceted nature of substitution and assesses the relative importance of five different types of substitution. Technology-for-element, grade-for-grade, and system-for-system substitution appear to have been more important than element-for-element and magnet-for-magnet substitution. Cost pass-through and absorption were also important responses.

  18. Ortho-substituted triptycene-based diamines, monomers, and polymers, methods of making and uses thereof

    Ghanem, Bader Saleh

    2017-04-13

    Described herein are ortho-dimethyl-substituted and tetramethyi-substituted triptycene-containing diamine monomers and microporous triptycene-based poiyimides and poiyamides, and methods of making the monomers and polymers.

  19. Eight Ways to Make Sure Substitute Teachers Aren't Baby-Sitters.

    Drury, William R.

    1988-01-01

    Substitutes might never be as good as regular teachers, but they still can provide high-quality instruction. Suggestions include meeting with them as a group twice a year, principal and peer support, and development workshops specifically for substitutes. (TE)

  20. Ortho-substituted triptycene-based diamines, monomers, and polymers, methods of making and uses thereof

    Ghanem, Bader Saleh; Pinnau, Ingo

    2017-01-01

    Described herein are ortho-dimethyl-substituted and tetramethyi-substituted triptycene-containing diamine monomers and microporous triptycene-based poiyimides and poiyamides, and methods of making the monomers and polymers.